Substrate processing method and substrate processing apparatus

Abstract

The present invention provides a substrate processing method and a substrate processing apparatus. The substrate processing method includes: a liquid film forming step of forming a liquid film containing a sulfuric acid liquid on a main surface of a substrate; an ozone-containing gas exposure step of filling a processing chamber capable of accommodating the substrate with an ozone-containing gas to expose the liquid film to the ozone-containing gas; and a substrate heating step of heating the substrate in a state where the substrate is disposed in the processing chamber filled with the ozone-containing gas and the liquid film is formed on the main surface of the substrate.

Description

[0001] This application claims priority based on Japanese Patent Application No. 2021-141268 filed on August 31, 2021, the entire content of which is incorporated herein by reference. Technical Field

[0002] The present invention relates to a substrate processing method for processing a substrate and a substrate processing apparatus for processing a substrate. Substrates to be processed include, for example, semiconductor wafers, substrates for flat panel displays (FPDs) such as liquid crystal display devices and organic electroluminescence (EL) display devices, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like. Background Art

[0003] In the substrate processing apparatus disclosed in US2014 / 0045339A1, ozone gas is supplied into a pipe to sulfuric acid to dissolve ozone in sulfuric acid to form sulfuric acid ozone. By mixing sulfuric acid and ozone, persulfuric acid (S2O8 2- ) is generated as an active species (etchant).

[0004] In the substrate processing apparatus of US2014 / 0045339A1, sulfuric acid ozone flows through a sulfuric acid ozone supply pipe and flows into a water mixing section to be mixed with water, thereby forming a sulfuric acid ozone / water mixture. The sulfuric acid ozone / water mixture is discharged from a sulfuric acid ozone / water nozzle onto the substrate. By supplying the sulfuric acid ozone / water mixture to the surface of the substrate while rotating the substrate, the resist on the substrate surface is removed. Summary of the Invention

[0005] In the substrate processing apparatus disclosed in US2014 / 0045339A1, due to the dilution heat generated by mixing water into sulfuric acid ozone, the temperature of the sulfuric acid ozone / water mixture becomes higher than the temperature of the sulfuric acid ozone before mixing. Therefore, even if relatively low-temperature sulfuric acid ozone is used as the sulfuric acid ozone before mixing, a sulfuric acid ozone / water mixture at a temperature required to remove the resist can be supplied to the surface of the substrate. In addition, by making 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.

[0006] However, in the apparatus of US2014 / 0045339A1, by mixing sulfuric acid ozone with water, the concentration of oxidizing persulfuric acid decreases. Therefore, sufficient oxidizing power may not be obtained.

[0007] Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of rapidly and sufficiently removing an organic film such as a resist from a substrate.

[0008] One embodiment of the present invention provides a substrate processing method, which includes: a liquid film forming step of forming a liquid film containing a sulfuric acid liquid on a main surface of a substrate; an ozone-containing gas exposure step of filling a processing chamber capable of accommodating the substrate with an ozone-containing gas to expose the liquid film to the ozone-containing gas; and a substrate heating step of disposing the substrate in the processing chamber filled with the ozone-containing gas and heating the substrate in a state where the liquid film is formed on the main surface of the substrate.

[0009] According to this method, by filling the processing chamber with the ozone-containing gas, the liquid film of the sulfuric acid liquid on the main surface of the substrate is exposed to the ozone-containing gas. Thereby, ozone in the ozone-containing gas can be dissolved in the sulfuric acid liquid constituting the liquid film on the main surface of the substrate to form peroxydisulfuric acid in the liquid film.

[0010] In addition, the substrate is heated in a state where the liquid film is formed on the main surface of the substrate. That is, the substrate is heated in a state where peroxydisulfuric acid is formed in the sulfuric acid liquid constituting the liquid film on the main surface of the substrate. Therefore, the oxidizing power of peroxydisulfuric acid can be enhanced.

[0011] Furthermore, the substrate is heated in a state where the processing chamber is filled with the ozone-containing gas. Therefore, even if the solubility of ozone in the sulfuric acid liquid decreases due to heating, a state where the ozone-containing gas containing a sufficient concentration of ozone is in contact with the sulfuric acid liquid can be maintained. Therefore, the vaporization of ozone in the sulfuric acid liquid can be suppressed.

[0012] As a result, an organic film such as a resist can be removed from the substrate quickly and sufficiently.

[0013] The ozone-containing gas contains gaseous ozone (ozone gas), and the sulfuric acid liquid contains sulfuric acid. The sulfuric acid liquid is, for example, an aqueous sulfuric acid solution.

[0014] In one embodiment of the present invention, the heating of the substrate in the substrate heating step starts before the liquid film forming step and the ozone-containing gas exposure step.

[0015] According to this method, the heating of the substrate starts before the formation of the liquid film of the sulfuric acid liquid and the exposure of the ozone-containing gas to the liquid film. Therefore, even when the time required for the temperature of the substrate to rise is longer than the time required for the formation of the liquid film and the time required for filling with the ozone-containing gas, the temperature of the substrate can quickly reach the desired temperature.

[0016] In one embodiment of the present invention, the ozone-containing gas exposure step includes a pressurized supply step of supplying the ozone-containing gas to the processing chamber in such a manner that the pressure in the processing chamber is higher than the pressure outside the processing chamber.

