Substrate processing apparatus and substrate processing method

Abstract

To provide a substrate processor and a method for processing a substrate that can suppress application of damage on the substrate.SOLUTION: A substrate processor 100 includes a tank 50, a route 70 including a first route C1, a heater 61, a hydrogen peroxide solution supply route C3, and a control unit 102. The first route C1 supplies sulfuric acid to a nozzle 36 from the tank 50. The heater 61 heats a heating region R1 of the first route C1. The control unit 102 mixes sulfuric acid and hydrogen peroxide solution heated by the heater 61, discharges the mixture from the nozzle 36 to a substrate W, and then, mixes sulfuric acid less hotter than the heated sulfuric acid and the hydrogen peroxide solution, and discharges the mixture from the nozzle 36 to the substrate W.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a substrate processing apparatus and a substrate processing method. [Background Art]

[0002] Conventionally, in the manufacturing process of devices including substrates such as semiconductor devices and liquid crystal display devices, a substrate processing apparatus that processes substrates is used. The substrate is, for example, a semiconductor wafer or a glass substrate for a liquid crystal display device.

[0003] Patent Document 1 describes a substrate processing apparatus that supplies a sulfuric acid-hydrogen peroxide mixture produced by mixing hydrogen peroxide solution at a flow rate of 0.1 to 0.35 with respect to sulfuric acid at 170°C or higher to the surface of a substrate. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Laid-Open No. 2009-16497 [Summary of the Invention] [Problem to be Solved by the Invention]

[0005] When a sulfuric acid-hydrogen peroxide mixture is supplied to the surface of a substrate as in the substrate processing apparatus described in Patent Document 1, sulfuric acid and hydrogen peroxide solution react with each other when they are mixed, so that the temperature of the sulfuric acid-hydrogen peroxide mixture increases. After supplying this high-temperature sulfuric acid-hydrogen peroxide mixture to a substrate to process the substrate, the sulfuric acid-hydrogen peroxide mixture remaining on the substrate is washed away with hydrogen peroxide solution.

[0006] Incidentally, if the supply of sulfuric acid is stopped and only hydrogen peroxide is supplied in order to wash away the high-temperature sulfuric acid-hydrogen peroxide mixture on the substrate, the high-temperature sulfuric acid-hydrogen peroxide mixture remaining on the substrate and the supplied hydrogen peroxide react violently, becoming even hotter, and the substrate also becomes hot. Subsequently, by continuing to supply hydrogen peroxide, the high-temperature sulfuric acid-hydrogen peroxide mixture is removed from the substrate, and the temperature of the substrate drops rapidly due to the supplied hydrogen peroxide.

[0007] However, with this method, the high-temperature sulfuric acid-hydrogen peroxide mixture becomes even hotter due to the hydrogen peroxide, and the temperature of the substrate changes rapidly. Therefore, there is a problem that the substrate may be damaged, such as the pattern peeling off. One way to improve this problem is to change the mixing ratio of sulfuric acid and hydrogen peroxide (the concentration of sulfuric acid), but adjusting the mixing ratio to the desired ratio takes time.

[0008] The present invention has been made in view of the above problems, and its objective is to provide a substrate processing apparatus and a substrate processing method that can suppress damage to the substrate. [Means for solving the problem]

[0009] A substrate processing apparatus according to one aspect of the present invention processes a substrate by supplying a processing liquid to the substrate from a nozzle. The substrate processing apparatus comprises a first tank, a path including a first path, a first valve, a first heater, a hydrogen peroxide supply path, a hydrogen peroxide valve, and a control unit. The first tank stores sulfuric acid. The first path supplies the sulfuric acid from the first tank to the nozzle. The first valve is interposed in the first path. The first heater heats the heating region of the first path. The hydrogen peroxide supply path supplies hydrogen peroxide to the nozzle. The hydrogen peroxide valve is interposed in the hydrogen peroxide supply path. The control unit controls the supply of sulfuric acid and hydrogen peroxide to the nozzle by controlling the opening and closing of the first valve and the hydrogen peroxide valve. The control unit mixes the sulfuric acid heated by the first heater with the hydrogen peroxide solution and discharges it from the nozzle onto the substrate, and then mixes sulfuric acid at a lower temperature than the heated sulfuric acid with the hydrogen peroxide solution and discharges it from the nozzle onto the substrate.

[0010] In one embodiment of the present invention, the path may further include a second path that supplies the sulfuric acid from the first tank to the nozzle without passing through the heating region. The substrate processing apparatus may further include a second valve interposed in the second path. The control unit may control the supply of the sulfuric acid and hydrogen peroxide to the nozzle by controlling the opening and closing of the first valve, the second valve and the hydrogen peroxide valve. The sulfuric acid passing through the second path may merge with the hydrogen peroxide at a lower temperature than the sulfuric acid passing through the first path. The control unit may control the first valve, the second valve and the hydrogen peroxide valve so that after the sulfuric acid and hydrogen peroxide heated by the first heater passing through the first path are mixed and discharged from the nozzle to the substrate, the sulfuric acid and hydrogen peroxide passing through the second path are mixed and discharged from the nozzle to the substrate.

[0011] In one embodiment of the present invention, the substrate processing apparatus may further include a first merging section and a second merging section. The first merging section is located between the heating region and the discharge port of the nozzle, and the first path and the hydrogen peroxide water supply path may merge there. The second merging section is located between the heating region and the first merging section, and the first path and the second path may merge there.

[0012] In one embodiment of the present invention, the first path and the second path may branch off upstream of the sulfuric acid flow direction with respect to the heating region and merge downstream of the sulfuric acid flow direction with respect to the heating region.

[0013] In one embodiment of the present invention, the sulfuric acid passing through the first path may have a first temperature by setting the first heater to a first output by the control unit. The sulfuric acid passing through the first path may have a second temperature lower than the first temperature by setting the first heater to a second output lower than the first output by the control unit.

[0014] In one embodiment of the present invention, the path may further include a circulation pipe that branches off from the first path and returns the sulfuric acid to the first tank. The first heater may be positioned upstream of the sulfuric acid flow direction with respect to the branching point where the first path and the circulation pipe diverge.

[0015] In one embodiment of the present invention, the path may further include a circulation pipe that branches off from the first path and returns the sulfuric acid to the first tank. The first heater may be positioned downstream in the direction of sulfuric acid flow from the branching point where the first path and the circulation pipe diverge.

[0016] In one embodiment of the present invention, the substrate processing apparatus may further include a second heater for maintaining the sulfuric acid in the first tank at a predetermined temperature.

[0017] In one embodiment of the present invention, the substrate processing apparatus may further include a second tank and a third heater. The second tank may be located downstream of the first tank in the flow direction of the sulfuric acid. The third heater may maintain the sulfuric acid in the second tank at a temperature higher than that of the sulfuric acid in the first tank.

[0018] A substrate processing method according to one aspect of the present invention processes a substrate by supplying a processing liquid to the substrate. The substrate processing method includes a first discharge step of discharging sulfuric acid supplied from a first tank, passing through a first path having a heating region and heated in the heating region, and hydrogen peroxide that has passed through a hydrogen peroxide supply path, onto the substrate; and a second discharge step, after the first discharge step, of discharging sulfuric acid supplied from the first tank at a lower temperature than the heated sulfuric acid, and hydrogen peroxide that has passed through the hydrogen peroxide supply path, onto the substrate.

[0019] In one embodiment of the present invention, in the second discharge step, sulfuric acid that has passed through the second path without passing through the heating region and hydrogen peroxide solution may be discharged onto the substrate.

[0020] In one embodiment of the present invention, the first path and the second path may branch off upstream of the sulfuric acid flow direction with respect to the heating region and merge downstream of the sulfuric acid flow direction with respect to the heating region.

[0021] In one embodiment of the present invention, a first flow step may be included prior to the first discharge step, in which the sulfuric acid passing through the first pathway is heated to obtain sulfuric acid having a first temperature, and a second flow step may be included prior to the second discharge step, in which the sulfuric acid passing through the first pathway is obtained to obtain sulfuric acid having a second temperature lower than the first temperature.

[0022] In one embodiment of the present invention, the sulfuric acid in the first tank may be maintained at a predetermined temperature.

[0023] In one aspect of the present invention, the sulfuric acid in a second tank disposed downstream of the first tank in the flow direction of the sulfuric acid may be maintained at a temperature higher than the temperature of the sulfuric acid in the first tank. Effects of the Invention

[0024] According to the present invention, it is possible to provide a substrate processing apparatus and a substrate processing method that can suppress damage to a substrate. Brief Description of the Drawings

[0025] [Figure 1] It is a schematic plan view of the substrate processing apparatus according to the first embodiment of the present invention. [Figure 2] It is a schematic diagram of a substrate processing unit in the substrate processing apparatus according to the first embodiment. [Figure 3] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to the first embodiment. [Figure 4] It is a block diagram of the substrate processing apparatus according to the first embodiment. [Figure 5] It is a flowchart of the substrate processing method of the substrate processing apparatus according to the first embodiment. [Figure 6] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a first modification. [Figure 7] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a second modification. [Figure 8] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a third modification. [Figure 9] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a fourth modification. [Figure 10] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a second embodiment of the present invention. [Figure 11] It is a flowchart of the substrate processing method of the substrate processing apparatus according to the second embodiment. [Figure 12] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a fifth modification. [Figure 13] It is a schematic diagram of a processing liquid supply unit of the substrate processing apparatus according to a sixth modification. [Figure 14]This is a schematic diagram of a substrate processing unit in a substrate processing apparatus according to the third embodiment. [Figure 15] This is a schematic diagram of the processing liquid supply section of the substrate processing apparatus according to the third embodiment. [Figure 16] This is a flowchart of the substrate processing method of the substrate processing apparatus of the third embodiment. [Figure 17] This is a schematic diagram of the processing liquid supply section of the substrate processing apparatus according to the seventh modified example. [Figure 18] This is a schematic diagram of the processing liquid supply section of the substrate processing apparatus according to the eighth modified example. [Figure 19] This is a schematic diagram of the processing liquid supply section of the substrate processing apparatus according to the fourth embodiment of the present invention. [Figure 20] This is a flowchart of the substrate processing method of the substrate processing apparatus of the fourth embodiment. [Figure 21] This is a schematic diagram of the processing liquid supply section of the substrate processing apparatus according to the ninth modified example. [Figure 22] This is a schematic diagram of the processing liquid supply section of the substrate processing apparatus according to the 10th modified example. [Modes for carrying out the invention]

[0026] Embodiments of the substrate processing method and substrate processing apparatus according to the present invention will be described below with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals and the description will not be repeated. In this specification, mutually orthogonal X, Y, and Z axes may be described to facilitate understanding of the invention. Typically, the X and Y axes are parallel to the horizontal direction, and the Z axis is parallel to the vertical direction.

