Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method and a substrate processing apparatus capable of quickly and sufficiently removing an organic film such as a resist from a substrate.SOLUTION: A liquid film 100 of a sulfuric acid-containing liquid is formed on the upper surface of a substrate W (liquid film forming step). A process chamber 12 capable of accommodating the substrate W is filled with ozone-containing gas, and the liquid film 100 is exposed to the ozone-containing gas (ozone-containing gas exposure step). The substrate W is placed in the process chamber 12 filled with ozone-containing gas, and the substrate W is heated in a state where the liquid film 100 is formed on the upper surface of the substrate W (substrate heating step).SELECTED DRAWING: Figure 6D

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method for processing a substrate, and a substrate processing apparatus for processing a substrate.

[0002] Substrates to be processed include, for example, semiconductor wafers, substrates for FPDs (Flat Panel Displays) such as liquid crystal displays and organic EL (Electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells. [Background technology]

[0003] In the substrate processing apparatus disclosed in Patent Document 1 below, ozone gas is supplied to sulfuric acid in a pipe, and ozone is dissolved in the sulfuric acid to form sulfuric acid ozone. By mixing sulfuric acid and ozone, peroxodisulfuric acid (SO2O8) is generated as an active species (etchant). 2- ) is generated.

[0004] In the substrate processing apparatus of Patent Document 1, sulfuric acid ozone flows through a sulfuric acid ozone supply pipe and flows into a water mixing section where it is mixed with water to form a sulfuric acid ozone / water mixture. The sulfuric acid ozone / water mixture is ejected from a sulfuric acid ozone / water nozzle toward the substrate, and the substrate is rotated while the sulfuric acid ozone / water mixture is supplied to the surface of the substrate, thereby removing the resist on the surface of the substrate. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-36101 Summary of the Invention [Problem to be solved by the invention]

[0006] In the substrate processing apparatus disclosed in Patent Document 1, the temperature of the sulfuric acid ozone / water mixture becomes higher than the temperature of the sulfuric acid ozone before mixing due to the heat of dilution generated by mixing sulfuric acid ozone with water. Therefore, even if a relatively low temperature of sulfuric acid ozone is used as the sulfuric acid ozone before mixing, the sulfuric acid ozone / water mixture can be supplied to the surface of the substrate at a temperature required for resist removal. Furthermore, by keeping the sulfuric acid ozone before mixing at a relatively low temperature, a large amount of ozone gas can be dissolved in the sulfuric acid ozone before mixing.

[0007] However, in the device of Patent Document 1, the concentration of peroxodisulfuric acid, which has oxidizing power, decreases when sulfuric acid ozone is mixed with water, which may result in insufficient oxidizing power being obtained.

[0008] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a substrate processing method and a substrate processing apparatus that can quickly and thoroughly remove an organic film such as a resist from a substrate. [Means for solving the problem]

[0009] One embodiment of the present invention provides a substrate processing method including: a liquid film forming step of forming a liquid film of a sulfuric acid-containing liquid on a main surface of a substrate; an ozone-containing gas exposure step of filling an ozone-containing gas into a processing chamber capable of accommodating the substrate and exposing the liquid film to the ozone-containing gas; and a substrate heating step of heating the substrate while the substrate is placed in the processing chamber filled with the ozone-containing gas and the liquid film is formed on the main surface of the substrate.

[0010] According to this method, the processing chamber is filled with an ozone-containing gas, and the liquid film of the sulfuric acid-containing liquid on the main surface of the substrate is exposed to the ozone-containing gas, whereby ozone in the ozone-containing gas is dissolved in the sulfuric acid-containing liquid that constitutes the liquid film on the main surface of the substrate, thereby forming peroxodisulfuric acid in the liquid film.

[0011] Furthermore, the substrate is heated in a state in which a liquid film is formed on the main surface of the substrate. That is, the substrate is heated in a state in which peroxodisulfuric acid is formed in the sulfuric acid-containing liquid that constitutes the liquid film on the main surface of the substrate. Therefore, the oxidizing power of peroxodisulfuric acid can be increased.

[0012] Furthermore, since the substrate is heated in a state in which the processing chamber is filled with an ozone-containing gas, even if the solubility of ozone in the sulfuric acid-containing liquid decreases due to heating, the ozone-containing gas containing a sufficient concentration of ozone can be maintained in contact with the sulfuric acid-containing liquid, thereby suppressing gasification of ozone in the sulfuric acid-containing liquid.

[0013] As a result, the organic film such as resist can be removed from the substrate quickly and thoroughly.

[0014] The ozone-containing gas contains gaseous ozone (ozone gas), and the sulfuric acid-containing liquid contains sulfuric acid, such as an aqueous sulfuric acid solution.

[0015] In one embodiment of the present invention, heating of the substrate in the substrate heating step is started before the liquid film forming step and the ozone-containing gas exposure step.

[0016] According to this method, heating of the substrate is started before the formation of the liquid film of the sulfuric acid-containing liquid and the exposure of the liquid film to the ozone-containing gas, so that the substrate temperature can be quickly raised to a desired temperature even if the time required to increase the temperature of the substrate is longer than the time required to form the liquid film and the time required to fill the liquid film with the ozone-containing gas.

[0017] In one embodiment of the present invention, the ozone-containing gas exposure step includes a pressurizing supply step of supplying the ozone-containing gas into the processing chamber so that the pressure inside the processing chamber is higher than the pressure outside the processing chamber.

[0018] According to this method, the pressure inside the processing chamber can be made higher than the pressure outside the processing chamber by supplying an ozone-containing gas. According to Henry's law, the amount of gas dissolved in a liquid is proportional to the pressure of the gas in contact with the liquid. Therefore, by supplying an ozone-containing gas into the processing chamber and increasing the pressure of the ozone-containing gas in contact with the sulfuric acid-containing liquid on the main surface of the substrate, the concentration of ozone in the sulfuric acid-containing liquid can be increased. This increases the concentration of peroxodisulfuric acid in the liquid film, thereby enabling the organic film to be removed quickly and thoroughly from the main surface of the substrate.

[0019] In one embodiment of the present invention, the substrate processing method further includes, after the substrate heating step, a rinse liquid supplying step of supplying a rinse liquid to the main surface of the substrate.

[0020] According to this method, the liquid film of the sulfuric acid-containing liquid can be removed from the main surface of the substrate by the rinse liquid, thereby preventing sulfuric acid from remaining on the main surface of the substrate after the organic film has been removed from the main surface of the substrate.

[0021] In one embodiment of the present invention, the liquid film forming step includes a sulfuric acid-containing liquid supplying step of supplying a sulfuric acid-containing liquid toward the main surface of the substrate, and a thinning step of forming the liquid film by rotating the substrate around a central axis passing through a center of the substrate after stopping the supply of the sulfuric acid-containing liquid to the main surface of the substrate.

[0022] Therefore, compared to the case where the sulfuric acid-containing liquid is supplied in a continuous flow onto the main surface of the substrate and spread over the entire main surface of the substrate, the time for supplying the sulfuric acid-containing liquid onto the main surface of the substrate can be shortened, and the amount of sulfuric acid-containing liquid used can be reduced.

[0023] Furthermore, compared to the case where the sulfuric acid-containing liquid is spread over the entire main surface of the substrate while a continuous flow of the sulfuric acid-containing liquid is supplied to the main surface of the substrate, the liquid film of the sulfuric acid-containing liquid on the main surface of the substrate can be made thinner, which reduces the time required to heat the liquid film of the sulfuric acid-containing liquid and realizes power saving.

[0024] Peroxodisulfuric acid, generated from the surface of the liquid film of the sulfuric acid-containing liquid by the reaction between ozone dissolved in the sulfuric acid-containing liquid and sulfuric acid, diffuses through the liquid film and reaches the main surface of the substrate, where it reacts with the organic film on the main surface of the substrate. Therefore, by thinning the liquid film of the sulfuric acid-containing liquid, peroxodisulfuric acid can more easily reach the main surface of the substrate. Therefore, the organic film can be quickly and thoroughly removed from the main surface of the substrate.

[0025] In one embodiment of the present invention, the ozone-containing gas exposure process includes a process of filling the processing chamber with ozone-containing gas by starting the supply of ozone-containing gas into the processing chamber while the substrate having the liquid film formed on its main surface is placed in the processing chamber.

[0026] When a liquid film of the sulfuric acid-containing liquid is formed after the supply of the ozone-containing gas to the processing chamber is terminated, the ozone concentration in the atmosphere in the processing chamber may be reduced due to the outflow of the ozone-containing gas from the processing chamber to the outside. Therefore, the amount of ozone dissolved in the sulfuric acid-containing liquid in the liquid film may be reduced. Therefore, if the supply of the ozone-containing gas is started after the liquid film of the sulfuric acid-containing liquid has already been formed, the liquid film of the sulfuric acid-containing liquid can be brought into contact with the atmosphere in the processing chamber while the ozone concentration in the atmosphere in the processing chamber is sufficiently high. Therefore, the amount of ozone dissolved in the sulfuric acid-containing liquid in the liquid film on the main surface of the substrate can be increased.

[0027] In one embodiment of the present invention, the substrate processing method further includes a hydrophilization step of hydrophilizing the main surface of the substrate before the formation of the liquid film is started in the liquid film forming step.

[0028] According to this method, the main surface of the substrate is hydrophilized before a liquid film of the sulfuric acid-containing liquid is formed on the main surface of the substrate. This improves the wettability of the main surface of the substrate, making it easier for the sulfuric acid-containing liquid to spread over the main surface of the substrate. This allows for a thinner liquid film of the sulfuric acid-containing liquid. Furthermore, by thinning the liquid film, ozone can more easily reach the main surface of the substrate, allowing for rapid and thorough removal of the organic film from the main surface of the substrate.

[0029] In one embodiment of the present invention, the hydrophilization process includes an ozone hydrophilization process in which, before the formation of the liquid film in the liquid film formation process is initiated, an ozone-containing gas is supplied to the processing chamber while the substrate is placed in the processing chamber, thereby exposing the main surface of the substrate to an ozone-containing gas.

[0030] According to this method, the main surface of the substrate can be hydrophilized by supplying an ozone-containing gas. Therefore, the ozone-containing gas can be used for both hydrophilizing the main surface of the substrate and removing the organic film from the main surface of the substrate. Therefore, compared with the case where a method other than supplying an ozone-containing gas is used for hydrophilizing the main surface of the substrate, the equipment required for substrate processing can be simplified.

[0031] In one embodiment of the present invention, method The ozone-containing gas exposure process further includes a substrate holding step of holding the substrate on a substrate holding member disposed in the chamber, and a substrate accommodating step of accommodating the substrate held by the substrate holding member into the processing chamber by moving the processing chamber relative to the substrate held by the substrate holding member within the chamber, an ozone-containing gas supply step of supplying an ozone-containing gas into the processing chamber with the substrate accommodated in the processing chamber, and a substrate removing step of removing the substrate held by the substrate holding member from the processing chamber after the ozone-containing gas supply step by moving the processing chamber relative to the substrate held by the substrate holding member within the chamber.

[0032] According to this method, the ozone-containing gas can be supplied to a processing chamber disposed in the chamber with the substrate placed therein, thereby filling the processing chamber with the ozone-containing gas, which can be achieved more quickly than when the chamber is filled with the ozone-containing gas.

[0033] Another embodiment of the present invention includes a substrate holding member that holds a substrate in a predetermined processing posture, a processing chamber that can accommodate the substrate held by the substrate holding member, a substrate heating member that heats the substrate held by the substrate holding member, an ozone-containing gas supply member that supplies an ozone-containing gas into the processing chamber, a sulfuric acid-containing liquid discharge member that discharges a sulfuric acid-containing liquid toward a main surface of the substrate held by the substrate holding member, and a controller that controls the substrate heating member, the ozone-containing gas supply member, and the sulfuric acid-containing liquid discharge member.

[0034] Then, while the substrate held by the substrate holding member is placed in the processing chamber and the substrate is heated by the substrate heating member, the controller causes the sulfuric acid-containing liquid discharge member to discharge the sulfuric acid-containing liquid toward the main surface of the substrate, forming a liquid film of the sulfuric acid-containing liquid on the main surface of the substrate, and causes the ozone-containing gas supply member to supply the ozone-containing gas to the processing chamber.

[0035] According to this apparatus, while a substrate placed in a processing chamber is heated, a liquid film of a sulfuric acid-containing liquid is formed on the main surface of the substrate, and an ozone-containing gas is supplied to the processing chamber. Therefore, a liquid film of a sulfuric acid-containing liquid is formed on the main surface of the substrate while the processing chamber is filled with an ozone-containing gas. Therefore, ozone in the ozone-containing gas can be dissolved in the sulfuric acid-containing liquid that constitutes the liquid film on the main surface of the substrate, thereby forming peroxodisulfuric acid in the liquid film.

[0036] Furthermore, the substrate is heated in a state in which peroxodisulfuric acid is formed in the sulfuric acid-containing liquid that forms the liquid film on the main surface of the substrate, thereby increasing the oxidizing power of peroxodisulfuric acid.