[0017] According to this method, by supplying an ozone-containing gas, the pressure in the processing chamber can be made higher than the pressure outside the processing chamber. Here, based on 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, if an ozone-containing gas is supplied to the processing chamber to increase 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. Thereby, the concentration of peroxydisulfuric acid in the liquid film can be increased, and thus the organic film can be quickly and sufficiently removed from the main surface of the substrate.

[0018] In one embodiment of the present invention, the substrate processing method further includes: a rinse liquid supply step of supplying a rinse liquid to the main surface of the substrate after the substrate heating step.

[0019] According to this method, the liquid film of the sulfuric acid-containing liquid can be removed from the main surface of the substrate by using the rinse liquid. Therefore, it is possible to suppress sulfuric acid from remaining on the main surface of the substrate after removing the organic film from the main surface of the substrate.

[0020] In one embodiment of the present invention, the liquid film forming step includes: a sulfuric acid-containing liquid supply step of supplying a sulfuric acid-containing liquid to the main surface of the substrate; and a thinning step of rotating the substrate around a central axis passing through the central portion of the substrate to thin the sulfuric acid-containing liquid on the main surface of the substrate after stopping the supply of the sulfuric acid-containing liquid to the main surface of the substrate, thereby forming the liquid film.

[0021] Therefore, compared with the case where a continuous flow of the sulfuric acid-containing liquid is supplied to the main surface of the substrate while spreading the sulfuric acid-containing liquid over the entire main surface of the substrate, the time for supplying the sulfuric acid-containing liquid to the main surface of the substrate can be shortened. Therefore, the amount of the sulfuric acid-containing liquid used can be reduced.

[0022] Furthermore, compared with the case where a continuous flow of the sulfuric acid-containing liquid is supplied to the main surface of the substrate while spreading the sulfuric acid-containing liquid over the entire main surface of the substrate, the liquid film of the sulfuric acid-containing liquid on the main surface of the substrate can be thinned. Therefore, the time required for heating the liquid film of the sulfuric acid-containing liquid can be reduced, achieving power saving.

[0023] Peroxydisulfuric acid generated by the reaction of ozone dissolved in the sulfuric acid-containing liquid from the surface of the liquid film of the sulfuric acid-containing liquid with sulfuric acid diffuses in the liquid film and reaches the main surface of the substrate, thereby reacting with the organic film on the main surface of the substrate. Therefore, if the liquid film of the sulfuric acid-containing liquid is thinned, peroxydisulfuric acid can easily reach the main surface of the substrate. Therefore, the organic film can be quickly and sufficiently removed from the main surface of the substrate.

[0024] In one embodiment of the present invention, the ozone-containing gas exposure step includes: a step of starting to supply an ozone-containing gas to the processing chamber in a state where the substrate having the liquid film formed on the main surface is disposed in the processing chamber, so that the processing chamber is filled with the ozone-containing gas.

[0025] When the supply of the ozone-containing gas to the processing chamber is completed and a liquid film of sulfuric acid-containing liquid is formed, the ozone concentration in the atmosphere in the processing chamber may decrease 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 in a state where 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 in a state where 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 formed on the main surface of the substrate can be increased.

[0026] In one embodiment of the present invention, the substrate processing method further includes: a hydrophilic treatment step of hydrophilizing the main surface of the substrate before the start of the formation of the liquid film in the liquid film formation step.

[0027] According to this method, before the liquid film of the sulfuric acid-containing liquid is formed on the main surface of the substrate, the main surface of the substrate is hydrophilized. Therefore, the wettability of the main surface of the substrate is improved, and the sulfuric acid-containing liquid easily spreads on the main surface of the substrate. Therefore, thinning of the liquid film of the sulfuric acid-containing liquid can be achieved. Furthermore, by thinning the liquid film, ozone can easily reach the main surface of the substrate, and the organic film can be quickly and sufficiently removed from the main surface of the substrate.

[0028] In one embodiment of the present invention, the hydrophilic treatment step includes: an ozone hydrophilization treatment step of supplying an ozone-containing gas to the processing chamber in a state where the substrate is disposed in the processing chamber before the start of the formation of the liquid film in the liquid film formation step, so that the main surface of the substrate is exposed to the ozone-containing gas.

[0029] According to this method, the main surface of the substrate can be hydrophilized by supplying the ozone-containing gas. Therefore, the ozone-containing gas can be used for both hydrophilization of the main surface of the substrate and removal of the organic film from the main surface of the substrate. Therefore, compared with the case of using a method other than the supply of the ozone-containing gas for hydrophilization of the main surface of the substrate, the equipment required for substrate processing can be simplified.

[0030] In an embodiment of the present invention, the substrate processing method further includes: a substrate holding step of holding the substrate on a substrate holding member disposed in a chamber. And, the ozone-containing gas exposure step includes: a substrate accommodating step of relatively moving the processing chamber with respect to the substrate held on the substrate holding member in the chamber to accommodate the substrate held on the substrate holding member in the processing chamber; an ozone-containing gas supply step of supplying an ozone-containing gas to the processing chamber in a state where the substrate is accommodated in the processing chamber; and a substrate discharging step of relatively moving the processing chamber with respect to the substrate held on the substrate holding member in the chamber after the ozone-containing gas supply step to discharge the substrate held on the substrate holding member from the processing chamber.

[0031] According to this method, in a state where a substrate is disposed in a processing chamber disposed in a chamber, an ozone-containing gas can be supplied to the processing chamber to fill the processing chamber with the ozone-containing gas. Therefore, compared with the case where the chamber is filled with the ozone-containing gas, the ozone-containing gas can be filled quickly.