[0027] (First Embodiment) First, a substrate processing apparatus 100 according to the first embodiment of the present invention will be described with reference to Figure 1. Figure 1 is a schematic plan view of the substrate processing apparatus 100 of this embodiment.

[0028] The substrate processing apparatus 100 processes the substrate W. The substrate processing apparatus 100 processes the substrate W by performing at least one of the following: etching, surface treatment, characterization, formation of a treatment film, removal of at least a portion of the film, and cleaning.

[0029] The substrate W is used as a semiconductor substrate. The substrate W includes a semiconductor wafer. For example, the substrate W is roughly disc-shaped. Here, the substrate processing apparatus 100 processes the substrate W one sheet at a time.

[0030] As shown in Figure 1, the substrate processing apparatus 100 comprises a plurality of substrate processing units 10, a processing liquid box 110, a processing liquid cabinet 120, a plurality of load ports LP, an indexer robot IR, a center robot CR, and a control device 101. The control device 101 controls the load ports LP, the indexer robot IR, and the center robot CR. The control device 101 includes a control unit 102 and a storage unit 104.

[0031] Each load port LP accommodates multiple substrates W stacked together. The indexer robot IR transports the substrates W between the load port LP and the center robot CR. The center robot CR transports the substrates W between the indexer robot IR and the substrate processing unit 10. Each of the substrate processing units 10 processes the substrates W by discharging a processing liquid onto them. The processing liquid cabinet 120 contains the processing liquid.

[0032] Specifically, the multiple substrate processing units 10 form multiple towers TW (four towers TW in Figure 1) arranged to surround the central robot CR in a plan view. Each tower TW contains multiple substrate processing units 10 (three substrate processing units 10 in Figure 1) stacked vertically. Each processing liquid box 110 corresponds to one of the towers TW. The processing liquid in the processing liquid cabinet 120 is supplied to the tower TW corresponding to one of the processing liquid boxes 110. Note that the substrate processing units 10 and the processing liquid cabinet 120 may be supplied with gas as well as processing liquid.

[0033] The treatment solution may contain a so-called chemical solution. The chemical solution contains hydrofluoric acid. For example, hydrofluoric acid may be heated to 40°C to 70°C or to 50°C to 60°C. However, hydrofluoric acid does not need to be heated. The chemical solution may also contain water or phosphoric acid.

[0034] Furthermore, the chemical solution may contain hydrogen peroxide. The chemical solution may also contain sulfuric acid or a mixture of sulfuric acid and hydrogen peroxide. Additionally, the chemical solution may contain SC1 (ammonia and hydrogen peroxide mixture), SC2 (hydrochloric acid and hydrogen peroxide mixture), or aqua regia (a mixture of concentrated hydrochloric acid and concentrated nitric acid).

[0035] Alternatively, the treatment solution may include a so-called rinsing solution. For example, the rinsing solution may include deionized water (DIW), carbonated water, electrolyzed ionized water, ozonated water, ammonia water, hydrochloric acid water at a diluted concentration (e.g., about 10 ppm to 100 ppm), or reduced water (hydrogen water).

[0036] The processing liquid cabinet 120 partitions a specific space within the substrate processing apparatus 100. In the substrate processing apparatus 100, a boundary wall BW is placed between the area where the center robot CR and the substrate processing unit 10 are installed and the area where the processing liquid cabinet 120 is installed. The processing liquid cabinet 120 partitions a portion of the space in the area outside the boundary wall BW within the substrate processing apparatus 100.

[0037] The processing liquid cabinet 120 partitions a specific space within the substrate processing apparatus 100 by its housing. The processing liquid cabinet 120 has processing liquid piping through which the processing liquid flows within its housing. Typically, the processing liquid cabinet 120 also has a preparation tank for preparing the processing liquid. The processing liquid cabinet 120 may have a preparation tank for one type of processing liquid, or it may have preparation tanks for multiple types of processing liquids. The processing liquid cabinet 120 may also have a pump, nozzles, and / or filters for circulating the processing liquid.

[0038] Here, the processing liquid cabinet 120 has a first processing liquid housing 122a and a second processing liquid housing 122b. In Figure 1, in order to avoid making the drawing excessively complex, the flow of the processing liquid in the first processing liquid housing 122a is shown, supplied to the tower TW corresponding to one of the processing liquid boxes 110 via one of the processing liquid boxes 110, and the flow of the processing liquid in the second processing liquid housing 122b is omitted.

[0039] The control device 101 controls various operations of the substrate processing device 100. The control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 has a processor. The control unit 102 may have, for example, a central processing unit (CPU). Alternatively, the control unit 102 may have a general-purpose arithmetic unit.

[0040] The storage unit 104 stores data and computer programs. The data includes recipe data. The recipe data includes information indicating multiple recipes. Each of the multiple recipes specifies the processing content and processing procedure for the substrate W.

[0041] The storage unit 104 includes a main memory and an auxiliary storage device. The main memory is, for example, a semiconductor memory. The auxiliary storage device is, for example, a semiconductor memory and / or a hard disk drive. The storage unit 104 may also include removable media. The control unit 102 executes the computer program stored in the storage unit 104 to perform board processing operations.

[0042] Next, with reference to Figure 2, the substrate processing unit 10 in the substrate processing apparatus 100 of this embodiment will be described. Figure 2 is a schematic diagram of the substrate processing unit 10 in the substrate processing apparatus 100.

[0043] The substrate processing unit 10 comprises a chamber 12 and a substrate holding section 20. The chamber 12 houses the substrate W. The substrate holding section 20 holds the substrate W.

[0044] Chamber 12 is a roughly box-shaped chamber with an internal space. Chamber 12 houses the substrate W. Here, the substrate processing apparatus 100 is a single-wafer type that processes substrates W one at a time, and each chamber 12 houses one substrate W. The substrate W is housed in and processed within Chamber 12. Chamber 12 houses at least a portion of the substrate holding section 20 and the processing liquid supply section 30, which will be described later.

[0045] The substrate holder 20 holds the substrate W. The substrate holder 20 holds the substrate W horizontally so that the top surface (front surface) Wa of the substrate W faces upward and the back surface (bottom surface) Wb of the substrate W faces vertically downward. The substrate holder 20 also rotates the substrate W while holding it. The substrate holder 20 rotates the substrate W while holding it.

[0046] For example, the substrate holder 20 may be a clamping type that clamps the edges of the substrate W. Alternatively, the substrate holder 20 may have any mechanism for holding the substrate W from the back surface Wb. For example, the substrate holder 20 may be a vacuum type. In this case, the substrate holder 20 holds the substrate W horizontally by adhering the central part of the back surface Wb of the substrate W, which is the non-device forming surface, to its upper surface. Alternatively, the substrate holder 20 may combine a clamping type and a vacuum type, where a plurality of chuck pins contact the peripheral edge surface of the substrate W.

[0047] For example, the substrate holding section 20 includes a spin base 21, a chuck member 22, a shaft 23, an electric motor 24, and a housing 25. The chuck member 22 is provided on the spin base 21. The chuck member 22 chucks the substrate W. Typically, the spin base 21 is provided with multiple chuck members 22.

[0048] The shaft 23 is a hollow shaft. The shaft 23 extends vertically along the rotation axis Ax. The spin base 21 is coupled to the upper end of the shaft 23. The substrate W is placed above the spin base 21.

[0049] The spin base 21 is disc-shaped and horizontally supports the substrate W. The shaft 23 extends downward from the center of the spin base 21. The electric motor 24 provides rotational force to the shaft 23. By rotating the shaft 23 in the rotational direction, the electric motor 24 rotates the substrate W and the spin base 21 around the rotation axis Ax. The housing 25 surrounds the shaft 23 and the electric motor 24.

[0050] The substrate processing apparatus 100 further comprises a processing liquid supply unit 30. The processing liquid supply unit 30 supplies processing liquid to the substrate W. Typically, the processing liquid supply unit 30 supplies processing liquid to the upper surface Wa of the substrate W.

[0051] The processing liquid supply unit 30 includes piping 40, a valve 34, a nozzle 36, and a heater 60 (see Figure 3), which will be described later. The nozzle 36 discharges the processing liquid onto the upper surface Wa of the substrate W. The nozzle 36 may, for example, discharge the processing liquid to the center of the substrate W, or to the area between the center and the periphery of the substrate W. The nozzle 36 has an outlet 36a (see Figure 3), and discharges the processing liquid from the outlet 36a. The nozzle 36 is connected to the piping 40. The processing liquid is supplied to the piping 40 from a supply source. The valve 34 opens and closes the flow path in the piping 40. It is preferable that the nozzle 36 is configured to be movable relative to the substrate W. The nozzle 36 can move horizontally and / or vertically according to a movement mechanism controlled by the control unit 102. Note that in this specification, the movement mechanism is omitted to avoid making the drawings excessively complex.

[0052] Valve 34 adjusts the flow rate of the processing fluid supplied to pipe 40 by adjusting the opening degree of pipe 40. Specifically, valve 34 includes a valve body (not shown) with a valve seat inside, a valve element that opens and closes the valve seat, and an actuator (not shown) that moves the valve element between an open position and a closed position.

[0053] The substrate processing apparatus 100 further includes a cup 80. The cup 80 collects processing liquid that has splashed from the substrate W. The cup 80 moves up and down. For example, the cup 80 rises vertically upward to the side of the substrate W during the period when the processing liquid supply unit 30 supplies processing liquid to the substrate W. In this case, the cup 80 collects processing liquid that splashes from the substrate W due to the rotation of the substrate W. The cup 80 then descends vertically downward from the side of the substrate W when the period during which the processing liquid supply unit 30 supplies processing liquid to the substrate W ends.

[0054] As described above, the control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 controls the substrate holding unit 20, the processing liquid supply unit 30 and / or the cup 80. In one example, the control unit 102 controls the electric motor 24 and the valve 34.

[0055] The substrate processing apparatus 100 of this embodiment is suitably used for manufacturing semiconductor devices on which semiconductors are provided. Typically, in a semiconductor device, a conductive layer and an insulating layer are laminated on a substrate. The substrate processing apparatus 100 is suitably used for cleaning and / or processing (e.g., etching, property change, etc.) the conductive layer and / or insulating layer during the manufacturing of semiconductor devices. The substrate processing apparatus 100 is also suitably used for removing the insulating layer (e.g., the resist layer).

[0056] In the substrate processing unit 10 shown in Figure 2, the processing liquid supply unit 30 can supply one type of processing liquid to the substrate W, but the processing liquid supply unit 30 may also be capable of supplying multiple types of processing liquids to the substrate W. For example, the processing liquid supply unit 30 may include multiple pipes 40, valves 34, and nozzles 36.

[0057] Next, the processing liquid supply unit 30 of the substrate processing apparatus 100 of this embodiment will be described in detail with reference to Figures 1 to 3. Figure 3 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of this embodiment.