[0037] Furthermore, since the substrate is heated in a state in which the processing chamber is filled with an ozone-containing gas, even if the solubility of ozone in the sulfuric acid-containing liquid decreases due to heating, the ozone-containing gas containing a sufficient concentration of ozone can be maintained in contact with the sulfuric acid-containing liquid, thereby suppressing gasification of ozone in the sulfuric acid-containing liquid.

[0038] As a result, the organic film such as resist can be removed from the substrate quickly and thoroughly.

[0039] In another embodiment of the present invention, the substrate processing apparatus further includes a temperature sensor for detecting the temperature of the substrate heating member, and the controller includes a temperature determination unit for determining whether the temperature detected by the temperature sensor is within a processing temperature range, and a first start unit for starting at least one of the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member and the supply of the ozone-containing gas from the ozone-containing gas supply member when the temperature determination unit determines that the temperature detected by the temperature sensor is within the processing temperature range.

[0040] According to this device, when the temperature detected by the temperature sensor reaches a temperature within the processing temperature range, at least one of the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member and the supply of the ozone-containing gas from the ozone-containing gas supply member is started. Therefore, in a state where the substrate is heated to a sufficiently high temperature, the discharge of the sulfuric acid-containing liquid is started. Out At least one of the discharge of the sulfuric acid-containing liquid from the member and the supply of the ozone-containing gas from the ozone-containing gas supply member is started, so that the removal of the organic film from the main surface of the substrate can be started quickly.

[0041] In another embodiment of the present invention, the first start unit starts the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member when the temperature determination unit determines that the temperature detected by the temperature sensor is within the processing temperature range. The controller further includes a time elapse determination unit that determines whether a liquid film formation time has elapsed after the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member has started, and a second start unit that starts the supply of the ozone-containing gas from the ozone-containing gas supply member when the time elapse determination unit determines that the liquid film formation time has elapsed.

[0042] According to this device, when the temperature detected by the temperature sensor falls within the processing temperature range, the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member is initiated. Therefore, the sulfuric acid-containing liquid supplied to the main surface of the substrate can be quickly heated. Furthermore, after the discharge of the sulfuric acid-containing liquid is initiated and the liquid film formation time has elapsed, the supply of the ozone-containing gas to the processing chamber is initiated. Therefore, after the liquid film is formed, the supply of the ozone-containing gas to the processing chamber is quickly initiated. Therefore, the substrate can be processed with high reproducibility, and the organic film can be removed from the main surface of the substrate with high reproducibility.

[0043] In another embodiment of the present invention, the substrate processing apparatus further includes a chamber that accommodates the substrate holding member and the processing chamber, and a processing chamber drive mechanism that moves the processing chamber relative to the substrate holding member so that the substrate held by the substrate holding member moves relatively between inside and outside the processing chamber.

[0044] According to this apparatus, with a substrate placed in a processing chamber housed in the chamber, an ozone-containing gas can be supplied to the processing chamber to fill it with the ozone-containing gas, which allows the processing chamber to be filled with the ozone-containing gas more quickly than when the chamber is filled with the ozone-containing gas.

[0045] In another embodiment of the present invention, the sulfuric acid-containing-liquid discharge member includes a sulfuric acid-containing-liquid nozzle that discharges the sulfuric acid-containing liquid, and the substrate processing apparatus further includes a nozzle drive mechanism that moves the sulfuric acid-containing-liquid nozzle to a processing position between the processing chamber and the main surface of the substrate when the substrate held by the substrate holding member is located outside the processing chamber.

[0046] According to this apparatus, when the substrate is located outside the processing chamber, the sulfuric acid-containing liquid is supplied from the sulfuric acid-containing liquid nozzle onto the main surface of the substrate to form a liquid film of the sulfuric acid-containing liquid on the main surface of the substrate, and then the substrate can be placed inside the processing chamber. Thus, in a configuration in which the sulfuric acid-containing liquid nozzle is provided separately from the processing chamber, the ozone-containing gas can be quickly supplied to the liquid film of the sulfuric acid-containing liquid on the main surface of the substrate.

[0047] In another embodiment of the present invention, the processing chamber includes a housing that defines an internal space of the processing chamber, and the ozone-containing gas supply member is exposed from the housing and has a plurality of ozone-containing gas outlet ports that are connected to the internal space, thereby enabling the ozone-containing gas to be quickly supplied to the entire interior of the processing chamber (internal space).

[0048] In another embodiment of the present invention, the substrate processing apparatus further includes a sulfuric acid-containing-liquid recovery unit that recovers the sulfuric acid-containing liquid discharged from the main surface of the substrate held by the substrate holding member, and a sulfuric acid-containing-liquid supply unit that supplies the sulfuric acid-containing liquid recovered by the sulfuric acid-containing-liquid recovery unit to the sulfuric acid-containing-liquid discharge member. With this configuration, the sulfuric acid-containing liquid supplied to the main surface of the substrate from the sulfuric acid-containing-liquid supply member can be recovered and reused, thereby reducing the amount of sulfuric acid waste. [Brief explanation of the drawings]

[0049] [Figure 1] FIG. 1 is a plan view illustrating an example of the configuration of a substrate processing apparatus according to a first embodiment of the present invention. [Figure 2] FIG. 2 is a schematic diagram for explaining the configuration of a processing unit provided in the substrate processing apparatus. [Figure 3] FIG. 3 is a schematic diagram for explaining the configuration of a sulfuric acid-containing liquid supply unit provided in the substrate processing apparatus. [Figure 4] FIG. 4 is a block diagram for explaining the electrical configuration of the substrate processing apparatus. [Figure 5] FIG. 5 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus. [Figure 6A] FIG. 6A is a schematic diagram for explaining the state of the substrate and its surroundings when the substrate processing is being performed. [Figure 6B] FIG. 6B is a schematic diagram for explaining the state of the substrate and its surroundings when the substrate processing is being performed. [Figure 6C]FIG. 6C is a schematic diagram for explaining the state of the substrate and its surroundings when the substrate processing is being performed. [Figure 6D] FIG. 6D is a schematic diagram for explaining the state of the substrate and its surroundings when the substrate processing is being performed. [Figure 6E] FIG. 6E is a schematic diagram for explaining the state of the substrate and its surroundings when the substrate processing is being performed. [Figure 7] FIG. 7 is a block diagram for explaining the functional configuration of a controller provided in the substrate processing apparatus. [Figure 8] FIG. 8 is a flowchart illustrating an example of an organic film removal process performed by the controller. [Figure 9A] FIG. 9A is a flowchart illustrating the substrate processing according to the first modified example. [Figure 9B] FIG. 9B is a flowchart illustrating the substrate processing according to the second modified example. [Figure 9C] FIG. 9C is a flowchart illustrating substrate processing according to the third modified example. [Figure 10] FIG. 10 is a schematic view for explaining the configurations of a sulfuric acid-containing liquid supply unit and a sulfuric acid-containing liquid recovery unit provided in a substrate processing apparatus according to the second embodiment. [Figure 11] FIG. 11 is a schematic view for explaining the configuration of a processing unit provided in a substrate processing apparatus according to the third embodiment. [Figure 12] FIG. 12 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus according to the third embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0050] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.

[0051] <Configuration of the Substrate Processing Apparatus According to the First Embodiment> FIG. 1 is a plan view illustrating an example of the configuration of a substrate processing apparatus 1 according to a first embodiment of the present invention.

[0052] The substrate processing apparatus 1 is a single-wafer processing apparatus that processes each substrate W. In this embodiment, the substrate W has a disk shape. The substrate W is a substrate W such as a silicon wafer, and has a pair of main surfaces.

[0053] The substrate processing apparatus 1 includes a plurality of processing units 2 for processing substrates W, a load port LP (container holding unit) on which a carrier C (container) for accommodating a plurality of substrates W to be processed in the processing units 2 is placed, transport robots (first transport robot IR and second transport robot CR) for transporting the substrates W between the load port LP and the processing units 2, and a controller 3 for controlling each component provided in the substrate processing apparatus 1.

[0054] The first transport robot IR transports the substrate W between the carrier C and the second transport robot CR. The second transport robot CR transports the substrate W between the first transport robot IR and the processing unit 2. Each transport robot is, for example, an articulated arm robot.

[0055] The processing units 2 are arranged on both sides of the transport path TR along which the substrates W are transported by the second transport robot CR, and are stacked in the vertical direction. The processing units 2 have, for example, the same configuration.

[0056] The multiple processing units 2 form four processing towers TW arranged at four horizontally spaced positions. Each processing tower TW includes multiple processing units 2 stacked vertically. The four processing towers TW are arranged two on each side of the transfer path TR extending from the load port LP toward the second transfer robot CR.

[0057] The substrate processing apparatus 1 includes a plurality of fluid boxes 4 that house valves, pipes, etc., and a storage box 5 that houses tanks for storing sulfuric acid-containing liquid, chemical liquid, rinse liquid, organic solvent, or these raw materials. The processing units 2 and the fluid boxes 4 are arranged inside a frame 6 that is generally rectangular in plan view.

[0058] The processing unit 2 has a chamber 7 that accommodates the substrate W during substrate processing. The chamber 7 includes an entrance / exit (not shown) through which the second transport robot CR loads the substrate W into the chamber 7 and unloads the substrate W from the chamber 7, and a shutter unit (not shown) that opens and closes the entrance. The processing liquid supplied to the substrate W in the chamber 7 includes, as will be described in detail later, a sulfuric acid-containing liquid, a chemical liquid, a rinse liquid, an organic solvent, etc.

[0059] <Configuration of processing unit according to the first embodiment> FIG. 2 is a schematic diagram for explaining the configuration of the processing unit 2. As shown in FIG.

[0060] The processing unit 2 further includes a spin chuck 8 that rotates the substrate W around a rotation axis A1 while holding the substrate W in a predetermined processing posture, a plurality of movable nozzles (a first movable nozzle 9, a second movable nozzle 10, a third movable nozzle 11) that eject processing liquid toward the substrate W, and a processing chamber 12 that can accommodate the substrate W held on the spin chuck 8.

[0061] The processing unit 2 further includes an ozone-containing gas supply member 13 that supplies an ozone-containing gas into the processing chamber 12, a substrate heating member 14 that heats the substrate W held on the spin chuck 8, and a processing cup 15 that receives processing liquid splashed from the substrate W held on the spin chuck 8.

[0062] The spin chuck 8, the plurality of moving nozzles, the processing chamber 12, the ozone-containing gas supply member 13, the substrate heating member 14, and the processing cup 15 are disposed within the chamber 7.

[0063] The rotation axis A1 passes through the center of the substrate W and is perpendicular to each main surface of the substrate W held in the processing posture. The processing posture is, for example, the posture of the substrate W shown in FIG. 2, which is a horizontal posture in which the main surface of the substrate W is in a horizontal plane, but is not limited to a horizontal posture. In other words, the processing posture may be a posture in which the main surface of the substrate W is inclined relative to the horizontal plane, unlike that shown in FIG. 2. When the processing posture is a horizontal posture, the rotation axis A1 extends vertically.

[0064] The spin chuck 8 is an example of a substrate holding member that holds the substrate W in a processing posture, and is also an example of a rotary holding member that rotates the substrate W around the rotation axis A1 while holding the substrate W in the processing posture.

[0065] The spin chuck 8 includes a spin base 21 having a disk shape extending horizontally, a plurality of gripping pins 20 that grip the substrate W above the spin base 21 and grip the peripheral edge of the substrate W above the spin base 21, a rotation shaft 22 that is connected to the spin base 21 and extends vertically, and a rotation drive mechanism 23 that rotates the rotation shaft 22 around its central axis (rotation axis A1). The spin base 21 is an example of a disk-shaped base.

[0066] The multiple gripping pins 20 are arranged on the upper surface of the spin base 21 at intervals in the circumferential direction of the spin base 21. The rotation drive mechanism 23 includes an actuator such as an electric motor. The rotation drive mechanism 23 rotates the rotation shaft 22, thereby rotating the spin base 21 and the multiple gripping pins 20 around the rotation axis A1. As a result, the substrate W is rotated together with the spin base 21 and the multiple gripping pins 20 around the rotation axis A1.

[0067] The multiple gripping pins 20 are movable between a closed position in which they contact the peripheral edge of the substrate W to grip the substrate W, and an open position in which they release their grip on the substrate W. The multiple gripping pins 20 are moved by an opening / closing mechanism (not shown).

[0068] When positioned in the closed position, the multiple gripping pins 20 grip the peripheral edge of the substrate W to hold the substrate W horizontally. When positioned in the open position, the multiple gripping pins 20 release their grip on the substrate W while supporting the peripheral edge of the substrate W from below. The opening / closing mechanism includes, for example, a link mechanism and an actuator that applies a driving force to the link mechanism.

[0069] The multiple mobile nozzles include a first mobile nozzle 9 that ejects a continuous flow of sulfuric acid-containing liquid toward the upper surface (upper main surface) of the substrate W held on the spin chuck 8, a second mobile nozzle 10 that selectively ejects a continuous flow of chemical liquid and a continuous flow of rinse liquid toward the upper surface of the substrate W held on the spin chuck 8, and a third mobile nozzle 11 that ejects an organic solvent toward the upper surface of the substrate W held on the spin chuck 8.