[0032] 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 on the substrate holding member; a substrate heating member that heats the substrate held on the substrate holding member; an ozone-containing gas supply member that supplies an ozone-containing gas to the processing chamber; a sulfuric acid-containing liquid discharging member that discharges sulfuric acid-containing liquid toward a main surface of the substrate held on 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 discharging member.

[0033] And, the controller discharges sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharging member toward the main surface of the substrate in a state where the substrate held on the substrate holding member is disposed in the processing chamber and the substrate is heated by the substrate heating member, forms a liquid film of 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.

[0034] According to this apparatus, in a state where the substrate disposed in the processing chamber is heated, a liquid film of 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, in a state where the processing chamber is filled with the ozone-containing gas, a liquid film of sulfuric acid-containing liquid is formed on the main surface of the substrate. Therefore, ozone in the ozone-containing gas can be dissolved in the sulfuric acid-containing liquid constituting the liquid film on the main surface of the substrate to form peroxydisulfuric acid in the liquid film.

[0035] In addition, the substrate is heated in a state where persulfuric acid is formed in the sulfuric acid-containing liquid of the liquid film on the main surface of the substrate. As a result, the oxidizing power of persulfuric acid can be enhanced.

[0036] In addition, the substrate is heated in a state where the processing chamber 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 state where the ozone-containing gas containing a sufficient concentration of ozone is in contact with the sulfuric acid-containing liquid can be maintained. As a result, the vaporization of ozone in the sulfuric acid-containing liquid can be suppressed.

[0037] As a result, an organic film such as a resist can be rapidly and sufficiently removed from the substrate.

[0038] In other embodiments of the present invention, the substrate processing apparatus further includes a temperature sensor that detects the temperature of the substrate heating member. And, the controller includes: a temperature determination unit that determines whether the detected temperature based on the temperature sensor is within a processing temperature range; and a first start unit that, when the temperature determination unit determines that the detected temperature of 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.

[0039] According to this apparatus, when the detected temperature of the temperature sensor is 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, 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. As a result, the removal of the organic film from the main surface of the substrate can be started rapidly.

[0040] In other embodiments 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 detected temperature of the temperature sensor is within the processing temperature range. Moreover, the controller further includes: a time elapse determination unit that determines whether a liquid film formation time has elapsed after starting the discharge of the sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member; 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.

[0041] According to this apparatus, when the detected temperature of the temperature sensor is within the processing temperature range, the sulfuric acid-containing liquid is started to be discharged from the sulfuric acid-containing liquid discharging member. Therefore, the sulfuric acid-containing liquid supplied to the main surface of the substrate can be heated rapidly. Further, after starting to discharge the sulfuric acid-containing liquid, if the liquid film formation time has elapsed, the ozone-containing gas is started to be supplied to the processing chamber. Therefore, after forming the liquid film, the ozone-containing gas is rapidly started to be supplied to the processing chamber. Accordingly, the substrate can be processed with high reproducibility, and thus the organic film can be removed from the main surface of the substrate with high reproducibility.

[0042] In another embodiment of the present invention, the substrate processing apparatus further includes: a chamber that houses the substrate holding member and the processing chamber; and a processing chamber driving mechanism that relatively moves the processing chamber with respect to the substrate holding member in such a manner that the substrate held by the substrate holding member relatively moves between inside and outside the processing chamber.

[0043] According to this apparatus, in a state where the substrate is disposed in the processing chamber housed in the chamber, the ozone-containing gas can be supplied to the processing chamber to fill the processing chamber with the ozone-containing gas. Therefore, compared with the case of filling the chamber with the ozone-containing gas, the ozone-containing gas can be filled rapidly.

[0044] In other embodiments of the present invention, the sulfuric acid-containing liquid discharging member includes a sulfuric acid-containing liquid nozzle that discharges the sulfuric acid-containing liquid. Further, the substrate processing apparatus further includes 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 in a state where the substrate held by the substrate holding member is outside the processing chamber.

[0045] According to this apparatus, when the substrate is outside the processing chamber, the sulfuric acid-containing liquid is supplied from the sulfuric acid-containing liquid nozzle to the main surface of the substrate, and after forming a liquid film of the sulfuric acid-containing liquid on the main surface of the substrate, the substrate can be disposed in the processing chamber. Thereby, in a configuration in which the sulfuric acid-containing liquid nozzle and the processing chamber are separately provided, the ozone-containing gas can be rapidly supplied to the liquid film of the sulfuric acid-containing liquid on the main surface of the substrate.

[0046] In other embodiments of the present invention, the processing chamber has a housing that divides an internal space of the processing chamber. Further, the ozone-containing gas supply member has a plurality of ozone-containing gas discharge ports that protrude from the housing and are connected to the internal space. Therefore, the ozone-containing gas can be rapidly supplied to the whole inside of the processing chamber (internal space).

[0047] In other embodiments 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. According to this structure, it is possible to recover the sulfuric acid-containing liquid supplied to the main surface of the substrate from the sulfuric acid-containing liquid supply member and reuse the sulfuric acid-containing liquid. Thereby, the amount of sulfuric acid to be discarded can be reduced.

[0048] Referring to the accompanying drawings, the above or other objects, features, and effects of the present invention will be clarified by the description of the embodiments described below. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 It is a plan view for explaining a configuration example of a substrate processing apparatus according to a first embodiment of the present invention.

[0050] Figure 2 It is a schematic diagram for explaining the configuration of a processing unit included in the substrate processing apparatus.