[0058] As shown in Figure 3, the processing liquid supply unit 30 includes a tank 50, a path 70, a hydrogen peroxide water supply path C3, and a heater 61 as the heater 60. The tank 50 stores sulfuric acid. The path 70 is a path for supplying sulfuric acid from the tank 50 to the nozzle 36. In this embodiment, the path 70 includes a first path C1 and a second path C2. Note that the tank 50 is an example of the "first tank" of the present invention. Also, the heater 61 is an example of the "first heater" of the present invention.

[0059] The first pathway C1 is the pathway for supplying sulfuric acid from the tank 50 to the nozzle 36. Heater 61 heats the heating region R1 of the first pathway C1. Therefore, the temperature of the sulfuric acid passing through the heating region R1 rises. For example, the temperature of the sulfuric acid passing through the heating region R1 becomes 170°C to 190°C or higher. Although heaters other than heater 61 may be placed in the first pathway C1, heater 61 is the heater placed at the downstream end in the direction of sulfuric acid flow in the first pathway C1.

[0060] The second pathway C2 is a pathway that supplies sulfuric acid from the tank 50 to the nozzle 36 without passing through the heating region R1. In this embodiment, no heater is placed in the second pathway C2. The sulfuric acid that has passed through the second pathway C2 is at a lower temperature than the sulfuric acid that has passed through the first pathway C1 and been heated.

[0061] The hydrogen peroxide supply path C3 is a path that supplies hydrogen peroxide to the nozzle 36. The hydrogen peroxide supply path C3 is a path that supplies hydrogen peroxide to the nozzle 36 from, for example, a hydrogen peroxide tank (not shown). Note that there is no heater in the hydrogen peroxide supply path C3, and the hydrogen peroxide passing through the hydrogen peroxide supply path C3 is at room temperature (for example, 25°C).

[0062] The processing liquid supply unit 30 includes the first pipe 41, second pipe 42, and third pipe 43 as the piping 40 described above. In this embodiment, the first route C1 is made up of the first pipe 41, the second route C2 is made up of the second pipe 42, and the hydrogen peroxide water supply route C3 is made up of the third pipe 43.

[0063] Furthermore, the processing liquid supply unit 30 includes a first valve 34a, a second valve 34b, and a hydrogen peroxide valve 34c, which are the valves 34 described above. The first valve 34a is inserted into the first path C1 and opens and closes the flow path of the first path C1. The second valve 34b is inserted into the second path C2 and opens and closes the flow path of the second path C2. The hydrogen peroxide valve 34c is inserted into the hydrogen peroxide supply path C3 and opens and closes the flow path of the hydrogen peroxide supply path C3.

[0064] In this embodiment, sulfuric acid passing through the first path C1 and hydrogen peroxide passing through the hydrogen peroxide supply path C3 merge at the first merging section P1. The first merging section P1 is located between the heating region R1 and the discharge port 36a of the nozzle 36, and is the part where the first path C1 and the hydrogen peroxide supply path C3 merge. In this embodiment, the first merging section P1 is located, for example, inside the nozzle 36.

[0065] For example, the mixing ratio of sulfuric acid and hydrogen peroxide passing through the first pathway C1 is set such that the sulfuric acid concentration is greater than 8:2 in volume ratio. Alternatively, the mixing ratio of sulfuric acid and hydrogen peroxide passing through the first pathway C1 is set such that the sulfuric acid:hydrogen peroxide concentration is, for example, 8.5-9.5:1.5-0.5 in volume ratio. The combined sulfuric acid and hydrogen peroxide react with each other to form a high-temperature (e.g., above 200°C) hydrogen peroxide mixture.

[0066] Furthermore, the sulfuric acid passing through the second pathway C2 and the hydrogen peroxide supply pathway C3 merge, for example, within the nozzle 36. The sulfuric acid passing through the second pathway C2 merges with the hydrogen peroxide at a lower temperature than the sulfuric acid passing through the first pathway C1. Therefore, the merged sulfuric acid and hydrogen peroxide react with each other, but form a relatively low-temperature hydrogen peroxide mixture. The flow rate (amount flowing per unit time) of the sulfuric acid passing through the second pathway C2 is not particularly limited, but in this embodiment, it is approximately the same as the flow rate of the sulfuric acid passing through the first pathway C1.

[0067] The control unit 102 controls the first valve 34a, the second valve 34b, and the hydrogen peroxide valve 34c so that after the sulfuric acid and hydrogen peroxide solution passing through the first path C1 are mixed and discharged onto the substrate W from the nozzle 36, the sulfuric acid and hydrogen peroxide solution passing through the second path C2 are mixed and discharged onto the substrate W from the nozzle 36. Therefore, when the supply of sulfuric acid is stopped in order to wash away the sulfuric acid and hydrogen peroxide solution mixture on the substrate W with hydrogen peroxide, it is possible to suppress the high temperature of the sulfuric acid and hydrogen peroxide solution mixture from becoming even hotter, and to suppress a rapid change in the temperature of the substrate W. Thus, it is possible to suppress damage to the substrate W, such as pattern peeling.

[0068] In detail, when sulfuric acid and hydrogen peroxide passing through the first pathway C1 are mixed, the combined sulfuric acid and hydrogen peroxide react with each other to form a high-temperature (e.g., 200°C or higher) sulfuric acid-hydrogen peroxide mixture. After this high-temperature sulfuric acid-hydrogen peroxide mixture is discharged onto the substrate W, the supply of sulfuric acid is stopped, and the high-temperature sulfuric acid-hydrogen peroxide mixture and hydrogen peroxide combine on the substrate W. At this time, the sulfuric acid-hydrogen peroxide mixture remaining on the substrate W is at a high temperature and reacts violently with the hydrogen peroxide, becoming even hotter, and the substrate W also becomes hot. Subsequently, by supplying more hydrogen peroxide onto the substrate W, the sulfuric acid-hydrogen peroxide mixture is removed from the substrate W, and the temperature of the substrate W rapidly decreases due to the supplied hydrogen peroxide.

[0069] On the other hand, in this embodiment, sulfuric acid and hydrogen peroxide passing through the first pathway C1 are mixed and discharged from the nozzle 36 onto the substrate W, and then sulfuric acid and hydrogen peroxide passing through the second pathway C2 are mixed and discharged from the nozzle 36 onto the substrate W. The sulfuric acid passing through the second pathway C2 merges with the hydrogen peroxide at a lower temperature than the sulfuric acid passing through the first pathway C1. Therefore, the merged sulfuric acid and hydrogen peroxide react with each other, but form a relatively low-temperature hydrogen peroxide mixture. After this relatively low-temperature sulfuric acid-hydrogen peroxide mixture is discharged onto the substrate W, the supply of sulfuric acid is stopped, and the relatively low-temperature sulfuric acid-hydrogen peroxide mixture and hydrogen peroxide merge on the substrate W. At this time, since the sulfuric acid-hydrogen peroxide mixture remaining on the substrate W is relatively low temperature, vigorous reaction with hydrogen peroxide is suppressed. Therefore, the temperature rise of the sulfuric acid-hydrogen peroxide mixture is suppressed, and the temperature rise of the substrate W is also suppressed. Subsequently, by supplying hydrogen peroxide solution to the substrate W, the sulfuric acid-hydrogen peroxide mixture is removed from the substrate W, and the temperature of the substrate W decreases relatively slowly due to the supplied hydrogen peroxide solution.

[0070] Furthermore, in this embodiment, since it is not necessary to adjust the mixing ratio of sulfuric acid and hydrogen peroxide solution to a desired ratio in order to suppress damage to the substrate W, the time required can be reduced compared to methods that adjust the mixing ratio to a desired ratio.

[0071] Furthermore, in this embodiment, by providing a second path C2 that supplies sulfuric acid from the tank 50 to the nozzle 36 without passing through the heating region R1, sulfuric acid at a lower temperature than the sulfuric acid heated by passing through the first path C1 can be easily mixed with hydrogen peroxide solution.

[0072] Next, the substrate processing apparatus 100 of this embodiment will be described with reference to Figures 1 to 4. Figure 4 is a block diagram of the substrate processing apparatus 100.

[0073] As shown in Figure 4, the control device 101 controls various operations of the substrate processing apparatus 100. The control device 101 controls the indexer robot IR, the center robot CR, the substrate holding unit 20, and the processing liquid supply unit 30. Specifically, the control device 101 controls the indexer robot IR, the center robot CR, the substrate holding unit 20, and the processing liquid supply unit 30 by transmitting control signals to them.

[0074] Specifically, the control unit 102 controls the indexer robot IR to transfer the substrate W using the indexer robot IR.

[0075] The control unit 102 controls the center robot CR to transfer the substrate W to the center robot CR. For example, the center robot CR receives an unprocessed substrate W and transports it to one of the substrate processing units 10. The center robot CR also receives the processed substrate W from the substrate processing unit 10 and transports the substrate W out.

[0076] The control unit 102 controls the substrate holder 20 to control the start of rotation of the substrate W, the change in rotation speed, and the stop of rotation of the substrate W. For example, the control unit 102 can change the rotation speed of the substrate holder 20 by controlling the substrate holder 20. Specifically, the control unit 102 can change the rotation speed of the substrate W by changing the rotation speed of the electric motor 24 of the substrate holder 20.

[0077] The control unit 102 can control the valve 34 of the processing liquid supply unit 30 to switch the state of the valve 34 between an open state and a closed state. Specifically, by controlling the valve 34 of the processing liquid supply unit 30 to open the valve 34, the control unit 102 can allow the processing liquid flowing through the piping 40 to pass towards the nozzle 36. Conversely, by controlling the valve 34 of the processing liquid supply unit 30 to close the valve 34, the control unit 102 can stop the supply of the processing liquid flowing through the piping 40 towards the nozzle 36. In other words, the control unit 102 controls the supply of sulfuric acid and hydrogen peroxide to the nozzle 36 by, for example, controlling the opening and closing of the first valve 34a, the second valve 34b, and the hydrogen peroxide valve 34c.

[0078] The control unit 102 controls the heater 60 to heat the tank 50 and the piping 40 to a predetermined temperature. Specifically, the control unit 102 controls the heater 60 to turn on and off to maintain the temperature of at least one of the sulfuric acid in the tank 50 and the sulfuric acid passing through the piping 40 at a predetermined temperature. In this embodiment, the control unit 102 controls the heater 60 to heat the sulfuric acid passing through the heating region R1 of the first path C1 to a predetermined temperature.

[0079] Next, the substrate processing method of the substrate processing apparatus 100 of this embodiment will be described with reference to Figures 1 to 5. Figure 5 is a flowchart of the substrate processing method of the substrate processing apparatus 100 of this embodiment. Step S103 is an example of the "first discharge step" of the present invention. Step S107 is an example of the "second discharge step" of the present invention.