[0070] The first moving nozzle 9 is an example of a sulfuric acid-containing liquid discharge member that discharges a sulfuric acid-containing liquid toward the main surface (upper surface) of the substrate W held by the spin chuck 8. The second moving nozzle 10 is an example of a chemical liquid discharge member that discharges a chemical liquid toward the main surface (upper surface) of the substrate W held by the spin chuck 8, and is an example of a rinse liquid discharge member that discharges a rinse liquid toward the main surface (upper surface) of the substrate W held by the spin chuck 8. The third moving nozzle 11 is an example of an organic solvent discharge member that discharges an organic solvent toward the main surface (upper surface) of the substrate W held by the spin chuck 8.

[0071] The plurality of movable nozzles are moved in the horizontal direction by a plurality of nozzle drive mechanisms (first nozzle drive mechanism 25, second nozzle drive mechanism 26, and third nozzle drive mechanism 27).

[0072] Each nozzle driving mechanism can move the corresponding movable nozzle between a central position and a retracted position. The central position is a position where the movable nozzle faces a central region of the upper surface of the substrate W. The central region of the upper surface of the substrate W is a region on the upper surface of the substrate W that includes the center of rotation (central portion) and the area surrounding the center of rotation. The retracted position is a position where the movable nozzle does not face the upper surface of the substrate W and is outside the processing cup 15.

[0073] Each nozzle drive mechanism includes an arm (first arm 25a, second arm 26a, or third arm 27a) that supports the corresponding movable nozzle, and an arm drive mechanism (first arm drive mechanism 25b, second arm drive mechanism 26b, or third arm drive mechanism 27b) that moves the corresponding arm in the horizontal direction. Each arm drive mechanism includes an actuator such as an electric motor or an air cylinder.

[0074] The movable nozzle may be a rotary nozzle that rotates around a predetermined rotation axis, or a linear nozzle that moves linearly in the direction in which the corresponding arm extends. The movable nozzle may also be configured to be movable in the vertical direction.

[0075] The sulfuric acid-containing liquid discharged from the first moving nozzle 9 is, for example, an aqueous sulfuric acid solution. The aqueous sulfuric acid solution contains sulfuric acid (H2SO4) and water (H2O). The aqueous sulfuric acid solution is, for example, dilute sulfuric acid or concentrated sulfuric acid. The sulfuric acid-containing liquid may contain substances other than sulfuric acid and water. The sulfuric acid-containing liquid may be formed by mixing sulfuric acid with water such as DIW (deionized water).

[0076] The processing unit 2 further includes a sulfuric acid-containing liquid supply unit 16 that supplies a sulfuric acid-containing liquid to the first moving nozzle 9. The sulfuric acid-containing liquid supply unit 16 includes a sulfuric acid-containing liquid pipe 40, a sulfuric acid-containing liquid valve 50A, and a sulfuric acid-containing liquid flow rate adjustment valve 50B.

[0077] The sulfuric acid-containing liquid piping 40 is connected to the first moving nozzle 9 and guides the sulfuric acid-containing liquid to the first moving nozzle 9. The sulfuric acid-containing liquid valve 50A and the sulfuric acid-containing liquid flow rate adjustment valve 50B are provided on the sulfuric acid-containing liquid piping 40.

[0078] Providing the sulfuric acid-containing liquid valve 50A in the sulfuric acid-containing liquid piping 40 may mean that the sulfuric acid-containing liquid valve 50A is interposed in the sulfuric acid-containing liquid piping 40. The same applies to other valves described below.

[0079] The sulfuric acid-containing liquid valve 50A opens and closes the sulfuric acid-containing liquid piping 40. The sulfuric acid-containing liquid flow rate control valve 50B adjusts the flow rate of the sulfuric acid-containing liquid in the sulfuric acid-containing liquid piping 40. The configuration of the sulfuric acid-containing liquid supply unit 16 will be described in detail later. When the sulfuric acid-containing liquid valve 50A is opened, the sulfuric acid-containing liquid is discharged from the first moving nozzle 9 in a continuous flow.

[0080] Although not shown, the sulfuric acid-containing liquid valve 50A includes a valve body with a valve seat provided therein, a valve element that opens and closes the valve seat, and an actuator that moves the valve element between an open position and a closed position. Other valves have similar configurations.

[0081] The chemical solution ejected from the second moving nozzle 10 contains, for example, hydrogen peroxide (H2O2), hydrofluoric acid (HF), dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrochloric acid (HCl), HPM liquid (hydrochloric acid-hydrogen peroxide mixture), ammonia water, TMAH liquid (tetramethylammonium hydroxide solution), or APM liquid (ammonia-hydrogen peroxide mixture).

[0082] The rinse liquid discharged from the second moving nozzle 10 is, for example, water such as DIW. However, the rinse liquid is not limited to DIW. The rinse liquid is not limited to DIW, and may be DIW, carbonated water, electrolytic ion water, diluted hydrochloric acid water (for example, 1 ppm or more and 100 ppm or less), diluted ammonia water (for example, 1 ppm or more and 100 ppm or less), reduced water (hydrogen water), or a mixture containing at least two of these.

[0083] The second moving nozzle 10 is connected to a common pipe 41 that guides a fluid to the second moving nozzle 10. A chemical liquid pipe 42 that supplies a chemical liquid to the common pipe 41 and a rinse liquid pipe 43 that supplies a rinse liquid to the common pipe 41 are connected to the common pipe 41. The common pipe 41 may be connected to the chemical liquid pipe 42 and the rinse liquid pipe 43 via a mixing valve (not shown).

[0084] The common pipe 41 is provided with a common valve 51 that opens and closes the common pipe 41. The chemical pipe 42 is provided with a chemical valve 52A that opens and closes the chemical pipe 42 and a chemical flow rate adjustment valve 52B that adjusts the flow rate of the chemical liquid in the chemical pipe 42. The rinse liquid pipe 43 is provided with a rinse liquid valve 53A that opens and closes the rinse liquid pipe 43 and a rinse liquid flow rate adjustment valve 53B that adjusts the flow rate of the rinse liquid in the rinse liquid pipe 43.

[0085] When the chemical liquid valve 52A and the common valve 51 are opened, a continuous flow of the chemical liquid is discharged from the second moving nozzle 10. When the rinse liquid valve 53A and the common valve 51 are opened, a continuous flow of the rinse liquid is discharged from the second moving nozzle 10.

[0086] The organic solvent ejected from the third moving nozzle 11 contains at least one of alcohols such as ethanol (EtOH) and isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone.

[0087] An organic solvent pipe 44 that guides the organic solvent to the third moving nozzle 11 is connected to the third moving nozzle 11. The organic solvent pipe 44 is provided with an organic solvent valve 54A that opens and closes the organic solvent pipe 44, and an organic solvent flow rate adjustment valve 54B that adjusts the flow rate of the organic solvent in the organic solvent pipe 44.

[0088] The processing cup 15 includes a plurality of guards 28 (three in FIG. 2) that receive processing liquid splashed outward from the substrate W held on the spin chuck 8, a plurality of cups 29 (three in FIG. 2) that each receive processing liquid guided downward by the plurality of guards 28, and a cylindrical outer wall member 30 that surrounds the plurality of guards 28 and the plurality of cups 29.

[0089] Each guard 28 has a cylindrical shape in a plan view that surrounds the spin chuck 8. The upper end of each guard 28 is inclined inward toward the center of the guard 28. Each cup 29 has the shape of an annular groove that opens upward. The multiple guards 28 and the multiple cups 29 are arranged coaxially.

[0090] The multiple guards 28 are individually raised and lowered by a guard lifting drive mechanism (not shown). The guard lifting drive mechanism includes, for example, multiple actuators that drive the lifting and lowering of each of the multiple guards 28. The multiple actuators include at least one of an electric motor and an air cylinder.

[0091] The processing unit 2 includes a blower unit 31, such as an FFU (fan filter unit), that sends an inert gas from outside the chamber 7 into the chamber 7, and an exhaust pipe 32 that exhausts the air from the chamber 7. The blower unit 31 is disposed on the upper wall 7a of the chamber 7. The exhaust pipe 32 is connected to the outer wall member 30. The inert gas sent to the chamber 7 by the blower unit 31 may be, for example, nitrogen gas, a rare gas, or a mixture of these. The rare gas is, for example, argon gas.

[0092] The exhaust pipe 32 is connected to an exhaust duct (not shown). The atmosphere in the exhaust duct is sucked by a suction device (not shown). The atmosphere in the chamber 7 is exhausted to the exhaust duct via the exhaust pipe 32. The suction device includes a suction pump or the like that sucks the exhaust duct. The suction device is installed in or connected to the exhaust duct. The exhaust duct and the suction device are provided in a clean room in which the substrate processing apparatus 1 is installed or in a facility associated with the clean room. The exhaust duct and the suction device may be part of the substrate processing apparatus 1.

[0093] An ozone removal device 33 (ozone detoxifier) is provided between the exhaust pipe 32 and the exhaust duct or in the exhaust pipe 32. Ozone gas contained in the atmosphere exhausted from the chamber 7 is decomposed when passing through the ozone removal device 33.

[0094] By the action of the blower unit 31 and the exhaust pipe 32, an air current directed downward is formed in the internal space 7c of the chamber 7. The air current passes through the inside of the processing cup 15 and flows into the exhaust pipe 32.

[0095] The processing liquid supplied to the substrate W splashes from the peripheral edge of the substrate W and is received by one of the guards 28. The processing liquid received by the guard 28 is guided to the corresponding cup 29 and is collected or discarded by a drainage pipe (not shown) corresponding to each cup 29.

[0096] The substrate heating member 14 has the form of a disk-shaped hot plate that heats the substrate W from below. The substrate heating member 14 is disposed between the upper surface of the spin base 21 and the lower surface of the substrate W. The substrate heating member 14 has a heating surface 14a that faces the lower surface of the substrate W from below.

[0097] The substrate heating member 14 includes a plate body 60 and a heater 61. The plate body 60 is slightly smaller than the substrate W in a plan view. The upper surface of the plate body 60 forms the heating surface 14a. The heater 61 may be a resistor built into the plate body 60. When electricity is applied to the heater 61, the heating surface 14a is heated.

[0098] The heater 61 is configured to heat the substrate W within a temperature range from room temperature (for example, 5°C or higher and 25°C or lower) to 400°C or lower.

[0099] The processing unit 2 further includes a temperature sensor 62 that detects the temperature of the substrate heating member 14. In the example shown in Fig. 2, the temperature sensor 62 is built into the plate body 60, but the location of the temperature sensor 62 is not particularly limited. The temperature sensor 62 may be attached to the plate body 60 from the outside, for example.

[0100] A current supply unit 63 is connected to the heater 61 via a power supply line 64. The temperature of the heater 61 is adjusted by adjusting the current supplied from the current supply unit 63 to the heater 61. For example, the current supplied from the current supply unit 63 to the heater 61 is adjusted based on the temperature detected by the temperature sensor 62.

[0101] A heater lift shaft 65 is connected to the lower surface of the substrate heating member 14. The heater lift shaft 65 is inserted into a through-hole 21a formed in the center of the spin base 21 and into the internal space of the rotation shaft 22.

[0102] The processing unit 2 further includes a heater drive mechanism 66 that drives the movement of the substrate heating member 14 in the vertical direction. The heater drive mechanism 66 includes, for example, a heater actuator (not shown) that drives the movement of the heater lift shaft 65 in the vertical direction. The heater actuator includes, for example, at least one of an electric motor and an air cylinder. The heater drive mechanism 66 moves the substrate heating member 14 in the vertical direction via the heater lift shaft 65. The substrate heating member 14 is movable in the vertical direction between the lower surface of the substrate W and the upper surface of the spin base 21.

[0103] When the substrate heating member 14 rises, it can receive the substrate W from the multiple gripping pins 20 that are positioned in the open position. The substrate heating member 14 can heat the substrate W by being positioned at a contact position where the heating surface 14a is in contact with the underside of the substrate W, or at a proximity position where the heating surface 14a is in close proximity to the underside of the substrate W but not in contact with it. A position where the substrate heating member 14 is sufficiently retracted from the underside of the substrate W so that heating of the substrate W by the substrate heating member 14 is alleviated is called a retracted position. Sufficiently alleviating heating of the substrate W can be said to mean that heating of the substrate W is stopped.

[0104] The amount of heat transferred from the substrate heating member 14 to the substrate W when the substrate heating member 14 is located at the retracted position is smaller than the amount of heat transferred from the substrate heating member 14 to the substrate W when the substrate heating member 14 is located at the proximity position. The contact position and the proximity position are also referred to as heating positions. The retracted position is also referred to as a heating relaxation position or a heating stop position.

[0105] The processing chamber 12 has an internal space 70 capable of accommodating a substrate W, a housing 71 that defines the internal space 70, and an opening 70a that is provided in the housing 71 and that opens the internal space 70 to the outside of the processing chamber 12. The housing 71 has, for example, a cylindrical inner circumferential surface 71a that is larger in diameter than the substrate W in a plan view, and a flat bottom surface 71b that is connected to the inner circumferential surface 71a.