[0051] Figure 3 It is a schematic diagram for explaining the configuration of a sulfuric acid-containing liquid supply unit included in the substrate processing apparatus.

[0052] Figure 4 It is a block diagram for explaining the electrical configuration of the substrate processing apparatus.

[0053] Figure 5 It is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus.

[0054] Figures 6A - 6E It is a schematic diagram for explaining the situation of the substrate and its surroundings when performing the substrate processing.

[0055] Figure 7 It is a block diagram for explaining the functional configuration of a controller included in the substrate processing apparatus.

[0056] Figure 8 It is a flowchart for explaining an example of an organic film removal process performed by the controller.

[0057] Figure 9A It is a flowchart for explaining the substrate processing of a first modification example.

[0058] Figure 9B It is a flowchart for explaining the substrate processing of a second modification example.

[0059] Figure 9C It is a flowchart for explaining the substrate processing of a third modification example.

[0060] Figure 10 It is a schematic diagram showing the configuration of a sulfuric acid-containing liquid supply unit and a sulfuric acid-containing liquid recovery unit included in the substrate processing apparatus according to the second embodiment.

[0061] Figure 11 It is a schematic diagram showing the configuration of a processing unit included in the substrate processing apparatus according to the third embodiment.

[0062] Figure 12 It is a flowchart showing an example of substrate processing performed by the substrate processing apparatus according to the third embodiment. Detailed Embodiments

[0063] <Configuration of the Substrate Processing Apparatus According to the First Embodiment>

[0064] Figure 1 It is a top view showing a configuration example of the substrate processing apparatus 1 according to the first embodiment of the present invention.

[0065] The substrate processing apparatus 1 is a single-sheet type apparatus that processes substrates W one by one. In this embodiment, the substrate W has a disc shape. The substrate W is a substrate W such as a silicon wafer and has a pair of main surfaces.

[0066] The substrate processing apparatus 1 includes: a plurality of processing units 2 that process the substrate W; a loading port LP (container holding unit) on which a carrier C (container) that houses a plurality of substrates W processed by the processing unit 2 is placed; a transfer robot (first transfer robot IR and second transfer robot CR) that transfers the substrate W between the loading port LP and the processing unit 2; and a controller 3 that controls each component included in the substrate processing apparatus 1.

[0067] The first transfer robot IR transfers the substrate W between the carrier C and the second transfer robot CR. The second transfer robot CR transfers the substrate W between the first transfer robot IR and the processing unit 2. Each transfer robot is, for example, a multi-joint arm robot.

[0068] The plurality of processing units 2 are arranged on both sides of the transfer path TR along which the second transfer robot CR transfers the substrate W and are stacked and arranged in the vertical direction. The plurality of processing units 2 have, for example, the same configuration.

[0069] The plurality of processing units 2 form four processing towers TW respectively arranged at four horizontally separated positions. Each processing tower TW includes a plurality of processing units 2 stacked in the vertical direction. Two of the four processing towers TW are arranged on each side of the transfer path TR extending from the loading port LP toward the second transfer robot CR.

[0070] The substrate processing apparatus 1 includes a plurality of fluid tanks 4 that house valves, piping, etc., and a storage tank 5 that houses a sulfuric acid-containing liquid, a chemical solution, a rinsing solution, an organic solvent, or tanks for storing these raw materials. The processing unit 2 and the fluid tanks 4 are disposed inside a frame 6 having a substantially quadrilateral shape in plan view.

[0071] The processing unit 2 has a chamber 7 that houses a substrate W during substrate processing. The chamber 7 includes: an entrance / exit (not shown) through which the substrate W is carried into or out of the chamber 7 by a second transfer robot CR; and a gate unit (not shown) that opens and closes the entrance / exit. As the processing liquid supplied to the substrate W in the chamber 7, which will be described in detail later, examples include a sulfuric acid-containing liquid, a chemical solution, a rinsing solution, an organic solvent, etc.

[0072] <Configuration of the processing unit according to the first embodiment>

[0073] Figure 2 is a schematic diagram for explaining the configuration of the processing unit 2.

[0074] The processing unit 2 further includes: a rotating chuck 8 that holds the substrate W in a predetermined processing posture and rotates the substrate W around a rotation axis A1; a plurality of moving nozzles (a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11) that discharge a processing liquid toward the substrate W; and a processing chamber 12 that can house the substrate W held by the rotating chuck 8.

[0075] 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 by the rotating chuck 8; and a processing cup 15 that receives the processing liquid scattered from the substrate W held by the rotating chuck 8.

[0076] The rotating 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 inside the chamber 7.

[0077] The rotation axis A1 passes through the central portion of the substrate W and is orthogonal to each main surface of the substrate W held in the processing posture. The processing posture is, for example, Figure 2 the posture of the substrate W shown, which is a horizontal posture in which the main surface of the substrate W is a horizontal plane, but is not limited to the horizontal posture. That is, different from Figure 2 the processing posture may also be a posture in which the main surface of the substrate W is inclined with respect to the horizontal plane. When the processing posture is a horizontal posture, the rotation axis A1 extends vertically.

[0078] The rotary chuck 8 is an example of a substrate holding member (substrate holder) that holds the substrate W in a processing position, 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 position.

[0079] The rotary chuck 8 includes: a rotary base 21 having a disk shape along the horizontal direction; a plurality of holding pins 20 that hold the substrate W above the rotary base 21 and hold the peripheral portion of the substrate W at a position above the rotary base 21; a rotary shaft 22 that is connected to the rotary base 21 and extends in the vertical direction; and a rotary drive mechanism 23 that rotates the rotary shaft 22 around its central axis (rotation axis A1). The rotary base 21 is an example of a disk-shaped base.