[0080] As shown in Figure 5, in step S101, the control unit 102 combines the sulfuric acid that has passed through the heating region R1 with hydrogen peroxide solution. At this time, the second valve 34b is closed, and the heater 61 is turned on. Hereafter, the sulfuric acid that has passed through the heating region R1 may be referred to as relatively high-temperature sulfuric acid.

[0081] Specifically, the control unit 102 switches the first valve 34a from the closed state to the open state. The control unit 102 also switches the hydrogen peroxide valve 34c from the closed state to the open state. As a result, sulfuric acid is supplied from the tank 50 to the nozzle 36. The sulfuric acid is heated to a predetermined temperature (for example, 170°C to 190°C or higher) by the heater 61 in the heating region R1 of the first pipe 41. Hydrogen peroxide solution is also supplied to the nozzle 36.

[0082] The relatively high-temperature sulfuric acid heated in the heating region R1 merges with hydrogen peroxide. The relatively high-temperature sulfuric acid merges with hydrogen peroxide between the heating region R1 and the discharge port 36a of the nozzle 36. In this embodiment, the relatively high-temperature sulfuric acid merges with hydrogen peroxide within the nozzle 36. Note that the hydrogen peroxide valve 34c may be opened before opening the first valve 34a.

[0083] Next, in step S103, a relatively high-temperature sulfuric acid and hydrogen peroxide solution are discharged onto the substrate W. Specifically, a high-temperature (e.g., 200°C or higher) sulfuric acid and hydrogen peroxide solution mixture, consisting of relatively high-temperature sulfuric acid and hydrogen peroxide solution, is discharged onto the substrate W from the discharge port 36a of the nozzle 36 for a predetermined time. This etches, for example, a predetermined area of ​​the resist layer (not shown) of the substrate W.

[0084] Next, in step S105, the control unit 102 combines the relatively low-temperature sulfuric acid with the hydrogen peroxide solution. Specifically, the control unit 102 switches the second valve 34b from the closed state to the open state. The control unit 102 also switches the first valve 34a from the open state to the closed state. As a result, the relatively low-temperature sulfuric acid is supplied from the tank 50 to the nozzle 36. At the same time, the supply of the relatively high-temperature sulfuric acid is stopped.

[0085] Furthermore, it is preferable to switch the second valve 34b from the closed state to the open state before switching the first valve 34a from the open state to the closed state. More specifically, it is preferable to switch the second valve 34b from the closed state to the open state so that relatively low-temperature sulfuric acid reaches the first confluence P1 in the nozzle 36 while relatively high-temperature sulfuric acid is present at the first confluence P1. This prevents only hydrogen peroxide from being supplied from the nozzle 36 to the high-temperature sulfuric acid-hydrogen peroxide mixture on the substrate W.

[0086] Next, in step S107, a relatively low-temperature sulfuric acid and hydrogen peroxide solution are discharged onto the substrate W. Specifically, a relatively low-temperature sulfuric acid and hydrogen peroxide solution mixture, consisting of relatively low-temperature sulfuric acid and hydrogen peroxide solution, is discharged onto the substrate W from the discharge port 36a of the nozzle 36 for a predetermined time.

[0087] Next, in step S109, the control unit 102 stops supplying sulfuric acid. Specifically, the control unit 102 switches the second valve 34b from the open state to the closed state. As a result, only hydrogen peroxide is supplied onto the substrate W. At this time, the hydrogen peroxide merges with the relatively low-temperature sulfuric acid-hydrogen peroxide mixture remaining on the substrate W, thus suppressing a violent reaction between the sulfuric acid-hydrogen peroxide mixture and hydrogen peroxide. Therefore, the temperature of the sulfuric acid-hydrogen peroxide mixture is suppressed from becoming high, and the temperature rise of the substrate W is also suppressed. Subsequently, by supplying more hydrogen peroxide onto the substrate W, the sulfuric acid-hydrogen peroxide mixture is removed from the substrate W, and the temperature of the substrate W decreases relatively slowly.

[0088] Next, in step S111, the control unit 102 stops the supply of hydrogen peroxide solution. Specifically, the control unit 102 switches the hydrogen peroxide valve 34c from the open state to the closed state. This stops the supply of the processing solution to the substrate W.

[0089] This concludes the substrate processing method of this embodiment.

[0090] (First variation) Next, with reference to Figure 6, a substrate processing apparatus 100 of the first modified embodiment of the present invention will be described. In the first modified embodiment, unlike the first embodiment described using Figures 1 to 5, an example will be described in which the first path C1 and the second path C2 merge upstream of the first confluence point P1 in the sulfuric acid flow direction. Figure 6 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of the first modified embodiment.

[0091] As shown in Figure 6, in the first modified example, the processing liquid supply unit 30 has a second junction P2. The second junction P2 is the part where the first path C1 and the second path C2 merge. The second junction P2 is located between the first junction P1 and the heating region R1, and merges the first path C1 and the second path C2.

[0092] Specifically, the portion of the first pipe 41 upstream of the heating region R1 (towards the tank 50) is designated as pipe 41a, and the portion downstream of the heating region R1 (towards the nozzle 36) is designated as pipe 41b. In this case, the second pipe 42 is connected to pipe 41b. The portion of pipe 41b downstream of the second junction P2 (towards the nozzle 36) forms a common path for the first path C1 and the second path C2. In the first modified example, the second path C2 is formed by the second pipe 42 and a portion of pipe 41b. The relatively low-temperature sulfuric acid is then supplied to the nozzle 36 by passing through the second pipe 42 and a portion of pipe 41b.

[0093] In the first modified example, the first pathway C1 and the second pathway C2 merge between the first confluence point P1 and the heating region R1. Therefore, both the relatively high-temperature sulfuric acid and the relatively low-temperature sulfuric acid merge with the hydrogen peroxide solution at the same point. Thus, the sulfuric acid and hydrogen peroxide solution can be stably mixed.

[0094] Furthermore, since a portion of the piping 41b can be made into a common piping for the first route C1 and the second route C2, it is possible to suppress the enlargement of the processing liquid supply unit 30.

[0095] Other structures, other effects, and substrate processing methods of the first modified example are the same as those of the first embodiment.

[0096] (Second variation) Next, with reference to Figure 7, a second modified substrate processing apparatus 100 of the present invention will be described. In the second modified example, unlike the first modified example described using Figure 6, a first path C1 and a second path C2 branch upstream of the sulfuric acid flow direction relative to the heating region R1 will be described. Figure 7 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of the second modified example.

[0097] As shown in Figure 7, in the second modified example, the processing liquid supply unit 30 has a branching section P3. The branching section P3 is the part where the first path C1 and the second path C2 diverge. The branching section P3 is located upstream of the sulfuric acid flow direction (towards the tank 50) relative to the heating region R1. In other words, the first path C1 and the second path C2 diverge upstream of the sulfuric acid flow direction relative to the heating region R1.

[0098] In the second modified example, the first path C1 and the second path C2 merge downstream of the sulfuric acid flow direction relative to the heating region R1 (towards the nozzle 36). Specifically, the processing liquid supply unit 30 has a second merging section P2 where the first path C1 and the second path C2 merge, similar to the first modified example. The second merging section P2 is located downstream of the sulfuric acid flow direction relative to the heating region R1.

[0099] In detail, the second pipe 42 is connected to pipes 41a and 41b of the first pipe 41. The portion of pipe 41a upstream of branch point P3 (towards the tank 50) forms a common path for the first path C1 and the second path C2. In the second modified example, the second path C2 is formed by a portion of pipe 41a, the second pipe 42, and a portion of pipe 41b. The relatively low-temperature sulfuric acid is then supplied to the nozzle 36 by passing through a portion of pipe 41a, the second pipe 42, and a portion of pipe 41b.

[0100] In the second modified example, the first valve 34a, which opens and closes the flow path of the first path C1, is located between the branching section P3 and the second junction section P2. The second valve 34b, which opens and closes the flow path of the second path C2, is located in the second piping 42.

[0101] In the second modified example, the first path C1 and the second path C2 branch off upstream of the heating region R1 and merge downstream of the heating region R1. Therefore, a portion of the piping 41a and a portion of the piping 41b can be made into common piping for the first path C1 and the second path C2, which further suppresses the need to enlarge the processing liquid supply unit 30.

[0102] The other structures, other effects, and substrate processing methods of the second modified example are the same as those of the first modified example.

[0103] (Third variation) Next, a third modified example of the substrate processing apparatus 100 of the present invention will be described with reference to Figure 8. In the third modified example, unlike the first embodiment described using Figures 1 to 5, an example in which the processing liquid supply unit 30 includes a heater 62 will be described. Figure 8 is a schematic diagram of the processing liquid supply unit 30 of the third modified example of the substrate processing apparatus 100.

[0104] As shown in Figure 8, in the third modified example, the processing liquid supply unit 30 further includes a heater 62 as the heater 60 described above. Note that heater 62 is an example of the "second heater" of the present invention. Heater 62 is a heater for maintaining the sulfuric acid in the tank 50 at a predetermined temperature. In the third modified example, heater 62 maintains the sulfuric acid in the tank 50 at a predetermined temperature by heating the tank 50. For example, the sulfuric acid in the tank 50 is maintained at 150°C or higher. Note that heater 62 does not necessarily have to heat the tank 50. For example, a circulation pipe for circulating sulfuric acid may be connected to the tank 50, and the circulation pipe may be heated by heater 62.

[0105] In the third modified example, by providing a heater 62 that maintains the sulfuric acid in the tank 50 at a predetermined temperature, the sulfuric acid passing through the heating region R1 can be easily heated to a desired temperature (for example, 170°C to 190°C or higher).

[0106] Other structures, effects, and substrate processing methods of the third modified example are the same as those of the first embodiment.

[0107] (Fourth variation) Next, with reference to Figure 9, a fourth modified example of the substrate processing apparatus 100 of the present invention will be described. In the fourth modified example, unlike the first modified example described using Figure 6, a third pipe 43 is connected to the first pipe 41. Figure 9 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of the fourth modified example.

[0108] As shown in Figure 9, in the fourth modified example, the first path C1 and the hydrogen peroxide supply path C3 merge between the nozzle 36 and the heating region R1.

[0109] Specifically, the third pipe 43 is connected to pipe 41b of the first pipe 41. Then, the third pipe 43 and a portion of pipe 41b form the hydrogen peroxide water supply path C3.

[0110] In the fourth modified example, the third pipe 43 is connected to pipe 41b between the second junction P2 and the nozzle 36. The portion of pipe 41b downstream of the first junction P1 (towards the nozzle 36) is a common pipe for the first route C1, the second route C2, and the hydrogen peroxide water supply route C3.

[0111] In the fourth modified example, by connecting the third pipe 43 to the first pipe 41, a portion of the first pipe 41 can be made into a common pipe, thus further suppressing the enlargement of the processing liquid supply unit 30. In addition, compared to the case where sulfuric acid and hydrogen peroxide are combined in the nozzle 36, the time from combination to discharge is longer, so the sulfuric acid and hydrogen peroxide can be mixed more uniformly.