[0106] A processing chamber lift shaft 72 is connected to the processing chamber 12. The processing unit 2 further includes a processing chamber drive mechanism 73 that drives the movement of the processing chamber 12 in the vertical direction. The processing chamber drive mechanism 73 includes, for example, a processing chamber actuator (not shown) that drives the movement of the processing chamber lift shaft 72 in the vertical direction. The processing chamber drive mechanism 73 moves the processing chamber 12 in the vertical direction via the processing chamber lift shaft 72. The processing chamber actuator includes, for example, at least one of an electric motor and an air cylinder.

[0107] By lowering the processing chamber 12, the substrate W can be relatively moved into the processing chamber 12 (internal space 70) through the opening 70a. The position of the processing chamber 12 when the processing chamber 12 accommodates the substrate W in the processing chamber 12 (internal space 70) is called the accommodation position. When the processing chamber 12 is located at the accommodation position, the inner peripheral surface 71a of the housing 71 faces the substrate W from the side. By raising the processing chamber 12 that is located at the accommodation position, the substrate W can be relatively moved outside the processing chamber 12 through the opening 70a. The position of the processing chamber 12 when the substrate W is located outside the processing chamber 12 is called the non-accommodation position.

[0108] In this way, the processing chamber drive mechanism 73 can move the processing chamber 12 relative to the spin chuck 8 so that the substrate W moves relatively between the inside and outside of the processing chamber 12. When the processing chamber 12 is located in the storage position, each nozzle movement mechanism cannot move the corresponding moving nozzle to a position facing the upper surface of the substrate W. When the processing chamber 12 is located in the non-storage position, each nozzle movement mechanism can move the corresponding moving nozzle to a position facing the upper surface of the substrate W.

[0109] The ozone-containing gas supply member 13 includes an ozone-containing gas flow path 75 provided inside the housing 71, and a plurality of ozone-containing gas discharge ports 76 exposed from the housing 71 and connected to one end of the ozone-containing gas flow path 75 and the internal space 70. Therefore, the ozone-containing gas can be quickly supplied to the entire internal space 70. In the example shown in FIG. 2, the plurality of ozone-containing gas discharge ports 76 are formed on the bottom surface 71b of the housing 71.

[0110] The ozone-containing gas flow path 75 may be formed, for example, by a communication hole formed in the processing chamber lifting shaft 72 and the housing 71, or by a pipe disposed in the communication hole. The ozone-containing gas flow path 75 may not be formed in the processing chamber lifting shaft 72, but may be formed only in the housing 71.

[0111] The ozone-containing gas discharged from the ozone-containing gas discharge port 76 may be ozone gas or a mixed gas of ozone gas and a gas other than ozone gas. The gas other than ozone gas may be, for example, an inert gas. The inert gas contained in the ozone-containing gas may be, for example, nitrogen gas, a rare gas, or a mixed gas thereof. The rare gas may be, for example, argon gas.

[0112] The ozone-containing gas flow path 75 of the ozone-containing gas supply member 13 is connected to an ozone-containing gas pipe 45 that guides the ozone-containing gas to the ozone-containing gas flow path 75. The ozone-containing gas pipe 45 is provided with an ozone-containing gas valve 55A that opens and closes the ozone-containing gas pipe 45, and an ozone-containing gas flow rate adjustment valve 55B that adjusts the flow rate of the ozone-containing gas in the ozone-containing gas pipe 45.

[0113] <Configuration of sulfuric acid-containing liquid supply unit> FIG. 3 is a schematic diagram for explaining the configuration of the sulfuric acid-containing liquid supply unit 16. As shown in FIG.

[0114] The sulfuric acid-containing liquid supply unit 16 further includes a storage tank 80 , a supply pipe 81 , a circulation pipe 82 , a liquid transfer pump 83 , a circulation valve 84 , a pipe heater 85 , and a tank heater 86 .

[0115] The storage tank 80 stores the sulfuric acid-containing liquid. The supply pipe 81 is connected to the storage tank 80 and the sulfuric acid-containing liquid pipe 40, and supplies the sulfuric acid-containing liquid in the storage tank 80 toward the sulfuric acid-containing liquid pipe 40. The circulation pipe 82 is connected to a connection position between the supply pipe 81 and the sulfuric acid-containing liquid pipe 40, and circulates the sulfuric acid-containing liquid in the storage tank 80 by returning the sulfuric acid-containing liquid in the supply pipe 81 to the storage tank 80. The liquid feed pump 83 generates a driving force to feed the sulfuric acid-containing liquid in the storage tank 80 to the supply pipe 81. The circulation valve 84 is provided in the circulation pipe 82, and opens and closes the circulation pipe 82.

[0116] The pipe heater 85 heats the sulfuric acid-containing liquid in the supply pipe 81. The tank heater 86 heats the sulfuric acid-containing liquid in the storage tank 80. The configurations of the pipe heater 85 and the tank heater 86 are not particularly limited. The pipe heater 85 heats the sulfuric acid-containing liquid passing through the supply pipe 81, for example, by heating the supply pipe 81 from the outside. The tank heater 86 is, for example, a heater attached to the outer surface of the wall of the storage tank 80.

[0117] The sulfuric acid-containing liquid supply unit 16 further includes a replenishment pipe 88 that replenishes new sulfuric acid-containing liquid (new liquid) from a sulfuric acid-containing liquid supply source 87 to the storage tank 80, and a replenishment valve 89 that opens and closes the replenishment pipe 88. When the replenishment valve 89 is opened, new liquid is supplied to the storage tank 80.

[0118] <Electrical Configuration of Substrate Processing According to First Embodiment> FIG. 4 is a block diagram for explaining the electrical configuration of the substrate processing apparatus 1. As shown in FIG.

[0119] The controller 3 is a computer including a computer main body 3a and a peripheral device 3d connected to the computer main body 3a. The computer main body 3a includes a processor (CPU) 3b that executes various instructions and a memory 3c that stores information.

[0120] The peripheral device 3d includes an auxiliary storage device 3e that stores information such as programs, a reading device 3f that reads information from removable media (not shown), and a communication device 3g that communicates with other devices such as a host computer (not shown).

[0121] The controller 3 is connected to an input device 3A, a display device 3B, and an alarm device 3C. The input device 3A is operated when an operator such as a user or a maintenance technician inputs information into the substrate processing apparatus 1. The information is displayed on the screen of the display device 3B. The input device 3A may be any of a keyboard, a pointing device, and a touch panel, or may be a device other than these. The substrate processing apparatus 1 may be provided with a touch panel display that serves as both the input device 3A and the display device 3B. The alarm device 3C issues an alarm using one or more of light, sound, characters, and figures. If the input device 3A is a touch panel display, the input device 3A may also serve as the alarm device 3C.

[0122] The auxiliary storage device 3e is a non-volatile memory that retains its memory even when power is not supplied, and is, for example, a magnetic storage device such as a hard disk drive.

[0123] The auxiliary storage device 3e stores a plurality of recipes. A recipe is information that defines the processing content, processing conditions, and processing procedure for the substrate W. The plurality of recipes differ from one another in at least one of the processing content, processing conditions, and processing procedure for the substrate W.

[0124] The controller 3 controls each member included in the substrate processing apparatus 1 so that the substrate W is processed in accordance with a recipe specified by an external device such as a host computer.

[0125] Control targets of the controller 3 include the first transport robot IR, the second transport robot CR, the rotation drive mechanism 23, the first nozzle drive mechanism 25, the second nozzle drive mechanism 26, the third nozzle drive mechanism 27, the processing chamber drive mechanism 73, the heater drive mechanism 66, the power supply unit 63, the air blower unit 31, the temperature sensor 62, the liquid supply pump 83, the piping heater 85, the tank heater 86, the sulfuric acid-containing liquid valve 50A, the sulfuric acid-containing liquid flow rate control valve 50B, the common valve 51, the chemical liquid valve 52A, the chemical liquid flow rate control valve 52B, the rinse liquid valve 53A, the rinse liquid flow rate control valve 53B, the organic solvent valve 54A, the organic solvent flow rate control valve 54B, the circulation valve 84, and the replenishment valve 89.

[0126] 4 illustrates representative components, but this does not mean that components not illustrated are not controlled by the controller 3, and the controller 3 can appropriately control each component included in the substrate processing apparatus 1. FIG. 4 also illustrates components that will be described in a second embodiment and a third embodiment, which will be described later, and these components are also controlled by the controller 3.

[0127] The following steps are performed by the controller 3 controlling the substrate processing apparatus 1. In other words, the controller 3 is programmed to perform the following steps.

[0128] <Example of substrate processing> Fig. 5 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus 1. Figs. 6A to 6E are schematic views illustrating the state of the substrate W and its surroundings when the substrate processing is being performed. An organic film such as a resist is formed on at least one of the pair of main surfaces of the substrate W used in the substrate processing.

[0129] 5, the substrate processing by the substrate processing apparatus 1 includes, for example, a substrate loading step (step S1), a substrate heating step (step S2), a liquid film forming step (step S3), an ozone-containing gas exposure step (step S4), a first rinsing step (step S5), an ozone-containing gas removal step (step S6), a chemical liquid supply step (step S7), a second rinsing step (step S8), an organic solvent supply step (step S9), a spin-drying step (step S10), and a substrate unloading step (step S11). Details of the substrate processing will be described below, mainly with reference to FIGS. 2 and 5. FIGS. 6A to 6E will also be referenced as appropriate.

[0130] First, an unprocessed substrate W is carried from the carrier C into the processing unit 2 by the second transport robot CR (see FIG. 1) and handed over to the spin chuck 8 (substrate carrying-in step: step S1). As a result, the substrate W is held horizontally by the spin chuck 8 (substrate holding step). At this time, the substrate W is held by the spin chuck 8 so that the main surface on which the organic film is formed faces upward. The substrate W continues to be held by the spin chuck 8 until the spin dry step (step S10) is completed.

[0131] With the substrate W held by the spin chuck 8, the rotation drive mechanism 23 starts rotating the substrate W (substrate rotation process). During substrate processing, an airflow from above to below is constantly generated in the internal space 7c of the chamber 7, and the airflow passes through the inside of the processing cup 15 and flows into the exhaust pipe 32.

[0132] After the second transport robot CR retreats from the chamber 7, a substrate heating step (step S2) is performed to heat the substrate W. Specifically, the energizing unit 63 supplies current to the heater 61, causing the temperature of the heater 61 to start rising. Then, the heater driving mechanism 66 moves the substrate heating member 14 from the retreated position to the proximal position. As shown in FIG. 6A, the temperature of the heater 61 starts to rise, and the substrate heating member 14 is disposed at the proximal position, thereby starting heating of the substrate W (substrate heating start step: step S21).

[0133] Then, when the temperature detected by the temperature sensor 62 reaches the processing temperature range, a liquid film forming step (step S3) is performed to form a liquid film 100 (see FIG. 6C) of the sulfuric acid-containing liquid on the upper surface of the substrate W. Specifically, the first nozzle driving mechanism 25 moves the first moving nozzle 9 to the processing position. The processing position is, for example, the central position.

[0134] With the first moving nozzle 9 positioned at the processing position, the sulfuric acid-containing liquid valve 50A is opened. As a result, as shown in Fig. 6B, the sulfuric acid-containing liquid is discharged from the first moving nozzle 9, and the supply of the sulfuric acid-containing liquid to the upper surface of the substrate W is started (sulfuric acid-containing liquid supply start step: step S31). The sulfuric acid-containing liquid that has landed on the upper surface of the substrate W moves toward the peripheral edge of the upper surface of the substrate W, and the sulfuric acid-containing liquid spreads over the entire upper surface of the substrate W.

[0135] When a predetermined period of time has elapsed since the supply of the sulfuric acid-containing liquid was started, the sulfuric acid-containing liquid valve 50A is closed. This stops the supply of the sulfuric acid-containing liquid to the upper surface of the substrate W (sulfuric acid-containing liquid supply stopping step: step S32). The discharge period of the sulfuric acid-containing liquid is, for example, about 1 second.

[0136] The sulfuric acid-containing liquid on the upper surface of the substrate W is thinned by removing the sulfuric acid-containing liquid on the upper surface of the substrate W by the centrifugal force of the rotation of the substrate W without supplying the sulfuric acid-containing liquid to the upper surface of the substrate W (thinning process). As a result, a thin liquid film 100 of the sulfuric acid-containing liquid is formed on the upper surface of the substrate W, as shown in Fig. 6C. The liquid film 100 has a thickness of, for example, 1 µm or more and 2 mm or less.

[0137] At the time when the discharge of the sulfuric acid-containing liquid is stopped, the sulfuric acid-containing liquid does not need to have spread over the entire upper surface of the substrate W, and after the supply of the sulfuric acid-containing liquid is stopped, the sulfuric acid-containing liquid may have spread to the peripheral portion of the upper surface of the substrate W. If the discharge of the sulfuric acid-containing liquid is stopped before the sulfuric acid-containing liquid has spread over the entire substrate W, the supply amount of the sulfuric acid-containing liquid can be further reduced.