[0080] The plurality of holding pins 20 are arranged at intervals in the circumferential direction of the rotary base 21 on the upper surface of the rotary base 21. The rotary drive mechanism 23 includes, for example, an actuator such as an electric motor. The rotary drive mechanism 23 rotates the rotary base 21 and the plurality of holding pins 20 around the rotation axis A1 by rotating the rotary shaft 22. Thereby, the substrate W rotates around the rotation axis A1 together with the rotary base 21 and the plurality of holding pins 20.

[0081] The plurality of holding pins 20 can move between a closed position where they contact the peripheral portion of the substrate W to hold the substrate W and an open position where the holding of the substrate W is released. The plurality of holding pins 20 are moved by an opening and closing mechanism (not shown).

[0082] When the plurality of holding pins 20 are in the closed position, they hold the peripheral portion of the substrate W to hold the substrate W horizontally. When the plurality of holding pins 20 are in the open position, the holding of the substrate W is released, and on the other hand, the peripheral portion of the substrate W is supported from below. The opening and closing mechanism includes, for example, a link mechanism and an actuator that applies a driving force to the link mechanism.

[0083] The plurality of moving nozzles include: a first moving nozzle 9 that discharges a continuous flow of sulfuric acid-containing liquid toward the upper surface (upper main surface) of the substrate W held by the rotary chuck 8; a second moving nozzle 10 that discharges a continuous flow of a chemical solution and a continuous flow of a rinsing liquid selectively toward the upper surface of the substrate W held by the rotary chuck 8; and a third moving nozzle 11 that discharges an organic solvent toward the upper surface of the substrate W held by the rotary chuck 8.

[0084] 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 rotary 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 rotary chuck 8, and is an example of a rinsing liquid discharge member that discharges a rinsing liquid toward the main surface (upper surface) of the substrate W held by the rotary 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 rotary chuck 8.

[0085] The plurality of moving nozzles are respectively moved in the horizontal direction by a plurality of nozzle drive mechanisms (the first nozzle drive mechanism 25, the second nozzle drive mechanism 26, and the third nozzle drive mechanism 27).

[0086] Each nozzle drive mechanism can move the corresponding moving nozzle between a central position and a retracted position. The central position is a position where the moving nozzle faces the central region of the upper surface of the substrate W. The central region of the upper surface of the substrate W refers to a region that includes the rotation center (central part) and the surrounding part of the rotation center on the upper surface of the substrate W. The retracted position is a position where the moving nozzle does not face the upper surface of the substrate W, and is a position outside the processing cup 15.

[0087] Each nozzle drive mechanism includes: an arm (the first arm 25a, the second arm 26a, and the third arm 27a) that supports the corresponding moving nozzle, and an arm drive mechanism (the first arm drive mechanism 25b, the second arm drive mechanism 26b, and the 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 a cylinder.

[0088] The moving nozzle can be a rotary nozzle that rotates around a specified rotation axis, or a linear motion nozzle that linearly moves in the direction in which the corresponding arm extends. The moving nozzle can also be configured to be able to move in the vertical direction.

[0089] 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. Substances other than sulfuric acid and water may also be contained in the sulfuric acid-containing liquid. The sulfuric acid-containing liquid can also be formed by mixing sulfuric acid with water such as DIW (deionized water).

[0090] The processing unit 2 further includes a sulfuric acid-containing liquid supply unit 16 that supplies the 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 regulating valve 50B.

[0091] The sulfuric acid-containing liquid pipe 40 is connected to the first moving nozzle 9 to guide the sulfuric acid-containing liquid to the first moving nozzle 9. A sulfuric acid-containing liquid valve 50A and a sulfuric acid-containing liquid flow regulating valve 50B are provided in the sulfuric acid-containing liquid pipe 40.

[0092] The sulfuric acid-containing liquid valve 50A being provided in the sulfuric acid-containing liquid pipe 40 may also mean that the sulfuric acid-containing liquid valve 50A is installed in the sulfuric acid-containing liquid pipe 40. The same applies to other valves described below.

[0093] The sulfuric acid-containing liquid valve 50A opens and closes the sulfuric acid-containing liquid pipe 40. The sulfuric acid-containing liquid flow regulating valve 50B adjusts the flow rate of the sulfuric acid-containing liquid in the sulfuric acid-containing liquid pipe 40. Details of the configuration of the sulfuric acid-containing liquid supply unit 16 will be described later. When the sulfuric acid-containing liquid valve 50A is opened, the sulfuric acid-containing liquid is continuously discharged from the first moving nozzle 9.

[0094] Although not shown, the sulfuric acid-containing liquid valve 50A includes: a valve body having a valve seat inside; a valve core that opens and closes the valve seat; and an actuator that moves the valve core between an open position and a closed position. Other valves have the same configuration.

[0095] The liquid medicine discharged from the second moving nozzle 10 contains, for example, hydrogen peroxide water (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).

[0096] The rinsing liquid discharged from the second moving nozzle 10 is, for example, water such as DIW. However, the rinsing liquid is not limited to DIW. The rinsing liquid may also be DIW, carbonated water, electrolyzed ionized water, hydrochloric acid water with a dilution concentration (for example, 1 ppm or more and 100 ppm or less), ammonia water with a dilution concentration (for example, 1 ppm or more and 100 ppm or less), or reduced water (hydrogen water), or a mixed liquid containing at least two of them.