[0112] The other structures, other effects, and substrate processing methods of the fourth modified example are the same as those of the first modified example.

[0113] (Second Embodiment) Next, with reference to Figure 10, a substrate processing apparatus 100 according to a second embodiment of the present invention will be described. In the second embodiment, unlike the first embodiment described using Figures 1 to 5, an example will be described in which the processing liquid supply unit 30 has tanks 50 and 51. Figure 10 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of this embodiment. The differences from the first embodiment will be mainly described below.

[0114] As shown in Figure 10, in the second embodiment, the processing liquid supply unit 30 includes a tank 50, a tank 51, a path 70 (first path C1, second path C2), a hydrogen peroxide water supply path C3, and heaters 61, 62, and 63. Tanks 50 and 51 store sulfuric acid. Path 70 is a path for supplying sulfuric acid from tank 51 to nozzle 36.

[0115] In this embodiment, tank 51 is an example of the "first tank" of the present invention. Tank 50 is an example of the "second tank" of the present invention. Heater 63 is an example of the "second heater" of the present invention. Heater 62 is an example of the "third heater" of the present invention.

[0116] In this embodiment, the first route C1 is a route for supplying sulfuric acid from the tank 51 to the nozzle 36. The second route C2 is a route for supplying sulfuric acid from the tank 51 to the nozzle 36.

[0117] Specifically, the processing liquid supply unit 30 includes the first pipe 41, second pipe 42, third pipe 43, and fourth pipe 44 as the piping 40 described above. The fourth pipe 44 connects tank 50 to tank 51. In this embodiment, the first route C1 is composed of the fourth pipe 44, tank 50, and first pipe 41. Also in this embodiment, the second pipe 42 connects tank 51 to nozzle 36. The second route C2 is composed of the second pipe 42.

[0118] The processing liquid supply unit 30 further includes a fourth valve 34d, which functions as a valve 34. The fourth valve 34d is located in the fourth pipe 44. The fourth valve 34d opens and closes the flow path of the fourth pipe 44. When the amount of sulfuric acid in the tank 50 falls below a predetermined amount, the control unit 102 switches the fourth valve 34d from a closed state to an open state. This supplies sulfuric acid from tank 51 to tank 50.

[0119] The processing liquid supply unit 30 includes heaters 61, 62, and 63 as heaters 60. Heater 62 is a heater for maintaining the sulfuric acid in the tank 50 at a predetermined temperature, similar to the third modified example. Since heater 62 is the same as in the third modified example, its description is omitted.

[0120] Heater 63 is a heater for maintaining the sulfuric acid in tank 51 at a predetermined temperature. In the second embodiment, heater 63 maintains the sulfuric acid in tank 51 at a predetermined temperature by heating tank 51. The sulfuric acid in tank 51 is maintained at a lower temperature than the sulfuric acid in tank 50. For example, the sulfuric acid in tank 51 is maintained at, for example, 120°C or higher and less than 150°C. Note that heater 62 does not necessarily have to heat tank 51. For example, a circulation pipe for circulating sulfuric acid may be connected to tank 51, and the circulation pipe may be heated by heater 63.

[0121] Furthermore, in this embodiment, the processing liquid supply unit 30 includes a return pipe 45 and a return pipe 46, and valves 34e and 34f. The return pipe 45 is connected to pipe 41b of the first pipe 41. Valve 34e is located in the return pipe 45. Valve 34e opens and closes the flow path of the return pipe 45.

[0122] The return pipe 46 is connected to the portion of the second pipe 42 downstream of the second valve 34b (towards the nozzle 36). Valve 34f is located in the return pipe 46. Valve 34f opens and closes the flow path of the return pipe 46.

[0123] The other configurations of the second embodiment are the same as those of the first embodiment.

[0124] Next, the substrate processing method of the substrate processing apparatus 100 of this embodiment will be described with reference to Figures 10 and 11. Figure 11 is a flowchart of the substrate processing method of the substrate processing apparatus 100 of this embodiment. Steps S201 to S211 of this embodiment correspond to steps S101 to S111 of the first embodiment. Step S203 is an example of the "first discharge step" of the present invention. Step S207 is an example of the "second discharge step" of the present invention. In this embodiment, the differences from the first embodiment will be mainly described.

[0125] As shown in Figure 11, in step S201, the control unit 102 combines the relatively high-temperature sulfuric acid that has passed through the heating region R1 with hydrogen peroxide solution. At this time, the second valves 34b, 34e, and 34f are closed. Also, heaters 61, 62, and 63 are turned on.

[0126] Next, in step S203, relatively high-temperature sulfuric acid and hydrogen peroxide solution are discharged onto the substrate W.

[0127] Next, in step S205, the control unit 102 combines relatively low-temperature sulfuric acid with hydrogen peroxide. Specifically, the control unit 102 switches the second valve 34b from the closed state to the open state. The control unit 102 also switches the first valve 34a from the open state to the closed state. As a result, relatively low-temperature sulfuric acid is supplied from the tank 51 to the nozzle 36.

[0128] Next, in step S207, relatively low-temperature sulfuric acid and hydrogen peroxide solution are discharged onto the substrate W.

[0129] Next, in step S209, the control unit 102 stops supplying sulfuric acid.

[0130] Next, in step S211, the control unit 102 stops the supply of hydrogen peroxide solution.

[0131] Next, in step S213, the control unit 102 opens valves 34e and 34f to prevent the processing liquid from dripping from the nozzle 36. Specifically, the control unit 102 switches valve 34e from the closed state to the open state. This draws the processing liquid remaining between the return pipe 45 and the discharge port 36a of the nozzle 36 back into the return pipe 45 by the siphon principle. The control unit 102 also switches valve 34f from the closed state to the open state. This draws the processing liquid remaining between the return pipe 46 and the discharge port 36a of the nozzle 36 back into the return pipe 46 by the siphon principle. Thus, it is possible to prevent the processing liquid from dripping from the discharge port 36a of the nozzle 36. After that, the control unit 102 closes valves 34e and 34f.

[0132] This concludes the substrate processing method of this embodiment.

[0133] Other effects of the second embodiment and other substrate processing methods are the same as those of the first embodiment.

[0134] (Fifth variation) Next, with reference to Figure 12, a fifth modified example of the substrate processing apparatus 100 of the present invention will be described. In the fifth modified example, unlike the second embodiment described using Figures 10 and 11, a first path C1 and a second path C2 branch upstream of the sulfuric acid flow direction relative to the heating region R1 will be described. Figure 12 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of the fifth modified example.

[0135] As shown in Figure 12, in the fifth modified example, similar to the second modified example, the processing liquid supply unit 30 has a branching section P3. The branching section P3 is the part where the first path C1 and the second path C2 diverge. The branching section P3 is located upstream of the heating region R1 in the direction of sulfuric acid flow. In other words, the first path C1 and the second path C2 diverge upstream of the heating region R1 in the direction of sulfuric acid flow.

[0136] Furthermore, in the fifth modified example, similar to the second modified example shown in Figure 7, the first path C1 and the second path C2 merge downstream of the heating region R1 in the direction of sulfuric acid flow. Specifically, the processing liquid supply unit 30 has a second merging section P2 where the first path C1 and the second path C2 merge, similar to the second modified example. The second merging section P2 is located downstream of the heating region R1 in the direction of sulfuric acid flow.

[0137] In detail, the second pipe 42 is connected to pipes 41a and 41b of the first pipe 41. The portion of pipe 41a upstream of branch point P3 (towards the tank 50) and the fourth pipe 44 form a common route for the first route C1 and the second route C2. In the fifth modified example, the first route C1 is formed by the fourth pipe 44 and the first pipe 41. The second route C2 is formed by the fourth pipe 44, a portion of pipe 41a, the second pipe 42, and a portion of pipe 41b.

[0138] In the fifth modified example, similar to the second modified example, the first valve 34a, which opens and closes the flow path of the first path C1, is located between the branching section P3 and the second junction section P2. The second valve 34b, which opens and closes the flow path of the second path C2, is located in the second piping 42.

[0139] In the fifth modified example, the first path C1 and the second path C2 branch off upstream of the heating region R1 and merge downstream of the heating region R1. Therefore, the fourth pipe 44, part of pipe 41a, and part of pipe 41b can be made into common piping for the first path C1 and the second path C2, thereby further suppressing the enlargement of the processing liquid supply unit 30.

[0140] Other structures, other effects, and substrate processing methods of the fifth modified example are the same as those of the second embodiment.

[0141] (Sixth variation) Next, with reference to Figure 13, a sixth modified example of the substrate processing apparatus 100 of the present invention will be described. Unlike the fifth modified example described using Figure 12, the sixth modified example describes an example in which a circulation pipe 47 for circulating sulfuric acid is provided. Figure 13 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of the sixth modified example.

[0142] As shown in Figure 13, in the sixth modified example, the processing liquid supply unit 30 has a circulation pipe 47. In the sixth modified example, the circulation pipe 47 is connected to pipe 41b. The circulation pipe 47 is connected, for example, to the portion of pipe 41b downstream of the second junction P2. The circulation pipe 47 connects, for example, pipe 41b to tank 51. The circulation pipe 47 returns the sulfuric acid passing through pipe 41b to tank 51. The circulation pipe 47 may also connect pipe 41a or the second pipe 42 to tank 51. Alternatively, the circulation pipe 47 may connect pipe 41a, the second pipe 42, or pipe 41b to tank 50, returning the sulfuric acid to tank 50.

[0143] The processing liquid supply unit 30 includes valves 34g and 34h. Valve 34g is located in the circulation pipe 47. Valve 34g opens and closes the flow path of the circulation pipe 47. Valve 34h is located downstream of the portion of pipe 41b to which the circulation pipe 47 is connected. Valve 34h opens and closes the flow path of pipe 41b.

[0144] When sulfuric acid is supplied to nozzle 36, valve 34g is closed and valve 34h is opened. On the other hand, when sulfuric acid is returned to tank 51 (or tank 50), valve 34g is opened and valve 34h is closed.

[0145] In the sixth modified example, if sulfuric acid is not supplied to the nozzle 36, the sulfuric acid in tank 50 is returned to tank 50, for example, via piping 41a, the second piping 42 (or heating region R1), piping 41b, circulation piping 47, tank 51, and the fourth piping 44. In other words, piping 41a, the second piping 42 (or heating region R1), piping 41b, circulation piping 47, tank 51, and the fourth piping 44 constitute a circulation path for circulating the sulfuric acid in tank 50. This makes it possible to maintain the temperature of the sulfuric acid inside piping 41a, the second piping 42, and piping 41b at a predetermined temperature.