[0138] After the discharge of the sulfuric acid-containing liquid is stopped, the first nozzle driving mechanism 25 retracts the first movable nozzle 9. When a predetermined period of time has elapsed since the discharge of the sulfuric acid-containing liquid is stopped, an ozone-containing gas exposure step (step S4) is performed. The ozone-containing gas exposure step is a step of exposing the liquid film 100 on the upper surface of the substrate W to the ozone-containing gas by filling the processing chamber 12 with the ozone-containing gas.

[0139] Specifically, when a predetermined period of time has elapsed since the discharge of the sulfuric acid-containing liquid was stopped, the processing chamber drive mechanism 73 lowers the processing chamber 12 from the non-accommodating position to the accommodating position. As a result, the substrate W is accommodated in the processing chamber 12 (substrate accommodating step). With the processing chamber 12 placed in the accommodating position, the ozone-containing gas valve 55A is opened. As a result, as shown in FIG. 6D, an ozone-containing gas is supplied into the processing chamber 12 (ozone-containing gas supply start step: step S41). By supplying the ozone-containing gas into the processing chamber 12, the processing chamber 12 is filled with the ozone-containing gas (ozone-containing gas supply step, ozone-containing gas filling step).

[0140] By placing the substrate W in the processing chamber 12 filled with an ozone-containing gas, the liquid film 100 on the upper surface of the substrate W can be exposed to the ozone-containing gas (ozone-containing gas exposure step).

[0141] By supplying the ozone-containing gas into the processing chamber 12, the pressure inside the processing chamber 12 can be increased (pressurized supply process). As a result, the pressure inside the processing chamber 12 becomes higher than the pressure outside the processing chamber 12. The pressure outside the processing chamber 12 in the chamber 7 is, for example, atmospheric pressure, or approximately 0.1 MPa. The pressure inside the processing chamber 12 is, for example, 0.1 MPa or higher and 0.2 MPa. By placing the substrate W in the processing chamber 12 and narrowing the opening 70a, the pressure inside the processing chamber 12 can be easily increased.

[0142] After a predetermined period of time has elapsed since the ozone-containing gas was supplied into the processing chamber 12, the ozone-containing gas valve 55A is closed, and the processing chamber drive mechanism 73 moves the processing chamber 12 from the accommodation position to the non-accommodation position.

[0143] Closing the ozone-containing gas valve 55A stops the supply of ozone-containing gas to the processing chamber 12 (ozone-containing gas supply stopping step: step S42). The processing chamber drive mechanism 73 raises the processing chamber 12 from the accommodation position to the non-accommodation position. This causes the substrate W to be removed from the processing chamber 12 (substrate removing step). Removing the substrate W from the processing chamber 12 stops the exposure of the liquid film 100 on the upper surface of the substrate W to the ozone-containing gas. This completes the ozone-containing gas exposure step (step S4). The substrate removing step may be performed before closing the ozone-containing gas valve 55A.

[0144] Strictly speaking, ozone-containing gas remains in the chamber 7. However, by placing the processing chamber 12 in the non-accommodation position, it is possible to reduce the concentration of ozone gas in the atmosphere in contact with the liquid film 100 on the upper surface of the substrate W. In this way, reducing the concentration of ozone gas in the atmosphere in contact with the liquid film 100 on the upper surface of the substrate W is referred to as stopping the exposure to the ozone-containing gas.

[0145] After the exposure of the ozone-containing gas to the liquid film 100 on the upper surface of the substrate W is stopped, the heater drive mechanism 66 moves the substrate heating member 14 from the proximity position to the retracted position. By placing the substrate heating member 14 at the retracted position (the position shown in FIG. 6E), heating of the substrate W is stopped (substrate heating stopping step: step S22). This completes the substrate heating step (step S2).

[0146] By performing the substrate heating step (step S2), the liquid film forming step (step S3), and the ozone-containing gas exposure step (step S4), the organic film on the substrate W is dissolved in the sulfuric acid-containing liquid and removed from the upper surface of the substrate W. In some cases, the organic film is not completely dissolved in the sulfuric acid-containing liquid and is peeled off from the upper surface of the substrate W by the liquid flow of the sulfuric acid-containing liquid.

[0147] After the substrate heating process (step S2), the liquid film forming process (step S3), and the ozone-containing gas exposure process (step S4), a first rinsing process (step S5) is performed to clean the upper surface of the substrate W by supplying a rinsing liquid for the upper surface of the substrate W.

[0148] Specifically, the second nozzle driving mechanism 26 moves the second movable nozzle 10 to the processing position. The processing position is, for example, a central position. With the second movable nozzle 10 positioned at the processing position, the common valve 51 and the rinse liquid valve 53A are opened. As a result, as shown in FIG. 6E, rinse liquid is ejected from the second movable nozzle 10, and the supply of rinse liquid to the upper surface of the substrate W begins (rinse liquid supply start step, rinse liquid supply step). The rinse liquid that has landed on the upper surface of the substrate W moves toward the peripheral edge of the upper surface of the substrate W, and the rinse liquid spreads over the entire upper surface of the substrate W.

[0149] When a predetermined period of time has elapsed since the supply of the rinse liquid started, the common valve 51 and the rinse liquid valve 53A are closed. This stops the supply of the rinse liquid to the upper surface of the substrate W (rinse liquid supply stopping step). This ends the first rinse step. The first rinse step causes the sulfuric acid-containing liquid to be discharged from the upper surface of the substrate W. The organic film peeled off from the upper surface of the substrate W is removed from the upper surface of the substrate W together with the sulfuric acid-containing liquid.

[0150] After the supply of the rinsing liquid to the upper surface of the substrate W is stopped, an ozone-containing gas removal step (step S6) is performed to remove the ozone-containing gas from the processing chamber 12 and the chamber 7. Specifically, the ozone-containing gas is removed from the processing chamber 12 and the chamber 7 by adjusting at least one of the supply flow rate of the inert gas by the blower unit 31 and the exhaust flow rate from the exhaust pipe 32.

[0151] After the ozone-containing gas removal process (step S6), a chemical liquid supply process (step S7) is performed to supply a chemical liquid to the upper surface of the substrate W. Specifically, the common valve 51 and the chemical liquid valve 52A are opened while the second moving nozzle 10 is positioned at the processing position. This stops the discharge of the rinsing liquid, and furthermore, a continuous flow of the chemical liquid is discharged (supplied) from the second moving nozzle 10 toward the upper surface of the substrate W (chemical liquid discharge process, chemical liquid supply process). This causes the upper surface of the substrate W to be processed with the chemical liquid.

[0152] After the chemical liquid supplying step (step S7), a second rinsing step (step S8) is performed in which a rinse liquid is supplied to the upper surface of the substrate W to clean the upper surface of the substrate W. Specifically, while the second moving nozzle 10 faces the upper surface of the substrate W and the common valve 51 is maintained in an open state, the chemical liquid valve 52A is closed and the rinse liquid valve 53A is opened. This stops the discharge of the chemical liquid from the second moving nozzle 10, and further, a continuous flow of the rinse liquid is discharged (supplied) from the second moving nozzle 10 toward the upper surface of the substrate W (rinsing liquid discharge step, rinse liquid supply step). This causes the chemical liquid on the upper surface of the substrate W to be discharged outside the substrate W together with the rinse liquid, and the upper surface of the substrate W is cleaned.

[0153] After the second rinsing step (step S8), an organic solvent supplying step (step S9) is performed to supply an organic solvent to the upper surface of the substrate W. Specifically, the discharge of the rinsing liquid from the second moving nozzle 10 is stopped, and the second moving nozzle 10 is retracted. Then, the third nozzle driving mechanism 27 positions the third moving nozzle 11 opposite the upper surface of the substrate W, and the organic solvent valve 54A is opened. As a result, a continuous flow of organic solvent is discharged (supplied) from the third moving nozzle 11 toward the upper surface of the substrate W (organic solvent discharge step, organic solvent supply step). As a result, the rinsing liquid on the upper surface of the substrate W is replaced with the organic solvent.

[0154] It is preferable that the organic solvent used in substrate processing is more volatile than the rinse liquid. If so, by replacing the rinse liquid with the organic solvent, the substrate W can be dried well in the subsequent spin-drying process (step S10). It is preferable that the organic solvent used in substrate processing has a lower surface tension than the rinse liquid. If so, when a concave-convex pattern is formed on the upper surface of the substrate W, the surface tension acting on the concave-convex pattern can be reduced when the upper surface of the substrate W is dried, and collapse of the concave-convex pattern can be suppressed.

[0155] Next, a spin-drying step (step S10) is performed in which the substrate W is rotated at high speed to dry the upper surface of the substrate W. Specifically, the organic solvent valve 54A is closed to stop the supply of the organic solvent to the upper surface of the substrate W. Then, the rotation drive mechanism 23 accelerates the rotation of the substrate W, causing the substrate W to rotate at high speed (for example, 1500 rpm). As a result, a large centrifugal force acts on the rinse liquid adhering to the substrate W, and the organic solvent is shaken off around the substrate W.

[0156] After the spin dry step (step S10), the rotation drive mechanism 23 stops the rotation of the substrate W. Thereafter, the second transport robot CR enters the processing unit 2, receives the processed substrate W from the spin chuck 8, and unloads it from the processing unit 2 (substrate unloading step: step S11). The substrate W is handed over from the second transport robot CR to the first transport robot IR, and is stored in the carrier C by the first transport robot IR.

[0157] <Controller functional configuration> Fig. 7 is a block diagram for explaining the functional configuration of the controller 3. Fig. 8 is a flowchart for explaining an example of an organic film removal process performed by the controller 3.

[0158] The controller 3 operates as a processing unit for various functions by executing a program stored in the memory 3c (see FIG. 4). When the controller 3 executes a program, the program stored in the auxiliary storage device 3e (see FIG. 4) is loaded into the memory 3c.

[0159] Specifically, the controller 3 is configured and programmed to function as a temperature determination unit 90, a first start unit 91, a first time elapse determination unit 92, a first stop unit 93, a second time elapse determination unit 94, a second start unit 95, a third time elapse determination unit 96, and a second stop unit 97. The controller 3 functions as these functional processing units, thereby performing an organic film removal process for removing an organic film from the upper surface of the substrate W.

[0160] The temperature determination unit 90 determines whether the temperature detected by the temperature sensor 62 is within the processing temperature range (step S13). The processing temperature range is, for example, from 50°C to 270°C. The processing temperature range is preferably from 50°C to 270°C, and more preferably from 80°C to 170°C. If the temperature detected by the temperature sensor 62 is outside the processing start temperature range (step S13: NO), the temperature determination unit 90 returns to step S13.

[0161] When the temperature determination unit 90 determines that the temperature detected by the temperature sensor 62 is within the processing temperature range (step S13: YES), the first start unit 91 outputs a command to start discharging sulfuric acid-containing liquid to the first nozzle drive mechanism 25 and the sulfuric acid-containing liquid valve 50A (step S14). As a result, the first movable nozzle 9 is moved toward the processing position, and discharging of the sulfuric acid-containing liquid from the first movable nozzle 9 is started. Therefore, the sulfuric acid-containing liquid supplied to the upper surface of the substrate W can be quickly heated.

[0162] The sulfuric acid-containing liquid discharge start command includes, for example, a processing position movement command that is output to the first nozzle driving mechanism 25 to move the first moving nozzle 9, and a first open command that is output to the sulfuric acid-containing liquid valve 50A to open the sulfuric acid-containing liquid valve 50A after the first movement command is output and when the first moving nozzle 9 is positioned at the processing position.

[0163] After the command to start discharging the sulfuric acid-containing liquid is output, that is, after the discharging of the sulfuric acid-containing liquid from the first moving nozzle 9 is started, the first time elapse determination unit 92 determines whether the supply stop time has elapsed (step S15). If the supply stop time has not elapsed (step S15: NO), the first time elapse determination unit 92 returns to step S15.

[0164] If the first time elapse determination unit 92 determines that the supply stop time has elapsed (step S15: YES), the first stop unit 93 outputs a sulfuric acid-containing liquid discharge stop command to the first nozzle drive mechanism 25 and the sulfuric acid-containing liquid valve 50A (step S16). This stops the discharge of the sulfuric acid-containing liquid from the first movable nozzle 9, and moves the first movable nozzle 9 toward the retracted position. Therefore, the discharge time of the sulfuric acid-containing liquid can be controlled with high reproducibility. The supply stop time is set in advance based on the rotation speed of the substrate W and the supply flow rate of the sulfuric acid-containing liquid.

[0165] The sulfuric acid-containing liquid discharge stop command includes, for example, a first close command that is output to the sulfuric acid-containing liquid valve 50A to close the sulfuric acid-containing liquid valve 50A, and a retract position movement command that is output to the first nozzle driving mechanism 25 after the first close command is output to move the first moving nozzle 9.

[0166] After the command to stop discharging the sulfuric acid-containing liquid is output, that is, after the discharging of the sulfuric acid-containing liquid from the first movable nozzle 9 is stopped, the second time elapse determination unit 94 determines whether the liquid film formation time has elapsed (step S17). The liquid film formation time is, for example, the time elapsed from the point in time when the discharging of the sulfuric acid-containing liquid from the first movable nozzle 9 is started. The liquid film formation time is a time longer than the discharging time. If the liquid film formation time has not elapsed (step S17: NO), the second time elapse determination unit 94 returns to step S17.