[0097] The second moving nozzle 10 is connected to a common pipe 41 that guides fluid to the second moving nozzle 10. A liquid medicine pipe 42 that supplies liquid medicine to the common pipe 41 and a rinsing liquid pipe 43 that supplies rinsing liquid to the common pipe 41 are connected to the common pipe 41. The common pipe 41 may also be connected to the liquid medicine pipe 42 and the rinsing liquid pipe 43 via a mixing valve (not shown).

[0098] A common valve 51 for opening and closing the common pipe 41 is provided in the common pipe 41. A chemical solution valve 52A for opening and closing the chemical solution pipe 42 and a chemical solution flow rate regulating valve 52B for adjusting the flow rate of the chemical solution in the chemical solution pipe 42 are provided in the chemical solution pipe 42. A rinsing liquid valve 53A for opening and closing the rinsing liquid pipe 43 and a rinsing liquid flow rate regulating valve 53B for adjusting the flow rate of the rinsing liquid in the rinsing liquid pipe 43 are provided in the rinsing liquid pipe 43.

[0099] When the chemical solution valve 52A and the common valve 51 are opened, a continuous flow of the chemical solution is discharged from the second moving nozzle 10. When the rinsing liquid valve 53A and the common valve 51 are opened, a continuous flow of the rinsing liquid is discharged from the second moving nozzle 10.

[0100] The organic solvent discharged from the third moving nozzle 11 contains at least one of alcohols such as ethanol (EtOH) and isopropyl alcohol (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), lactate 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.

[0101] An organic solvent pipe 44 for guiding the organic solvent to the third moving nozzle 11 is connected to the third moving nozzle 11. An organic solvent valve 54A for opening and closing the organic solvent pipe 44 and an organic solvent flow rate regulating valve 54B for adjusting the flow rate of the organic solvent in the organic solvent pipe 44 are provided in the organic solvent pipe 44.

[0102] The processing cup 15 includes a plurality of (three in Figure 2 this case) baffles 28 for receiving the processing liquid scattered outward from the substrate W held by the rotary chuck 8, a plurality of (three in Figure 2 this case) cups 29 for receiving the processing liquid guided downward by the plurality of baffles 28, and a cylindrical outer wall member 30 surrounding the plurality of baffles 28 and the plurality of cups 29.

[0103] Each baffle 28 has a cylindrical shape surrounding the rotary chuck 8 in a plan view. The upper end portion of each baffle 28 is inclined inward toward the center side of the baffle 28. Each cup 29 has a shape of an upwardly open annular groove. The plurality of baffles 28 and the plurality of cups 29 are arranged coaxially.

[0104] A plurality of baffles 28 can be individually lifted and lowered by a baffle lifting drive mechanism (not shown). The baffle lifting drive mechanism includes, for example, a plurality of actuators that individually drive the lifting and lowering of the plurality of baffles 28. The plurality of actuators include at least one of an electric motor and a cylinder.

[0105] The processing unit 2 includes an air supply unit 31 such as an FFU (Fan Filter Unit) that conveys an inert gas from outside the chamber 7 into the chamber 7, and a discharge pipe 32 that exhausts the atmosphere inside the chamber 7. The air supply unit 31 is disposed on the upper wall 7a of the chamber 7. The discharge pipe 32 is connected to the outer wall member 30. The inert gas conveyed into the chamber 7 by the air supply unit 31 can be, for example, nitrogen, a noble gas, or a mixed gas thereof. The noble gas is, for example, argon.

[0106] The discharge pipe 32 is connected to an exhaust pipe (not shown). The atmosphere inside the exhaust pipe is sucked by a suction device (not shown). The atmosphere inside the chamber 7 is discharged into the exhaust pipe via the discharge pipe 32. The suction device includes a suction pump or the like that sucks the exhaust pipe. The suction device is installed in the exhaust pipe or connected to the exhaust pipe. The exhaust pipe and the suction device are provided in a clean room where the substrate processing apparatus 1 is installed or in equipment attached to the clean room. The exhaust pipe and the suction device can also be a part of the substrate processing apparatus 1.

[0107] An ozone removal device 33 (ozone exterminator) is provided between the discharge pipe 32 and the exhaust pipe or in the discharge pipe 32. The ozone gas contained in the atmosphere discharged from the chamber 7 is decomposed when passing through the ozone removal device 33.

[0108] Due to the action of the air supply unit 31 and the discharge pipe 32, an air flow from above to below is formed in the internal space 7c of the chamber 7. The air flow flows into the discharge pipe 32 through the inside of the processing cup 15.

[0109] The processing liquid supplied to the substrate W scatters from the peripheral portion of the substrate W and is received by any one of the baffles 28. The processing liquid received by the baffle 28 is guided to the corresponding cup 29 and recovered or discarded by a drain pipe (not shown) corresponding to each cup 29.

[0110] The substrate heating member 14 has the form of a disc-shaped heating plate that heats the substrate W from below. The substrate heating member 14 is disposed between the upper surface of the rotating 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.

[0111] The substrate heating member 14 includes a plate body 60 and a heater 61. When viewed from above, the plate body 60 is slightly smaller than the substrate W. The upper surface of the plate body 60 constitutes the heating surface 14a. The heater 61 can also be a resistor body built into the plate body 60. By energizing the heater 61, the heating surface 14a is heated.