[0146] In the sixth modification, an example was shown in which the tank 50 is heated by the heater 62 to circulate sulfuric acid at a predetermined temperature, but the present invention is not limited to this. For example, the pipe 41a may be heated by the heater 62 to circulate sulfuric acid at a predetermined temperature.

[0147] The other structures and effects of the sixth modified example are the same as those of the second embodiment. Furthermore, the substrate processing method for the sixth modified example is the same as that of the second modified example.

[0148] (Third embodiment) Next, a substrate processing apparatus 100 according to a third embodiment of the present invention will be described with reference to Figures 14, 15, and 16. In the third embodiment, unlike the first and second embodiments, an example will be described in which a relatively low-temperature hydrogen peroxide aqueous solution is obtained using sulfuric acid that has passed through the first pathway C1. Figure 14 is a schematic diagram of the substrate processing unit 10 in the substrate processing apparatus 100 of the third embodiment. The differences from the first embodiment will be mainly described below.

[0149] As shown in Figure 14, the substrate processing apparatus 100 includes a shielding member 90. The shielding member 90 is housed in the chamber 12. The shielding member 90 shields the substrate W held in the substrate holding section 20 from the vertically upward side.

[0150] The shielding member 90 is positioned above the substrate holding portion 20. The shielding member 90 faces the substrate W. The outer diameter of the shielding member 90 is approximately equal to, or slightly larger than, the outer diameter of the substrate W. The shielding member 90 also moves relative to the substrate W between a proximity position and a retracted position. The substrate processing apparatus 100 is equipped with a movement mechanism (not shown) for moving the shielding member 90 between the proximity position and the retracted position. When the shielding member 90 is in the proximity position, it descends and approaches the upper surface Wa of the substrate W at a predetermined distance. In the proximity position, the shielding member 90 covers the upper surface Wa of the substrate W, shielding the upper part of the substrate W. When the shielding member 90 is in the retracted position, it is located further vertically upward than the proximity position. When the shielding member 90 changes from the proximity position to the retracted position, it rises and moves away from the substrate W.

[0151] The shielding member 90 catches any liquid splashing from the substrate W when the processing liquid is discharged from the nozzle 36 onto the substrate W. This prevents the processing liquid from splashing around the substrate holding part 20 and other surrounding parts.

[0152] The substrate processing apparatus 100 further comprises a fluid supply unit 130. The fluid supply unit 130 comprises a pipe 140, a valve 134, and a nozzle 136. The nozzle 136 is positioned on the shielding member 90. The nozzle 136 discharges fluid onto the upper surface Wa of the substrate W. The fluid includes a processing liquid or a gas. The processing liquid is not particularly limited, but may include, for example, a rinsing liquid or IPA. The gas is not particularly limited, but may include, for example, nitrogen gas or clean air.

[0153] Furthermore, the nozzle 136 may, for example, discharge fluid to the central part of the substrate W, or to the region between the central part and the peripheral part of the substrate W. The nozzle 136 has an outlet (not shown) and discharges fluid from the outlet. The number of outlets is not particularly limited and may be one or two or more. In this embodiment, multiple outlets are arranged. The nozzle 136 is connected to the piping 140. Fluid is supplied to the piping 140 from a supply source. The valve 134 opens and closes the flow path in the piping 140.

[0154] Valve 134 adjusts the flow rate of fluid supplied to pipe 140 by adjusting the opening degree of pipe 140. Specifically, valve 134 includes a valve body (not shown) with a valve seat inside, a valve element that opens and closes the valve seat, and an actuator (not shown) that moves the valve element between an open position and a closed position.

[0155] Next, with reference to Figure 15, the processing liquid supply unit 30 of the substrate processing apparatus 100 of this embodiment will be described. Figure 15 is a schematic plan view of the substrate processing apparatus 100 of this embodiment.

[0156] As shown in Figure 15, in the third embodiment, similar to the first embodiment, the processing liquid supply unit 30 includes a tank 50, a path 70, a hydrogen peroxide water supply path C3, and a heater 61. Path 70 includes a first path C1. In this embodiment, unlike the first embodiment, path 70 does not include a second path C2. Tank 50 stores sulfuric acid. Note that tank 50 is an example of the "first tank" of the present invention. Also, heater 61 is an example of the "first heater" of the present invention.

[0157] The heater 61 is capable of heating the heating region R1 of the first path C1. In this embodiment, the heater 61 is switched on and off by the control unit 102. That is, the heater 61 can be switched between a heating state in which the heating region R1 is heated and a non-heating state in which the heating region R1 is not heated.

[0158] When heater 61 heats heating region R1, the temperature of sulfuric acid passing through heating region R1 rises. For example, the temperature of sulfuric acid that has passed through heating region R1 and been heated in heating region R1 becomes the first temperature. The first temperature is, for example, 170°C to 190°C or higher.

[0159] On the other hand, if heater 61 does not heat heating region R1, the temperature of the sulfuric acid passing through heating region R1 does not rise. If heater 61 does not heat heating region R1, the sulfuric acid that has passed through heating region R1 has a second temperature. The second temperature is, for example, room temperature to 150°C. In other words, the sulfuric acid that is not heated in heating region R1 has a lower temperature than the sulfuric acid that is heated in heating region R1 when passing through it. Hereinafter, sulfuric acid heated in heating region R1 may be referred to as relatively high-temperature sulfuric acid, and sulfuric acid that is not heated in heating region R1 may be referred to as relatively low-temperature sulfuric acid.

[0160] The processing liquid supply unit 30 includes a first pipe 41 and a third pipe 43 as piping 40. In this embodiment, unlike the first embodiment, the processing liquid supply unit 30 does not include a second pipe 42.

[0161] Furthermore, the processing liquid supply unit 30 includes a first valve 34a and a superhydrogen valve 34c, which function as valves 34. In this embodiment, unlike the first embodiment, the processing liquid supply unit 30 does not include a second valve 34b.

[0162] In this embodiment, the relatively high-temperature sulfuric acid and hydrogen peroxide solution heated in the heating region R1 react with each other to form a high-temperature (e.g., 200°C or higher) hydrogen peroxide solution mixture.

[0163] On the other hand, the relatively low-temperature sulfuric acid that was not heated in heating region R1 merges with the hydrogen peroxide solution at a lower temperature than the heated, relatively high-temperature sulfuric acid. Therefore, the relatively low-temperature sulfuric acid and the hydrogen peroxide solution react with each other, but form a relatively low-temperature hydrogen peroxide solution mixture. The flow rate (amount flowing per unit time) of the relatively low-temperature sulfuric acid is not particularly limited, but in this embodiment, it is approximately the same as the flow rate of the relatively high-temperature sulfuric acid.

[0164] The control unit 102 sets the heater 61 to a first output, thereby making the sulfuric acid passing through the first pathway C1 relatively hot. Relatively hot sulfuric acid has a first temperature. The first temperature is, for example, 170°C to 190°C or higher. The control unit 102 also sets the heater 61 to a second output, which is lower than the first output, thereby making the sulfuric acid passing through the first pathway C1 relatively cold. Relatively cold sulfuric acid has a second temperature, which is lower than the first temperature. The second temperature is, for example, room temperature to 150°C.

[0165] In this embodiment, the control unit 102 turns on the heater 61 to make the sulfuric acid passing through the first pathway C1 sulfuric acid having a first temperature. The control unit 102 also turns off the heater 61 to make the sulfuric acid passing through the first pathway C1 sulfuric acid having a second temperature.

[0166] In this embodiment, the control unit 102 controls the heater 61 so that after a mixture of relatively high-temperature sulfuric acid and hydrogen peroxide is discharged from the nozzle 36 onto the substrate W, a mixture of relatively low-temperature sulfuric acid and hydrogen peroxide is discharged from the nozzle 36 onto the substrate W. Therefore, when the supply of sulfuric acid is stopped in order to wash away the sulfuric acid-hydrogen peroxide mixture on the substrate W with hydrogen peroxide, it is possible to suppress the high temperature of the sulfuric acid-hydrogen peroxide mixture from becoming even hotter, and to suppress a rapid change in the temperature of the substrate W. Thus, it is possible to suppress damage to the substrate W, such as pattern peeling.

[0167] Furthermore, in this embodiment, as in the first embodiment, there is no need to adjust the mixing ratio of sulfuric acid and hydrogen peroxide solution to a desired ratio in order to suppress damage to the substrate W, thus reducing the time compared to methods that adjust the mixing ratio to a desired ratio.

[0168] Furthermore, unlike the first embodiment, this embodiment does not require the provision of a second path C2 and a second valve 34b, thus simplifying the configuration of the substrate processing apparatus 100.

[0169] Other structural features of the third embodiment are the same as those of the first embodiment.

[0170] Next, the substrate processing method of the substrate processing apparatus 100 of this embodiment will be described with reference to Figures 15 and 16. Figure 16 is a flowchart of the substrate processing method of the substrate processing apparatus 100 of this embodiment. Steps S301 to S311 of this embodiment correspond to steps S101 to S111 of the first embodiment. Step S301 is an example of the "first distribution process" of the present invention. Step S303 is an example of the "first discharge process" of the present invention. Step S305 is an example of the "second distribution process" of the present invention. Step S307 is an example of the "second discharge process" of the present invention. In this embodiment, the differences from the first embodiment will be mainly described.

[0171] As shown in Figure 16, in step S301, the control unit 102 combines the relatively hot sulfuric acid that has passed through the heating region R1 with hydrogen peroxide solution. At this time, the heater 61 is turned on, and the sulfuric acid from the tank 50 is heated in the heating region R1 to become relatively hot sulfuric acid.

[0172] Next, in step S303, relatively high-temperature sulfuric acid and hydrogen peroxide solution are discharged onto the substrate W.

[0173] Next, in step S305, the control unit 102 combines the relatively low-temperature sulfuric acid with the hydrogen peroxide solution. Specifically, the control unit 102 turns off the heater 61. This switches the heater 61 from the ON state to the OFF state. As a result, the sulfuric acid passing through the first path C1 is not heated in the heating region R1, and therefore, relatively low-temperature sulfuric acid is supplied toward the nozzle 36.

[0174] Next, in step S307, relatively low-temperature sulfuric acid and hydrogen peroxide solution are dispensed onto the substrate W.

[0175] Next, in step S309, the control unit 102 stops supplying sulfuric acid.

[0176] Next, in step S311, the control unit 102 stops the supply of hydrogen peroxide solution.

[0177] This concludes the substrate processing method of this embodiment.

[0178] In the third embodiment, a mixture of relatively high-temperature sulfuric acid and hydrogen peroxide is discharged onto the substrate W, and then the output of the heater 61 is switched to discharge a mixture of relatively low-temperature sulfuric acid and hydrogen peroxide onto the substrate W. Therefore, simply by switching the output of the heater 61, damage such as pattern peeling on the substrate W can be suppressed.