[0167] When the second time elapse determination unit 94 determines that the liquid film formation time has elapsed (step S17: YES), the second start unit 95 outputs an ozone-containing gas exposure start command to the processing chamber drive mechanism 73 and the ozone-containing gas valve 55A (step S18). As a result, the processing chamber 12 is moved toward the accommodation position, and the ozone-containing gas supply member 13 starts discharging the ozone-containing gas. Therefore, after the liquid film 100 of the sulfuric acid-containing liquid is formed, the supply of the ozone-containing gas to the processing chamber 12 starts promptly. The second time elapse determination unit 94 is an example of a time elapse determination unit.

[0168] The ozone-containing gas exposure start command includes, for example, a storage position movement command that is output to the processing chamber drive mechanism 73 to move the processing chamber 12 toward the storage position, and a second open command that is output to the ozone-containing gas valve 55A when the processing chamber 12 is placed in the storage position after the storage position movement command is output, to open the ozone-containing gas valve 55A.

[0169] After the ozone-containing gas exposure start command is output, the third time elapse determination unit 96 determines whether the exposure time has elapsed (step S19). The exposure time is the time elapsed from the point in time when the ozone-containing gas starts to be discharged from the ozone-containing gas supply member 13. If the exposure time has not elapsed (step S19: NO), the third time elapse determination unit 96 returns to step S19.

[0170] When the third time elapse determination unit 96 determines that the exposure time has elapsed (step S19: YES), the second stop unit 97 outputs an ozone-containing gas exposure stop command to the processing chamber drive mechanism 73 and the ozone-containing gas valve 55A (step S20). As a result, the processing chamber 12 is moved toward the non-accommodation position, and the discharge of the ozone-containing gas from the ozone-containing gas supply member 13 is stopped. Therefore, an appropriate amount of ozone is dissolved in the liquid film 100 of the sulfuric acid-containing liquid, and the organic film can be removed from the upper surface of the substrate W.

[0171] The ozone-containing gas exposure stop command includes, for example, a second close command that is output to the ozone-containing gas valve 55A to close the ozone-containing gas valve 55A, and a non-containment position movement command that is output to the processing chamber drive mechanism 73 after the second close command is output to move the processing chamber 12 toward the non-containment position.

[0172] As described above, the controller 3 functions as the above-mentioned functional processing unit, thereby enabling substrate processing with high reproducibility, and therefore organic films can be removed from the upper surface of the substrate W with high reproducibility.

[0173] <Summary of the First Embodiment> According to the first embodiment of the present invention, by filling the processing chamber 12 with an ozone-containing gas while the substrate W is placed in the processing chamber 12, the liquid film 100 of the sulfuric acid-containing liquid on the substrate W is exposed to the ozone-containing gas. This allows ozone in the ozone-containing gas to be dissolved in the sulfuric acid-containing liquid that constitutes the liquid film 100 on the substrate W, thereby forming peroxodisulfuric acid in the liquid film 100.

[0174] Furthermore, the substrate W is heated in a state in which the liquid film 100 is formed on the upper surface of the substrate W. That is, the substrate W is heated in a state in which peroxodisulfuric acid is formed in the sulfuric acid-containing liquid that constitutes the liquid film 100 on the upper surface of the substrate W. Therefore, the oxidizing power of peroxodisulfuric acid can be increased.

[0175] Furthermore, the substrate W is heated in a state where the processing chamber 12 is filled with an ozone-containing gas. Therefore, even if the solubility of ozone in the sulfuric acid-containing liquid decreases due to heating, the ozone-containing gas containing a sufficient concentration of ozone can be maintained in contact with the sulfuric acid-containing liquid on the upper surface of the substrate W. Therefore, gasification of ozone in the sulfuric acid-containing liquid can be suppressed.

[0176] As a result, the organic film such as resist can be removed from the substrate W quickly and thoroughly.

[0177] According to the first embodiment, heating of the substrate W in the substrate heating step (step S2) is started before the liquid film forming step (step S3) and the ozone-containing gas exposure step (step S4). Therefore, even if the time required to increase the temperature of the substrate W is longer than the time required to form the liquid film 100 and the time required to fill the substrate with the ozone-containing gas, the temperature of the substrate W can be quickly brought into the processing temperature range.

[0178] According to the first embodiment, the ozone-containing gas exposure step (step S4) includes a pressurizing supply step of supplying an ozone-containing gas to the processing chamber 12 so that the pressure inside the processing chamber 12 is higher than the pressure outside the processing chamber 12 while a liquid film 100 of the sulfuric acid-containing liquid is formed on the upper surface of the substrate W. Here, according to Henry's law, the amount of gas dissolved in a liquid is proportional to the pressure of the gas in contact with the liquid. Therefore, by supplying an ozone-containing gas into the processing chamber 12 and increasing the pressure of the ozone-containing gas in contact with the sulfuric acid-containing liquid on the upper surface of the substrate W, the concentration of ozone in the sulfuric acid-containing liquid can be increased. This increases the concentration of peroxodisulfuric acid in the liquid film 100, thereby enabling the organic film to be removed quickly and thoroughly from the upper surface of the substrate W.

[0179] According to the first embodiment, after the substrate heating step (step S2), a rinse liquid is supplied to the upper surface of the substrate W (rinse liquid supply step). Therefore, the rinse liquid can remove the liquid film 100 of the sulfuric acid-containing liquid from the upper surface of the substrate W. Therefore, it is possible to prevent sulfuric acid from remaining on the upper surface of the substrate W after the removal of the organic film from the upper surface of the substrate W is completed.

[0180] According to the first embodiment, in the liquid film forming step, the sulfuric acid-containing liquid is supplied toward the upper surface of the substrate W (sulfuric acid-containing liquid supplying step). After the supply of the sulfuric acid-containing liquid to the upper surface of the substrate W is stopped, the substrate W is rotated to thin the sulfuric acid-containing liquid on the upper surface of the substrate W, thereby forming the liquid film 100 (thinning step).

[0181] Therefore, the time required for supplying the sulfuric acid-containing liquid to the upper surface of the substrate W can be shortened compared to the case where the sulfuric acid-containing liquid is spread over the entire upper surface of the substrate W while being supplied in a continuous flow onto the upper surface of the substrate W. As described above, the discharge period of the sulfuric acid-containing liquid is, for example, about 1 second. Therefore, the amount of sulfuric acid-containing liquid used can be reduced.

[0182] Furthermore, compared to the case where a continuous flow of the sulfuric acid-containing liquid is supplied to the upper surface of the substrate W and the sulfuric acid-containing liquid is spread over the entire upper surface of the substrate W, the liquid film 100 of the sulfuric acid-containing liquid on the upper surface of the substrate W can be made thinner. Therefore, the time required to heat the liquid film 100 can be reduced, and power saving can be achieved.

[0183] Peroxodisulfuric acid, which is generated from the surface of the liquid film 100 by the reaction between ozone dissolved in the sulfuric acid-containing liquid and sulfuric acid, diffuses through the liquid film 100 and reaches the upper surface of the substrate W, where it reacts with the organic film on the upper surface of the substrate W. Therefore, by thinning the liquid film 100, it is possible to make it easier for peroxodisulfuric acid to reach the upper surface of the substrate W. Therefore, the organic film can be quickly and sufficiently removed from the upper surface of the substrate W.

[0184] According to the first embodiment, when the substrate W on which the liquid film 100 is formed is placed in the processing chamber 12, the supply of ozone-containing gas to the processing chamber 12 is started, thereby filling the processing chamber 12 with ozone-containing gas.

[0185] Unlike the first embodiment, when the liquid film 100 is formed after the supply of the ozone-containing gas to the processing chamber 12 is stopped, the ozone concentration in the atmosphere in the processing chamber 12 may be reduced due to the outflow of the ozone-containing gas from the processing chamber 12 to the outside. Therefore, the amount of ozone dissolved in the sulfuric acid-containing liquid in the liquid film 100 may be reduced. Therefore, if the supply of the ozone-containing gas is started when the liquid film 100 has already been formed, the liquid film 100 can be brought into contact with the atmosphere in the processing chamber 12 in a state where the ozone concentration in the atmosphere in the processing chamber 12 is sufficiently high. Therefore, the amount of ozone dissolved in the sulfuric acid-containing liquid in the liquid film 100 on the upper surface of the substrate W can be increased.

[0186] According to the first embodiment, the spin chuck 8 and the processing chamber 12 are housed in the chamber 7. The processing chamber 12 moves relative to the spin chuck 8 so that the substrate W moves relatively between the inside and outside of the processing chamber 12. Therefore, the processing chamber 12 can be lowered in the chamber 7 to house the substrate W in the processing chamber 12 (substrate housing step), and the processing chamber 12 can be raised in the chamber 7 to remove the substrate W from the processing chamber 12 (substrate removing step).

[0187] Therefore, with the substrate W placed in the processing chamber 12 that moves up and down within the chamber 7, the ozone-containing gas can be supplied to the processing chamber 12 to fill the processing chamber 12 with the ozone-containing gas. Therefore, the ozone-containing gas can be filled more quickly than when the chamber 7 is filled with the ozone-containing gas.

[0188] According to the first embodiment, when the substrate W is located outside the processing chamber 12, the sulfuric acid-containing liquid is supplied from the first moving nozzle 9 onto the upper surface of the substrate W to form a liquid film 100 on the upper surface of the substrate W, and then the substrate W can be placed inside the processing chamber 12. This allows the ozone-containing gas to be quickly supplied to the liquid film 100 on the upper surface of the substrate W in a configuration in which the first moving nozzle 9 is provided separately from the processing chamber 12.

[0189] The liquid film 100 of the sulfuric acid-containing liquid has a thickness (1 μm or more and 2 mm or less) and is thin enough to be heated quickly, so that the temperature of the liquid film 100 can be quickly increased by heating with the substrate heating member 14. Therefore, unlike the configuration shown in FIG. 3, the sulfuric acid-containing liquid supply unit 16 does not need to be provided with the tank heater 86 and the piping heater 85.

[0190] <Substrate Processing According to Modification> 9A to 9C are flowcharts for explaining substrate processing according to a modified example.

[0191] 9A differs from the substrate processing shown in FIG. 5 in that, in the substrate processing according to the first modification, a sulfuric acid-containing liquid discharge start step (step S31) is performed before a substrate heating start step (step S21). Specifically, the discharge of the sulfuric acid-containing liquid from the first movable nozzle 9 onto the upper surface of the substrate W is started before the substrate heating member 14 reaches the close position.

[0192] 9B differs from the substrate processing shown in FIG. 5 in that a substrate heating start step (step S21) is performed after an ozone-containing gas supply start step (step S41). Specifically, before the substrate heating member 14 reaches the proximity position, a liquid film of the sulfuric acid-containing liquid is formed, and the supply of the ozone-containing gas to the processing chamber 12 is started.

[0193] 9B, an ozone-containing gas supply stop step (step S42) may be performed before the substrate heating start step (step S21). Specifically, the supply of the ozone-containing gas to the processing chamber 12 may be stopped before the substrate heating member 14 reaches the proximity position.

[0194] On the other hand, heating of the substrate W does not necessarily have to be started when the processing chamber 12 is filled with an ozone-containing gas and a liquid film 100 is formed on the upper surface of the substrate W. That is, as in the substrate processing of Fig. 5, heating of the substrate W may be performed when the processing chamber 12 accommodating the substrate W is filled with an ozone-containing gas and a liquid film 100 is formed on the upper surface of the substrate W. In other words, regardless of the timing of starting heating of the substrate W, as long as the processing chamber 12 accommodating the substrate W is filled with an ozone-containing gas and the substrate W is heated in a state where the liquid film 100 is formed on the upper surface of the substrate W, an organic film can be quickly and sufficiently removed from the upper surface of the substrate W.

[0195] The substrate processing according to the third modified example shown in Figure 9C differs from the substrate processing shown in Figure 5 in that a hydrophilization process (step S12) is performed to hydrophilize the upper surface of the substrate W before a liquid film 100 of sulfuric acid-containing liquid is formed on the upper surface of the substrate W.

[0196] Specifically, after heating of the substrate W by the substrate heating member 14 is started, the processing chamber drive mechanism 73 moves the processing chamber 12 from the non-accommodating position to the accommodating position. Then, the ozone-containing gas valve 55A is opened. As a result, with the substrate W placed in the processing chamber 12, supply of ozone-containing gas into the processing chamber 12 is started (ozone-containing gas supply start step: step S121). By supplying the ozone-containing gas into the processing chamber 12, the processing chamber 12 is filled with the ozone-containing gas (ozone-containing gas supply step, ozone-containing gas filling step). By filling the processing chamber 12 with the ozone-containing gas, the upper surface of the substrate W is exposed to the ozone-containing gas (substrate upper surface exposing step).

[0197] After the upper surface of the substrate W has been exposed to the ozone-containing gas for a predetermined period of time, the ozone-containing gas valve 55A is closed. Then, with the ozone-containing gas valve 55A closed, the processing chamber drive mechanism 73 moves the processing chamber 12 from the accommodation position to the non-accommodation position. This stops the supply of ozone-containing gas into the processing chamber 12 (ozone-containing gas supply stopping step: step S122), and the exposure of the upper surface of the substrate W to the ozone-containing gas is stopped.