[0112] The heater 61 is configured to be able to heat the substrate W within a temperature range above room temperature (for example, a temperature of 5°C or higher and 25°C or lower) and 400°C or lower.

[0113] 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 Figure 2 , the temperature sensor 62 is built into the plate body 60, but the configuration of the temperature sensor 62 is not particularly limited. For example, the temperature sensor 62 can also be externally mounted on the plate body 60.

[0114] The heater 61 is connected to an energization unit 63 via a power supply line 64. The temperature of the heater 61 is adjusted by adjusting the current supplied from the energization unit 63 to the heater 61. For example, the current supplied from the energization unit 63 to the heater 61 is adjusted based on the detected temperature of the temperature sensor 62.

[0115] A heater lifting shaft 65 is connected to the lower surface of the substrate heating member 14. The heater lifting shaft 65 is inserted into a through hole 21a formed in the central portion of the rotating base 21 and the internal space of the rotating shaft 22.

[0116] The processing unit 2 further includes a heater drive mechanism 66 that drives the substrate heating member 14 to move in the vertical direction. The heater drive mechanism 66 includes, for example, a heater actuator (not shown) that drives the movement of the heater lifting shaft 65 in the vertical direction. The heater actuator includes, for example, at least one of an electric motor and a cylinder. The heater drive mechanism 66 moves the substrate heating member 14 in the vertical direction via the heater lifting shaft 65. The substrate heating member 14 can move in the vertical direction between the lower surface of the substrate W and the upper surface of the rotating base 21.

[0117] When the substrate heating member 14 rises, it can receive the substrate W from a plurality of holding pins 20 located at the open position. The substrate heating member 14 can heat the substrate W by being disposed at a contact position where the heating surface 14a contacts the lower surface of the substrate W, or at a proximity position where it non - contactingly approaches the lower surface of the substrate W. The position where the substrate heating member 14 is fully retracted from the lower surface of the substrate W to such an extent that the heating of the substrate W is alleviated is referred to as the retracted position. It can be said that the heating of the substrate W is sufficiently alleviated, in other words, the heating of the substrate W stops.

[0118] When the substrate heating member 14 is disposed at the retracted position, the amount of heat transferred from the substrate heating member 14 to the substrate W is less than the amount of heat transferred from the substrate heating member 14 to the substrate W when the substrate heating member 14 is disposed 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 alleviation position and also as a heating stop position.

[0119] The processing chamber 12 has an internal space 70 capable of accommodating the substrate W, a housing 71 partitioning the internal space 70, and an opening 70a provided in the housing 71 and opening the internal space 70 to the outside of the processing chamber 12. The housing 71 has, for example, a cylindrical inner peripheral surface 71a having a diameter larger than that of the substrate W in a plan view and a flat bottom surface 71b connected to the inner peripheral surface 71a.

[0120] The processing chamber 12 is connected to a processing chamber lifting shaft 72. The processing unit 2 further includes a processing chamber drive mechanism 73 that drives the processing chamber 12 to move in the vertical direction. The processing chamber drive mechanism 73 includes, for example, a processing chamber actuator (not shown) that drives the processing chamber lifting shaft 72 to move in the vertical direction. The processing chamber drive mechanism 73 moves the processing chamber 12 in the vertical direction via the processing chamber lifting shaft 72. The processing chamber actuator includes at least one of an electric motor and a cylinder.

[0121] By lowering the processing chamber 12, the substrate W can be relatively moved inside the processing chamber 12 (internal space 70) via the opening 70a. Regarding the processing chamber 12, the position of the processing chamber 12 when the substrate W is accommodated in the processing chamber 12 (internal space 70) is referred to as 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 disposed at the accommodation position, the substrate W can be relatively moved outside the processing chamber 12 via the opening 70a. The position of the processing chamber 12 when the substrate W is outside the processing chamber 12 is referred to as the non-accommodation position.

[0122] In this way, the processing chamber drive mechanism 73 can move the processing chamber 12 relative to the rotary chuck 8 so that the substrate W can be relatively moved between inside and outside the processing chamber 12. In addition, when the processing chamber 12 is located at the accommodation position, each nozzle moving 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 at the non-accommodation position, each nozzle moving mechanism can move the corresponding moving nozzle to a position facing the upper surface of the substrate W.

[0123] 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 rapidly supplied to the entire internal space 70. In Figure 2 the example shown, the plurality of ozone-containing gas discharge ports 76 are formed in the bottom surface 71b of the housing 71.

[0124] The ozone-containing gas flow path 75 can be constituted by, for example, a circulation hole formed in the processing chamber lifting shaft 72 and the housing 71, or can be constituted by a pipe disposed in the circulation hole. The ozone-containing gas flow path 75 can also be formed only in the housing 71 without being formed in the processing chamber lifting shaft 72.

[0125] The ozone-containing gas discharged from the ozone-containing gas discharge port 76 can be ozone gas, or can be a mixed gas of ozone gas and a gas other than ozone gas. The gas other than ozone gas is, for example, an inert gas. The inert gas contained in the ozone-containing gas can be, for example, nitrogen, a noble gas, or a mixed gas thereof. The noble gas is, for example, argon.

[0126] 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. An ozone-containing gas valve 55A for opening and closing the ozone-containing gas pipe 45 and an ozone-containing gas flow rate adjustment valve 55B for adjusting the flow rate of the ozone-containing gas in the ozone-containing gas pipe 45 are provided in the ozone-containing gas pipe 45.