[0179] In addition, during the substrate processing described above, a rinse liquid may be discharged from the nozzle 136 located on the shielding member 90. In this case, the rinse liquid may be discharged from the nozzle 136 onto the substrate W after step S311.

[0180] Furthermore, in the substrate processing described above, nitrogen gas may be discharged from the nozzle 136 located on the shielding member 90. For example, nitrogen gas may be discharged from the nozzle 136 while steps S303 to S309 are being executed. In this case, a downward airflow is generated above the substrate W, which suppresses splashing and scattering of the processing liquid discharged from the nozzle 36 onto the substrate W.

[0181] Other substrate processing methods and other effects of the third embodiment are the same as those of the first embodiment.

[0182] (Seventh variation) Next, with reference to Figure 17, a seventh modified example of the substrate processing apparatus 100 of the present invention will be described. In the seventh modified example, unlike the third embodiment described using Figures 15 and 16, an example in which the processing liquid supply unit 30 includes a heater 62 will be described. Figure 17 is a schematic diagram of the processing liquid supply unit 30 of the seventh modified example of the substrate processing apparatus 100.

[0183] As shown in Figure 17, in the seventh modification, the processing liquid supply unit 30 further includes a heater 62 as the heater 60 described above. Note that heater 62 is an example of the "second heater" of the present invention. Heater 62 is a heater for maintaining the sulfuric acid in the tank 50 at a predetermined temperature. In the seventh modification, heater 62 maintains the sulfuric acid in the tank 50 at a predetermined temperature by heating the tank 50. For example, the sulfuric acid in the tank 50 is maintained at 150°C or higher. Note that heater 62 does not necessarily have to heat the tank 50. For example, a circulation pipe for circulating sulfuric acid may be connected to the tank 50, and the circulation pipe may be heated by heater 62.

[0184] In the seventh modified example, by providing a heater 62 that maintains the sulfuric acid in the tank 50 at a predetermined temperature, the sulfuric acid passing through the heating region R1 can be easily heated to a desired temperature (for example, 170°C to 190°C or higher).

[0185] Other structures, other effects, and substrate processing methods of the seventh modified example are the same as those of the third embodiment.

[0186] (Variation 8) Next, with reference to Figure 18, the eighth modified substrate processing apparatus 100 of the present invention will be described. In the eighth modified example, unlike the third embodiment described using Figure 15, the third pipe 43 is connected to the first pipe 41. Figure 18 is a schematic diagram of the processing liquid supply unit 30 of the eighth modified substrate processing apparatus 100.

[0187] As shown in Figure 18, in the eighth modified example, the first path C1 and the hydrogen peroxide supply path C3 merge between the nozzle 36 and the heating region R1.

[0188] Specifically, the third pipe 43 is connected to pipe 41b of the first pipe 41. The third pipe 43 and a portion of pipe 41b then constitute the hydrogen peroxide water supply route C3. Furthermore, the portion of pipe 41b downstream of the first junction P1 (towards the nozzle 36) is a common pipe for the first route C1 and the hydrogen peroxide water supply route C3.

[0189] In the eighth modified example, by connecting the third pipe 43 to the first pipe 41, a portion of the first pipe 41 can be made into a common pipe, thus further suppressing the enlargement of the processing liquid supply unit 30. In addition, compared to the case where sulfuric acid and hydrogen peroxide are combined in the nozzle 36, the time from combination to discharge is longer, so the sulfuric acid and hydrogen peroxide can be mixed more uniformly.

[0190] Other structures, other effects, and substrate processing methods of the eighth modified example are the same as those of the third embodiment.

[0191] (Fourth Embodiment) Next, a substrate processing apparatus 100 according to a fourth embodiment of the present invention will be described with reference to Figures 19 and 20. In the fourth embodiment, unlike the third embodiment described with reference to Figures 15 and 16, an example will be described in which the processing liquid supply unit 30 has tanks 50 and 51. Figure 19 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of this embodiment. The differences from the third embodiment will be mainly described below.

[0192] As shown in Figure 19, in the fourth embodiment, the processing liquid supply unit 30 includes a tank 50, a tank 51, a path 70, a hydrogen peroxide water supply path C3, and heaters 61, 62, and 63. Tanks 50 and 51 store sulfuric acid. Path 70 includes the first path C1. In the fourth embodiment, unlike the second embodiment, path 70 does not include the second path C2.

[0193] In this embodiment, tank 51 is an example of the "first tank" of the present invention. Tank 50 is an example of the "second tank" of the present invention. Heater 63 is an example of the "second heater" of the present invention. Heater 62 is an example of the "third heater" of the present invention.

[0194] In this embodiment, the first path C1 is a path for supplying sulfuric acid from the tank 51 to the nozzle 36.

[0195] Specifically, the processing liquid supply unit 30 includes the first pipe 41, third pipe 43, and fourth pipe 44 as the piping 40 described above. The fourth pipe 44 connects tank 50 and tank 51. In this embodiment, the first route C1 is composed of the fourth pipe 44, tank 50, and first pipe 41.

[0196] The processing liquid supply unit 30 further includes a fourth valve 34d, which functions as a valve 34. The fourth valve 34d is located in the fourth pipe 44. The fourth valve 34d opens and closes the flow path of the fourth pipe 44. When the amount of sulfuric acid in the tank 50 falls below a predetermined amount, the control unit 102 switches the fourth valve 34d from a closed state to an open state. This supplies sulfuric acid from tank 51 to tank 50.

[0197] The processing liquid supply unit 30 includes heaters 61, 62, and 63 as heaters 60. Heater 62 is a heater for maintaining the sulfuric acid in the tank 50 at a predetermined temperature, similar to the seventh modification. Since heater 62 is the same as in the seventh modification, its description is omitted.

[0198] Heater 63 is a heater for maintaining the sulfuric acid in tank 51 at a predetermined temperature. In this embodiment, heater 63 maintains the sulfuric acid in tank 51 at a predetermined temperature by heating tank 51. The sulfuric acid in tank 51 is maintained at a lower temperature than the sulfuric acid in tank 50. For example, the sulfuric acid in tank 51 is maintained at, for example, 120°C or higher and less than 150°C. Note that heater 62 does not necessarily have to heat tank 51. For example, a circulation pipe for circulating sulfuric acid may be connected to tank 51, and the circulation pipe may be heated by heater 63.

[0199] Furthermore, in this embodiment, the processing liquid supply unit 30 includes a return pipe 45 and a valve 34e. The return pipe 45 is connected to pipe 41b of the first pipe 41. The valve 34e is located in the return pipe 45. The valve 34e opens and closes the flow path of the return pipe 45.

[0200] The other configurations of the fourth embodiment are the same as those of the third embodiment.

[0201] Next, the substrate processing method of the substrate processing apparatus 100 of this embodiment will be described with reference to Figures 19 and 20. Figure 20 is a flowchart of the substrate processing method of the substrate processing apparatus 100 of this embodiment. Steps S401 to S411 of this embodiment correspond to steps S301 to S311 of the third embodiment. Step S401 is an example of the "first distribution process" of the present invention. Step S403 is an example of the "first discharge process" of the present invention. Step S405 is an example of the "second distribution process" of the present invention. Step S407 is an example of the "second discharge process" of the present invention. In this embodiment, the differences from the third embodiment will be mainly described.

[0202] As shown in Figure 20, in step S401, the control unit 102 combines the relatively hot sulfuric acid that has passed through the heating region R1 with hydrogen peroxide solution. At this time, heaters 61, 62, and 63 are turned on, and the sulfuric acid from tank 50 is heated in the heating region R1 to become relatively hot sulfuric acid.

[0203] Next, in step S403, relatively high-temperature sulfuric acid and hydrogen peroxide solution are discharged onto the substrate W.

[0204] Next, in step S405, the control unit 102 combines relatively low-temperature sulfuric acid with hydrogen peroxide solution.

[0205] Next, in step S407, relatively low-temperature sulfuric acid and hydrogen peroxide solution are dispensed onto the substrate W.

[0206] Next, in step S409, the control unit 102 stops supplying sulfuric acid.

[0207] Next, in step S411, the control unit 102 stops the supply of hydrogen peroxide solution.

[0208] Next, in step S413, the control unit 102 opens valve 34e to prevent the processing liquid from dripping from nozzle 36. Specifically, the control unit 102 switches valve 34e from the closed state to the open state. As a result, the processing liquid remaining between the return pipe 45 and the discharge port 36a of nozzle 36 is drawn into the return pipe 45 by the siphon principle. Therefore, the processing liquid can be prevented from dripping from the discharge port 36a of nozzle 36. After that, the control unit 102 closes valve 34e.

[0209] This concludes the substrate processing method of this embodiment.

[0210] Other effects of the fourth embodiment and other substrate processing methods are the same as those of the third embodiment.

[0211] (9th variation) Next, with reference to Figure 21, a substrate processing apparatus 100 of the ninth modified example of the present invention will be described. In the ninth modified example, unlike the third and fourth embodiments, an example in which a circulation pipe 47 for circulating sulfuric acid is provided will be described. Figure 21 is a schematic diagram of the processing liquid supply unit 30 of the substrate processing apparatus 100 of the ninth modified example.

[0212] As shown in Figure 21, in the ninth modified example, the processing liquid supply unit 30 has a branching section P4 and a circulation pipe 47. The branching section P4 is the part where the first path C1 and the circulation pipe 47 branch off. In the ninth modified example, the branching section P4 is located in pipe 41b. In other words, in the ninth modified example, the circulation pipe 47 is connected to pipe 41b. The circulation pipe 47 connects, for example, pipe 41b to tank 51. The circulation pipe 47 returns the sulfuric acid passing through pipe 41b to tank 51. Alternatively, the circulation pipe 47 may connect pipe 41b to tank 50 and return the sulfuric acid to tank 50.

[0213] Furthermore, in the ninth modified example, the heater 61 is positioned upstream of the branching point P4 in the first path C1 in the direction of sulfuric acid flow. Therefore, the sulfuric acid passing through the circulation path can be heated by the heater 61.

[0214] The processing liquid supply unit 30 includes valves 34g and 34h. Valve 34g is located in the circulation piping 47. Valve 34g opens and closes the flow path of the circulation piping 47. Valve 34h is located downstream of the branching section P4 in the piping 41b. Valve 34h opens and closes the flow path of the piping 41b.

[0215] When sulfuric acid is supplied to nozzle 36, valve 34g is closed and valve 34h is opened. On the other hand, when sulfuric acid is returned to tank 51 (or tank 50), valve 34g is opened and valve 34h is closed.

[0216] In the ninth modified example, if sulfuric acid is not supplied to the nozzle 36, the sulfuric acid in the tank 50 is returned to the tank 50, for example, via piping 41a, heating region R1, piping 41b, circulation piping 47, tank 51, and fourth piping 44. In other words, piping 41a, heating region R1, piping 41b, circulation piping 47, tank 51, and fourth piping 44 constitute a circulation path for circulating the sulfuric acid in the tank 50. This makes it possible to maintain the temperature of the sulfuric acid inside piping 41a and piping 41b, etc., at a predetermined temperature.