[0198] In the substrate processing according to the third modified example, the upper surface of the substrate W is hydrophilized before a liquid film 100 of the sulfuric acid-containing liquid is formed on the upper surface of the substrate W. Specifically, the upper surface of the substrate W is oxidized with an ozone-containing gas, thereby increasing the hydrophilicity of the upper surface of the substrate W (ozone hydrophilization process). By hydrophilizing the upper surface of the substrate W, the wettability of the upper surface of the substrate W is improved, and the sulfuric acid-containing liquid can easily spread over the upper surface of the substrate W. Therefore, the liquid film 100 of the sulfuric acid-containing liquid can be made thinner. In turn, by making the liquid film 100 thinner, ozone can more easily reach the upper surface of the substrate W, and organic films can be quickly and sufficiently removed from the upper surface of the substrate W.

[0199] In the substrate processing according to the third modification, the upper surface of the substrate W can be made hydrophilic by supplying an ozone-containing gas. Therefore, the ozone-containing gas can be used both to make the upper surface of the substrate W hydrophilic and to remove an organic film from the upper surface of the substrate W. Therefore, compared to when the upper surface of the substrate W is made hydrophilic using a method other than supplying an ozone-containing gas, the equipment required for the substrate processing can be simplified.

[0200] In the substrate processing according to the third modified example shown in Fig. 9C, the ozone-containing gas supply start step (step S121) is performed after the substrate heating start step (step S21). Although not shown, unlike the substrate processing according to the third modified example shown in Fig. 9C, the ozone hydrophilization start step (step S121) may be started before the substrate start step (step S21).

[0201] <Substrate Processing Apparatus According to Second Embodiment> 10 is a schematic diagram for explaining the configuration of the sulfuric acid-containing-liquid supply unit 16 and the sulfuric acid-containing-liquid recovery unit 17 provided in the substrate processing apparatus 1A according to the second embodiment. In FIG. 10, the same reference numerals as in FIG. 1 and the like are used for the components equivalent to those shown in the above-described FIGS. 1 to 9C, and the description thereof will be omitted.

[0202] In the second embodiment Related The substrate processing apparatus 1A differs from the substrate processing apparatus 1 according to the first embodiment mainly in that the substrate processing apparatus 1A further includes a sulfuric acid-containing liquid recovery unit 17 that recovers the sulfuric acid-containing liquid discharged from the upper surface of the substrate W.

[0203] The sulfuric acid-containing liquid recovery unit 17 includes a plurality of (two in the example shown in FIG. 10 ) recovery tanks 110 for recovering the sulfuric acid-containing liquid discharged from the processing unit 2, a recovery pipe 111 connecting the processing unit 2 and the plurality of recovery tanks 110, and a liquid delivery pipe 112 for delivering the sulfuric acid-containing liquid from the plurality of recovery tanks 110 to the storage tank 80.

[0204] The recovery tank 110 is a tank with a closed top, and an internal space SP of the recovery tank 110 is connected to the outside via an exhaust pipe 117. The recovery tank 110 has an internal space SP that contacts the liquid surface of the sulfuric acid-containing liquid in the recovery tank 110. The exhaust pipe 117 exhausts air from the internal space SP of the recovery tank 110.

[0205] The recovery pipe 111 includes an upstream recovery pipe 126 connected to the processing cup 15 of the processing unit 2, and a plurality of downstream recovery pipes 127 branching from the upstream recovery pipe 126 and connected to the plurality of recovery tanks 110, respectively.

[0206] The liquid supply pipe 112 includes a downstream liquid supply pipe 128 connected to the storage tank 80, and a plurality of upstream liquid supply pipes 129 branched from the downstream liquid supply pipe 128 and connected to the plurality of recovery tanks 110, respectively.

[0207] The sulfuric acid-containing liquid recovery unit 17 includes an upstream recovery valve 113 provided in the upstream recovery pipe 126, a waste pipe 114 connected to the upstream recovery pipe 126 upstream of the upstream recovery valve 113 and for disposing of the sulfuric acid-containing liquid in the upstream recovery pipe 126, and a waste valve 115 provided in the waste pipe 114.

[0208] The sulfuric acid-containing liquid recovery unit 17 further includes a downstream recovery valve 131, an ozone concentration meter 118, a recovery tank heater 119, a recovery temperature sensor 120, a liquid feed filter 121, a liquid feed pump 122, an upstream liquid feed valve 123, a liquid feed circulation pipe 124, and a liquid feed circulation valve 125. Each of these components is provided for each recovery tank 110.

[0209] The downstream recovery valve 131 opens and closes the downstream recovery pipe 127. The ozone concentration meter 118 measures the ozone concentration in the internal space SP of the recovery tank 110. The recovery tank heater 119 heats the sulfuric acid-containing liquid in the recovery tank 110. The recovery temperature sensor 120 measures the temperature of the sulfuric acid-containing liquid in the recovery tank 110.

[0210] The ozone concentration meter 118 includes, for example, a measuring device body and a gas supply pipe having a tip located in the internal space SP of the collection tank 110 and supplying gas in the internal space SP of the collection tank 110 to the measuring device body.

[0211] The collection tank heater 119 is, for example, a heater attached to the outer surface of the wall of the collection tank 110, as shown in Fig. 10. Unlike Fig. 10, the collection tank heater 119 may be attached to the lower surface of the bottom wall of the collection tank 110, or may be attached to both the bottom wall and the side wall. The collection tank heater 119 may be a heater immersed in the sulfuric acid-containing liquid in the collection tank 110.

[0212] The liquid feed filter 121 removes impurities from the sulfuric acid-containing liquid passing through the upstream liquid feed piping 129. The liquid feed pump 122 is provided downstream of the liquid feed filter 121 in the upstream liquid feed piping 129 and feeds the sulfuric acid-containing liquid in the upstream liquid feed piping 129 toward the storage tank 80.

[0213] The upstream liquid feed valve 123 is provided downstream of the liquid feed pump 122 in the upstream liquid feed piping 129 and opens and closes the upstream liquid feed piping 129. The liquid feed circulation piping 124 is connected downstream of the liquid feed pump 122 and upstream of the upstream liquid feed valve 123 in the upstream liquid feed piping 129. The liquid feed circulation valve 125 opens and closes the liquid feed circulation piping 124.

[0214] According to the second embodiment, the sulfuric acid-containing liquid supplied from the first moving nozzle 9 to the upper surface of the substrate W can be recovered and reused. This reduces the amount of sulfuric acid waste. By heating the sulfuric acid-containing liquid recovered in the recovery tank 110, the ozone dissolved in the sulfuric acid-containing liquid can be vaporized. By vaporizing and removing the ozone from the sulfuric acid-containing liquid, the sulfuric acid-containing liquid from which the ozone has been sufficiently removed can be reused. This makes it possible to suppress fluctuations in the ozone concentration in the liquid film 100 of the sulfuric acid-containing liquid formed on the upper surface of the substrate W.

[0215] Furthermore, since a plurality of collection tanks 110 are provided, even if any of the collection tanks 110 is not ready, the sulfuric acid-containing liquid can be supplied from another collection tank 110 to the storage tank 80. When the collection tank 110 is not ready, it means that the amount of the sulfuric acid-containing liquid in the collection tank 110 is insufficient or that ozone has not been sufficiently removed from the sulfuric acid-containing liquid in the collection tank 110.

[0216] <Substrate Processing Apparatus According to Third Embodiment> Fig. 11 is a schematic diagram for explaining the configuration of a processing unit 2 provided in a substrate processing apparatus 1B according to a third embodiment. In Fig. 11, the same reference numerals as in Fig. 1 to 10 are used for components equivalent to those shown in Fig. 1 and the like, and descriptions thereof will be omitted. The same applies to Fig. 12 described later.

[0217] The processing unit 2 according to the third embodiment is mainly different from the processing unit 2 according to the first embodiment in that the processing unit 2 according to the third embodiment does not include the processing chamber 12.

[0218] More specifically, the ozone-containing gas supply member 13 provided in the processing unit 2 according to the third embodiment supplies an ozone-containing gas to the internal space 7c of the chamber 7. The ozone-containing gas supply member 13 includes, for example, an ozone-containing gas discharge nozzle 130 disposed in the chamber 7. An ozone-containing gas pipe 45 is connected to the ozone-containing gas discharge nozzle 130. The supply of the ozone-containing gas to the internal space 7c of the chamber 7 can be started by opening the ozone-containing gas valve 55A. In the third embodiment, the chamber 7 functions as a processing chamber.

[0219] Unlike in FIG. 11, the ozone-containing gas supply member 13 may have an outlet opening in the side wall 7b of the chamber 7.

[0220] In the third embodiment, the same substrate processing as that in the first embodiment (FIG. 5, FIGS. 9A to 9C) can be performed.

[0221] In the third embodiment, the substrate processing shown in Fig. 12 can also be performed. Fig. 12 is a flowchart for explaining an example of the substrate processing performed by the substrate processing apparatus 1B. In the substrate processing shown in Fig. 12, unlike the substrate processing shown in Fig. 9C, the supply of the ozone-containing gas to the processing chamber 12 is started before the liquid film forming step (step S3) and stopped after the liquid film forming step (step S3) is completed.

[0222] More specifically, current is supplied to the heater 61 by the power supply unit 63, and the temperature of the heater 61 begins to rise. Then, the heater drive mechanism 66 moves the substrate heating member 14 from the retracted position to the proximal position. The temperature of the heater 61 begins to rise, and the substrate heating member 14 is disposed at the proximal position, thereby starting heating of the substrate W (substrate heating start step: step S21). This executes the substrate heating step (step S2).

[0223] Before the discharge of the sulfuric acid-containing liquid onto the upper surface of the substrate W is started, the ozone-containing gas valve 55A is opened. This starts the supply of ozone-containing gas from the ozone-containing gas supply member 13 to the internal space 7c of the chamber 7 (ozone-containing gas supply start step: step S121). By continuing the supply of ozone-containing gas to the internal space 7c of the chamber 7, the chamber 7 can be filled with ozone-containing gas (ozone-containing gas supply step, ozone-containing gas filling step).

[0224] By filling the chamber 7 with an ozone-containing gas, the upper surface of the substrate W held on the spin chuck 8 is exposed to the ozone-containing gas (substrate upper surface exposing step). By exposing the upper surface of the substrate W to the ozone-containing gas, the upper surface of the substrate W is made hydrophilic (ozone hydrophilization step, hydrophilization step: step S12).

[0225] Thereafter, a liquid film forming step (step S3) is performed. With the liquid film 100 of the sulfuric acid-containing liquid formed on the upper surface of the substrate W, the inside of the chamber 7 can be pressurized by supplying an ozone-containing gas into the chamber 7 (pressurization supply step).

[0226] After the liquid film forming step (step S3), the ozone-containing gas valve 55A is closed. This stops the supply of ozone-containing gas from the ozone-containing gas supply member 13 to the internal space 7c of the chamber 7 (ozone-containing gas supply stopping step: step S41). With the supply of ozone-containing gas stopped, the ozone-containing gas is exhausted from the internal space 7c of the chamber 7 via the exhaust pipe 32, thereby stopping exposure of the upper surface of the substrate W to the ozone-containing gas.

[0227] Thereafter, the heater drive mechanism 66 moves the substrate heating member 14 from the proximity position to the retracted position. By placing the substrate heating member 14 in the retracted position, heating of the substrate W is stopped (substrate heating stopping step: step S22). This ends the substrate heating step (step S2).

[0228] Thereafter, the first rinse step (step S5) to the substrate unloading step (step S11) are carried out in sequence.

[0229] In this way, by using the substrate processing apparatus 1B according to the third embodiment, the supply of the ozone-containing gas can be started before the discharge of the sulfuric acid-containing liquid. Therefore, various substrate processes can be performed compared to the substrate processing apparatus 1 according to the first embodiment. be The substrate processing apparatus 1B according to the third embodiment has the same effects as the substrate processing apparatus 1 according to the first embodiment.

[0230] 12 , in a substrate processing in which the supply of the ozone-containing gas is started before the discharge of the sulfuric acid-containing liquid, the supply of the ozone-containing gas may be started based on the temperature detected by the temperature sensor 62. Specifically, when the temperature determination unit 90 determines that the temperature detected by the temperature sensor 62 is within the processing temperature range, the first start unit 91 starts the supply of the ozone-containing gas from the ozone-containing gas supply member 13. Therefore, the supply of the ozone-containing gas from the ozone-containing gas supply member 13 is started in a state in which the substrate W is heated to a sufficiently high temperature. Therefore, the removal of the organic film from the upper surface of the substrate W can be started promptly.

[0231] <Other embodiments> The present invention is not limited to the above-described embodiment, and can be embodied in other forms.

[0232] (1) In each of the above-described embodiments, the processing liquid is ejected from a plurality of movable nozzles. However, unlike the above-described embodiments, the processing liquid may be ejected from a fixed nozzle whose position in the horizontal direction is fixed, or all of the processing liquid may be ejected from a single nozzle.