[0217] In the ninth modification, an example was shown in which the tank 50 is heated by the heater 62 to circulate sulfuric acid at a predetermined temperature, but the present invention is not limited to this. For example, the pipe 41a may be heated by the heater 62 to circulate sulfuric acid at a predetermined temperature.

[0218] The other structures and effects of the ninth modified example are the same as those of the fourth embodiment. Furthermore, the substrate processing method for the ninth modified example is the same as that of the third embodiment.

[0219] (10th variation) Next, with reference to Figure 22, a substrate processing apparatus 100 of the tenth modified example of the present invention will be described. In the tenth modified example, unlike the ninth modified example, an example in which the heater 61 is located downstream of the branching section P4 will be described. Figure 22 is a schematic diagram of the processing liquid supply section 30 of the substrate processing apparatus 100 of the tenth modified example.

[0220] As shown in Figure 22, in the 10th modified example, the processing liquid supply unit 30 has a branching section P4 and a circulation pipe 47, similar to the 9th modified example. The branching section P4 is the part where the first path C1 and the circulation pipe 47 branch off. In the 10th modified example, the branching section P4 is located in pipe 41a. In other words, the circulation pipe 47 is connected to pipe 41a.

[0221] In the tenth modified example, the heater 61 is positioned downstream of the branching point P4 in the first path C1 in the direction of sulfuric acid flow. In other words, the heater 61 is positioned between the circulation path and the nozzle 36.

[0222] In the tenth modified example, as described above, the heater 61 is positioned downstream of the branch P4 in the first piping 41. Therefore, the heater 61 can be positioned close to the nozzle 36. Thus, it is possible to suppress the decrease in the temperature of the sulfuric acid before it reaches the nozzle 36 after being heated by the heater 61.

[0223] Other structures, effects, and substrate processing methods of the 10th modified example are the same as those of the 9th modified example.

[0224] Embodiments of the present invention have been described above with reference to the drawings. However, the present invention is not limited to the embodiments described above, and can be implemented in various forms without departing from its spirit. Furthermore, the multiple components disclosed in the above embodiments can be modified as appropriate. For example, some components from all the components shown in one embodiment may be added to the components of another embodiment, or some components from all the components shown in one embodiment may be deleted from the embodiment.

[0225] Furthermore, the drawings schematically show each component in order to facilitate understanding of the invention, and the thickness, length, number, spacing, etc. of each component shown may differ from the actual dimensions due to the convenience of drawing creation. Also, the configuration of each component shown in the above embodiments is merely an example and is not particularly limiting, and it goes without saying that various modifications are possible without substantially departing from the effects of the present invention.

[0226] For example, in the fourth modified example shown in Figure 9, an example is shown in which the first path C1 and the hydrogen peroxide supply path C3 merge between the nozzle 36 and the heating region R1, but the present invention is not limited thereto. In the first embodiment, the first to third modified examples, the second embodiment, the fifth modified example, the sixth modified example, the third embodiment, the seventh modified example, the fourth embodiment, the ninth modified example, and the tenth modified example, the first path C1 and the hydrogen peroxide supply path C3 may also merge between the nozzle 36 and the heating region R1.

[0227] Furthermore, while the second embodiment shown in Figures 10 and 11 illustrates an example in which return pipes 45 and 46 are provided to suppress the dripping of the processing liquid from the nozzle 36, the present invention is not limited thereto. In the first embodiment, the first to fourth modifications, the sixth modification, the third embodiment, the seventh modification, the eighth modification, the ninth modification, and the tenth modification, the return pipe 45 may also be provided. In addition, in the second embodiment, the return pipes 45 and 46 may not be provided.

[0228] Furthermore, although an example of providing a circulation pipe 47 is shown in the sixth modified example shown in Figure 13, the present invention is not limited thereto. In the first embodiment, the first to fourth modified examples, the second embodiment, the fifth modified example, the third embodiment, the seventh modified example, the eighth modified example, and the fourth embodiment, a circulation pipe 47 for circulating sulfuric acid may also be provided.

[0229] Furthermore, while the second embodiment shown in Figures 10 and 11 illustrates an example where sulfuric acid is supplied directly to the nozzle 36 from the upstream tank (tank 51) when there are two tanks, the present invention is not limited thereto. In the case of two tanks, sulfuric acid may also be supplied directly to the nozzle 36 from the downstream tank (tank 50).

[0230] Furthermore, although an example of providing a heater 61 is shown in the second embodiment shown in Figures 10 and 11, the present invention is not limited to this. For example, in the second embodiment, the heater 61 may not be provided. In this case, the heater 62 corresponds to the "first heater" of the present invention. Also, for example, the tank 50 corresponds to the "heating region" of the present invention.

[0231] Furthermore, although an example has been described in the third embodiment shown in Figures 14 to 16 in which the substrate processing apparatus 100 is equipped with a shielding member 90, the present invention is not limited thereto. In the first embodiment, the first to fourth modifications, the second embodiment, the fifth modification, and the sixth modification, the substrate processing apparatus 100 may also be equipped with a shielding member 90, and may further be equipped with a fluid supply unit 130.

[0232] Furthermore, in the third embodiment shown in Figures 14 to 16, an example was described in which the heater 61 is turned off when mixing relatively low-temperature sulfuric acid and hydrogen peroxide solution in step S305 (second flow process), but the present invention is not limited to this. The heater 61 may be turned on if the temperature of the sulfuric acid becomes lower than in step S301 (first flow process).

[0233] Furthermore, although the above embodiment shows an example in which relatively high-temperature sulfuric acid, relatively low-temperature sulfuric acid, and hydrogen peroxide solution are supplied to the substrate W from a single nozzle 36, the present invention is not limited thereto. For example, relatively high-temperature sulfuric acid, relatively low-temperature sulfuric acid, and hydrogen peroxide solution may be supplied to the substrate W from two or three nozzles. In other words, for example, relatively high-temperature sulfuric acid and hydrogen peroxide solution may be combined on the substrate W, or relatively low-temperature sulfuric acid and hydrogen peroxide solution may be combined on the substrate W. [Industrial applicability]

[0234] The present invention is applicable to the field of substrate processing apparatus and substrate processing methods. [Explanation of Symbols]

[0235] 34a: First valve 34b: Second valve 34c: Superwater valve 36: Nozzle 36a:Discharge port 50: Tanks (Tank 1, Tank 2) 51: Tank (Tank 1) 61: Heater (1st Heater) 62: Heater (2nd heater, 3rd heater) 63: Heater (Second Heater) 70: Route 100: Substrate processing equipment 102: Control Unit C1: First route C2: Second route C3: Hydrogen peroxide supply route P1: First junction P2: 2nd confluence section P4: Branching point R1: Heating area S301, S401: Step (First Distribution Process) S103, S203, S303, S403: Step (First discharge process) S305, S405: Step (Second Distribution Process) S107, S207, S307, S407: Step (Second discharge process) W: Circuit board

Claims

1. A substrate processing apparatus for processing a substrate by supplying a processing liquid to the substrate from a nozzle, The first tank for storing sulfuric acid, A path including a first path for supplying the sulfuric acid from the first tank to the nozzle, A first valve inserted into the first path, A first heater that heats the heating region of the first path, A hydrogen peroxide water supply path for supplying hydrogen peroxide water to the nozzle, A hydrogen peroxide valve inserted into the hydrogen peroxide water supply path, A control unit controls the supply of sulfuric acid and hydrogen peroxide solution to the nozzle by controlling the opening and closing of the first valve and the peroxide valve. Equipped with, The control unit, After mixing the sulfuric acid heated in the first heater with the hydrogen peroxide solution and discharging it from the nozzle onto the substrate, A mixture of sulfuric acid at a lower temperature than the heated sulfuric acid and the hydrogen peroxide solution is discharged from the nozzle onto the substrate. The aforementioned path further includes a second path that supplies the sulfuric acid from the first tank to the nozzle without passing through the heating region. The substrate processing apparatus further comprises a second valve inserted into the second path, The control unit controls the supply of sulfuric acid and hydrogen peroxide solution to the nozzle by controlling the opening and closing of the first valve, the second valve and the peroxide valve. The sulfuric acid passing through the second pathway merges with the hydrogen peroxide solution at a lower temperature than the sulfuric acid passing through the first pathway. The control unit, After passing through the first path and being heated by the first heater, the sulfuric acid and hydrogen peroxide solution are mixed and discharged from the nozzle onto the substrate, A substrate processing apparatus that controls the first valve, the second valve, and the hydrogen peroxide valve so that the sulfuric acid passing through the second pathway is mixed and discharged from the nozzle onto the substrate.

2. A first junction is located between the heating region and the nozzle outlet, where the first path and the hydrogen peroxide water supply path merge. A second merging section is located between the heating region and the first merging section, where the first path and the second path merge. The substrate processing apparatus according to claim 1, further comprising:

3. The substrate processing apparatus according to claim 1, wherein the first path and the second path branch off upstream of the sulfuric acid flow direction relative to the heating region and merge downstream of the sulfuric acid flow direction relative to the heating region.

4. The substrate processing apparatus according to any one of claims 1 to 3, further comprising a second heater for maintaining the sulfuric acid in the first tank at a predetermined temperature.

5. A second tank is positioned downstream of the first tank in the flow direction of the sulfuric acid, A third heater for maintaining the sulfuric acid in the second tank at a higher temperature than the sulfuric acid in the first tank, The substrate processing apparatus according to claim 4, further comprising:

6. A substrate processing method comprising supplying a processing solution to the substrate to process the substrate, A first discharge step involves discharging sulfuric acid, which is supplied from a first tank and passes through a first path having a heating region, and hydrogen peroxide, which has passed through a hydrogen peroxide supply path, onto the substrate. After the first discharge step, a second discharge step is performed in which sulfuric acid supplied from the first tank at a lower temperature than the heated sulfuric acid, and hydrogen peroxide that has passed through the hydrogen peroxide supply path are discharged onto the substrate. Includes, A substrate processing method comprising the following steps: in the second discharge step, sulfuric acid that has passed through a second path that does not involve the heating region, and hydrogen peroxide solution are discharged onto the substrate.

7. The substrate processing method according to claim 6, wherein the first path and the second path branch off upstream of the sulfuric acid flow direction relative to the heating region and merge downstream of the sulfuric acid flow direction relative to the heating region.

8. The substrate processing method according to claim 6 or claim 7, wherein the sulfuric acid in the first tank is maintained at a predetermined temperature.

9. The substrate processing method according to claim 8, wherein the sulfuric acid in the second tank, which is located downstream of the first tank in the flow direction of the sulfuric acid, is maintained at a temperature higher than the temperature of the sulfuric acid in the first tank.

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