[0233] For example, unlike the first embodiment, the first moving nozzle 9 may not be provided, and the sulfuric acid-containing liquid supply member may include a sulfuric acid-containing liquid nozzle having a discharge port exposed from the housing 71 of the processing chamber 12. In this case, the same substrate processing as in the third embodiment (for example, see FIG. 12) can be performed.

[0234] (2) In the above-described embodiment, a continuous flow of the sulfuric acid-containing liquid is supplied to the upper surface of the substrate W, and the sulfuric acid-containing liquid is spread by centrifugal force to form the liquid film 100. However, the liquid film 100 may also be formed on the upper surface of the substrate W by applying the sulfuric acid-containing liquid. Specifically, the liquid film 100 may be formed by moving a bar-shaped application member having the sulfuric acid-containing liquid adhered to its surface along the upper surface of the substrate W while contacting the upper surface of the substrate W. Alternatively, the liquid film 100 may be formed by supplying a continuous flow of the sulfuric acid-containing liquid to the upper surface of the substrate W, and then spreading the liquid film 100 over the entire upper surface of the substrate W with the bar-shaped application member.

[0235] (3) Examples of substrate processing are shown in FIGS. 5, 9A to 9C, and 12. However, examples of substrate processing are not limited to those described above. For example, after the supply of ozone-containing gas to the processing chamber 12 is completed, the processing chamber 12 may be moved to the accommodation position to expose the liquid film 100 to the ozone-containing gas. Alternatively, the discharge of the sulfuric acid-containing liquid and the supply of the ozone-containing gas may be started simultaneously. Furthermore, the substrate heating stopping step (step S22) may be stopped during the execution of the first rinsing step (step S5). Furthermore, the chemical liquid supplying step (step S7) to the organic solvent supplying step (step S9) may be omitted as appropriate.

[0236] When the discharge of the sulfuric acid-containing liquid and the supply of the ozone-containing gas are started simultaneously, the temperature detected by the temperature sensor 62 degree In detail, when the temperature determination unit 90 determines that the temperature detected by the temperature sensor 62 is within the processing temperature range, the first start unit 91 starts both the supply of the ozone-containing gas and the supply of the sulfuric acid-containing liquid. acid Alternatively, both the discharge of the liquid and the discharge of the containing liquid may be started.

[0237] (4) Heating of the substrate W is not limited to heating by the substrate heating member 14. Specifically, the substrate heating member may include an infrared lamp facing the upper surface of the substrate W, or may include a heater facing the upper surface of the substrate W. Alternatively, the substrate heating member may include a heating fluid nozzle that supplies a heating fluid such as nitrogen gas or hot water to the lower surface of the substrate W. The substrate heating member may be configured to heat the plate body 60 by circulating a heating fluid within the plate body 60. When a heating fluid is used, the temperature of the substrate W is adjusted by adjusting the opening of a valve that controls the flow rate of the heating fluid.

[0238] (5) The substrate processing apparatus 1 may be provided with a cooling plate (not shown) for cooling the substrate W. After the substrate heating stopping step (step S22), the substrate W may be cooled to room temperature by the cooling plate.

[0239] (6) In each of the above-described embodiments, the spin chuck 8 is a gripping-type spin chuck that grips the periphery of the substrate W with a plurality of gripping pins 20, but the spin chuck 8 is not limited to a gripping-type spin chuck. For example, the spin chuck 8 may be a vacuum suction-type spin chuck that suctions the substrate W to the spin base 21.

[0240] (7) The configuration of the processing chamber 12 is not limited to that shown in FIG. 2. For example, the processing chamber may be an openable / closable chamber. within 7 It may be provided in.

[0241] The spin base 21 may also be configured to move up and down. Therefore, the substrate accommodating step may be a step of raising (moving) the substrate W in the chamber 7 to accommodate the substrate W in the processing chamber 12, and the substrate removing step may be a step of lowering (moving) the substrate W in the chamber 7 to remove the substrate W from the processing chamber 12. In short, the substrate accommodating step may be a step of moving the processing chamber 12 relative to the substrate W in the chamber 7 to accommodate the substrate W in the processing chamber 12. Similarly, the substrate removing step may be a step of moving the processing chamber 12 relative to the substrate W in the chamber 7 to accommodate the substrate W in the processing chamber 12.

[0242] (8) The upper surface of the substrate W may be made hydrophilic by a method other than oxidation with an ozone-containing gas. For example, the upper surface of the substrate W may be made hydrophilic by irradiating the upper surface with ultraviolet light.

[0243] (9) In each of the above-described embodiments, the controller 3 controls the entire substrate processing apparatus 1. However, the controllers controlling the components of the substrate processing apparatus 1 may be distributed across multiple locations. Furthermore, the controller 3 does not need to directly control each component, and signals output from the controller 3 may be received by a slave controller that controls each component of the substrate processing apparatus 1.

[0244] (10) In the above-described embodiments, the substrate processing apparatus 1, 1A, 1B includes a transport robot (first transport robot IR and second transport robot CR), a plurality of processing units 2, and a controller 3. However, the substrate processing apparatus 1, 1A, 1B may be configured with a single processing unit 2 and a controller 3 and may not include a transport robot. Alternatively, the substrate processing apparatus 1, 1A, 1B may be configured with only a single processing unit 2. In other words, the processing unit 2 may be an example of the substrate processing apparatus.

[0245] (11) In the above-described embodiment, expressions such as "along," "horizontal," "vertical," and "cylindrical" are used. However, these expressions do not necessarily have to be "along," "horizontal," "vertical," and "cylindrical" in the strict sense. In other words, these expressions allow for deviations in manufacturing precision, installation precision, and the like.

[0246] (12) Although each component may be shown as a schematic block, the shape, size, and positional relationship of each block do not represent the shape, size, and positional relationship of each component.

[0247] In addition, various modifications can be made within the scope of the claims. [Explanation of symbols]

[0248] 1: Substrate processing equipment 1A: Substrate processing equipment 1B: Substrate processing equipment 3: Controller 7: Chamber (processing chamber) 7c: Internal space 8: Spin chuck (substrate holding member) 9: First moving nozzle (sulfuric acid-containing liquid discharge member) 12: Processing room 13: Ozone-containing gas supply member 14: Substrate heating element 16: Sulfuric acid-containing liquid supply unit 17: Sulfuric acid-containing liquid recovery unit 25: First nozzle drive mechanism (nozzle drive mechanism) 62: Temperature sensor 70: Interior space 71: Housing 73: Processing chamber drive mechanism 76: Ozone-containing gas outlet 90: Temperature determination unit 91: First starting unit 94: Second time lapse judgment unit (time lapse judgment unit) 95: Second starting unit W: Substrate

Claims

1. A liquid film forming step of forming a liquid film of a sulfuric acid-containing liquid on a main surface of a substrate having an organic film formed on the main surface; an ozone-containing gas exposure step of filling a processing chamber containing the substrate with an ozone-containing gas and exposing the liquid film to the ozone-containing gas, thereby dissolving ozone in the ozone-containing gas into the sulfuric acid-containing liquid that constitutes the liquid film, thereby forming peroxodisulfuric acid in the liquid film; a substrate heating step of heating the substrate by a substrate heating member while the substrate is placed in the processing chamber filled with an ozone-containing gas, the liquid film being formed on a main surface of the substrate, and peroxodisulfuric acid being formed in the liquid film.

2. 2. The substrate processing method according to claim 1, wherein heating of the substrate in the substrate heating step is started before the liquid film forming step and the ozone-containing gas exposing step.

3. 3. The substrate processing method according to claim 1, wherein the ozone-containing gas exposure step includes a pressurizing supply step of supplying the ozone-containing gas into the processing chamber so that the pressure inside the processing chamber is higher than the pressure outside the processing chamber.

4. 4. The substrate processing method according to claim 1, further comprising, after the substrate heating step, a rinse liquid supplying step of supplying a rinse liquid to the main surface of the substrate.

5. 5. The substrate processing method according to claim 1, wherein the liquid film forming step includes: a sulfuric acid-containing-liquid supplying step of supplying a sulfuric acid-containing liquid toward the main surface of the substrate; and a thinning step of rotating the substrate about a central axis passing through a center of the substrate after stopping the supply of the sulfuric acid-containing liquid to the main surface of the substrate, thereby thinning the sulfuric acid-containing liquid on the main surface of the substrate, thereby forming the liquid film.

6. 6. The substrate processing method according to claim 1, wherein the ozone-containing gas exposure step includes a step of filling the processing chamber with the ozone-containing gas by starting a supply of the ozone-containing gas into the processing chamber while the substrate having the liquid film formed on its main surface is placed in the processing chamber.

7. 7. The substrate processing method according to claim 1, further comprising a hydrophilization step of hydrophilizing the main surface of the substrate before the formation of the liquid film is started in the liquid film forming step.

8. 8. The substrate processing method according to claim 7, wherein the hydrophilization process includes an ozone hydrophilization process in which an ozone-containing gas is supplied to the processing chamber while the substrate is placed in the processing chamber before the formation of the liquid film in the liquid film forming process is started, thereby exposing the main surface of the substrate to an ozone-containing gas.

9. The method further includes a substrate holding step of holding the substrate on a substrate holding member disposed in a chamber, 9. The substrate processing method according to claim 1, wherein the ozone-containing gas exposure step includes: a substrate accommodating step of accommodating the substrate held by the substrate holding member in the processing chamber by moving the processing chamber relative to the substrate held by the substrate holding member in the chamber; an ozone-containing gas supplying step of supplying an ozone-containing gas into the processing chamber with the substrate accommodated in the processing chamber; and a substrate removing step of removing the substrate held by the substrate holding member from the processing chamber after the ozone-containing gas supplying step by moving the processing chamber relative to the substrate held by the substrate holding member in the chamber.

10. A substrate holding member that holds a substrate having an organic film formed on a main surface thereof in a predetermined processing posture; a processing chamber capable of accommodating the substrate held by the substrate holding member; a substrate heating member for heating the substrate held by the substrate holding member; an ozone-containing gas supply member for supplying an ozone-containing gas into the processing chamber; a sulfuric acid-containing liquid discharge member that discharges a sulfuric acid-containing liquid toward a main surface of the substrate held by the substrate holding member; a controller that controls the substrate heating member, the ozone-containing gas supply member, and the sulfuric acid-containing liquid discharge member; the controller, in a state in which the substrate held by the substrate holding member is placed in the processing chamber and the substrate is heated by the substrate heating member, discharges the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member toward the main surface of the substrate to form a liquid film of the sulfuric acid-containing liquid on the main surface of the substrate, and supplies an ozone-containing gas from the ozone-containing gas supply member to the processing chamber to expose the liquid film to the ozone-containing gas, thereby dissolving ozone in the ozone-containing gas into the sulfuric acid-containing liquid that constitutes the liquid film to form peroxodisulfuric acid in the liquid film, and heats the substrate with the substrate heating member in a state in which peroxodisulfuric acid has been formed in the liquid film.

11. a temperature sensor for detecting a temperature of the substrate heating member; 11. The substrate processing apparatus according to claim 10, wherein the controller includes: a temperature determination unit that determines whether the temperature detected by the temperature sensor is within a processing temperature range; and a first start unit that, when the temperature determination unit determines that the temperature detected by the temperature sensor is within the processing temperature range, starts at least one of the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member and the supply of the ozone-containing gas from the ozone-containing gas supply member.

12. When the temperature determination unit determines that the temperature detected by the temperature sensor is within the processing temperature range, the first start unit starts discharging the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharging member, The controller includes a time lapse determination unit that determines whether a liquid film formation time has elapsed after the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member has started; 12. The substrate processing apparatus according to claim 11, further comprising: a second start unit that starts supplying the ozone-containing gas from the ozone-containing gas supply member when the time elapse determination unit determines that the liquid film formation time has elapsed.

13. a chamber that accommodates the substrate holding member and the processing chamber; The substrate processing apparatus according to any one of claims 10 to 12, further comprising a processing chamber drive mechanism that moves the processing chamber relative to the substrate holding member so that the substrate held by the substrate holding member moves relatively between inside and outside the processing chamber.

14. the sulfuric acid-containing liquid discharge member includes a sulfuric acid-containing liquid nozzle that discharges the sulfuric acid-containing liquid, 14. The substrate processing apparatus according to claim 13, further comprising a nozzle driving mechanism that moves the sulfuric acid-containing liquid nozzle to a processing position between the processing chamber and the main surface of the substrate while the substrate held by the substrate holding member is located outside the processing chamber.

15. the processing chamber has a housing that defines an internal space of the processing chamber; 15. The substrate processing apparatus according to claim 13, wherein the ozone-containing gas supply member has a plurality of ozone-containing gas discharge ports exposed from the housing and connected to the internal space.

16. a sulfuric acid-containing liquid recovery unit that recovers a sulfuric acid-containing liquid discharged from a main surface of the substrate held by the substrate holding member; 16. The substrate processing apparatus according to claim 10, further comprising a sulfuric acid-containing liquid supply unit that supplies the sulfuric acid-containing liquid recovered by the sulfuric acid-containing liquid recovery unit to the sulfuric acid-containing liquid discharge member.

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