[0127] <Configuration of Sulfuric Acid Liquid Supply Unit>

[0128] Figure 3 It is a schematic diagram for explaining the configuration of the sulfuric acid liquid supply unit 16.

[0129] The sulfuric acid liquid supply unit 16 further includes a storage tank 80, a supply pipe 81, a circulation pipe 82, a liquid feed pump 83, a circulation valve 84, a pipe heater 85, and a tank heater 86.

[0130] The storage tank 80 stores the sulfuric acid liquid. The supply pipe 81 is connected to the storage tank 80 and the sulfuric acid liquid pipe 40, and supplies the sulfuric acid liquid in the storage tank 80 to the sulfuric acid liquid pipe 40. The circulation pipe 82 is connected to the connection positions of the supply pipe 81 and the sulfuric acid liquid pipe 40, and circulates the sulfuric acid liquid in the storage tank 80 by returning the sulfuric acid liquid in the supply pipe 81 to the storage tank 80. The liquid feed pump 83 generates a driving force for transporting the sulfuric acid 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.

[0131] The pipe heater 85 heats the sulfuric acid liquid in the supply pipe 81. The tank heater 86 heats the sulfuric acid liquid in the storage tank 80. The forms of the pipe heater 85 and the tank heater 86 are not particularly limited. The pipe heater 85 heats the sulfuric acid 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 installed on the outer side of the wall portion of the storage tank 80.

[0132] The sulfuric acid-containing liquid supply unit 16 further includes: a replenishment pipe 88 for replenishing new sulfuric acid-containing liquid (new liquid) from a sulfuric acid-containing liquid supply source 87 to a storage tank 80, and a replenishment valve 89 for opening and closing the replenishment pipe 88. By opening the replenishment valve 89, new liquid is supplied to the storage tank 80.

[0133] <Electrical Configuration of Substrate Processing in the First Embodiment>

[0134] Figure 4 It is a block diagram for explaining the electrical configuration of the substrate processing apparatus 1.

[0135] 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 for executing various commands and a memory 3c for storing information.

[0136] The peripheral device 3d includes: an auxiliary storage device 3e for storing information such as programs, a reading device 3f for reading information from a removable medium (not shown), and a communication device 3g for communicating with other devices such as a main computer (not shown).

[0137] 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 person inputs information to the substrate processing apparatus 1. Information is displayed on the screen of the display device 3B. The input device 3A can be any one of a keyboard, a pointing device, and a touch panel, or a device other than these. A touch panel display that also serves as the input device 3A and the display device 3B can be provided in the substrate processing apparatus 1. The alarm device 3C issues an alarm using one or more of light, sound, text, and graphics. In the case where the input device 3A is a touch panel display, the input device 3A can also serve as the alarm device 3C.

[0138] The auxiliary storage device 3e is a non-volatile memory that retains stored data even without power supply. The auxiliary storage device 3e is, for example, a magnetic storage device such as a hard disk drive.

[0139] The auxiliary storage device 3e stores a plurality of processes. A process is information that defines the processing content, processing conditions, and processing steps of the substrate W. The plurality of processes are different from each other in at least one of the processing content, processing conditions, and processing steps of the substrate W.

[0140] The controller 3 controls each component included in the substrate processing apparatus 1 to process the substrate W according to a process specified by an external device such as a main computer.

[0141] As control objects of the controller 3, the first transfer robot IR, the second transfer 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 supply unit 31, the temperature sensor 62, the liquid feed pump 83, the pipe heater 85, the tank heater 86, the sulfuric acid-containing liquid valve 50A, the sulfuric acid-containing liquid flow regulating valve 50B, the common valve 51, the chemical liquid valve 52A, the chemical liquid flow regulating valve 52B, the rinse liquid valve 53A, the rinse liquid flow regulating valve 53B, the organic solvent valve 54A, the organic solvent flow regulating valve 54B, the circulation valve 84, the replenishing valve 89, etc. can be cited.

[0142] In addition, Figure 4 illustrates representative components, but this does not mean that components not illustrated are not controlled by the controller 3. The controller 3 can appropriately control each component included in the substrate processing apparatus 1. In Figure 4 components described in the second and third embodiments described later are also described, and these components are also controlled by the controller 3.

[0143] The following respective processes are executed by controlling the substrate processing apparatus 1 with the controller 3. In other words, the controller 3 is programmed to execute the following respective processes.

[0144] <An example of substrate processing>

[0145] Figure 5 is a flowchart for explaining an example of the substrate processing executed by the substrate processing apparatus 1. Figures 6A - 6E is a schematic diagram for explaining the substrate W and its surroundings during substrate processing. An organic film such as a resist is formed on at least one of a pair of main surfaces of the substrate W used for substrate processing.

[0146] In the substrate processing of the substrate processing apparatus 1, for example, as Figure 5 shows, a substrate loading process (step S1), a substrate heating process (step S2), a liquid film forming process (step S3), an ozone-containing gas exposure process (step S4), a first rinsing process (step S5), an ozone-containing gas removal process (step S6), a chemical liquid supply process (step S7), a second rinsing process (step S8), an organic solvent supply process (step S9), a spin drying process (step S10), and a substrate unloading process (step S11) are executed. Hereinafter, mainly with reference to Figure 2 and Figure 5 , the details of the substrate processing will be described. Appropriate reference is made to Figures 6A - 6E .

[0147] First, the unprocessed substrate W is transferred by the second transfer robot CR (refer to Figure 1)It is carried from the carrier C into the processing unit 2 and transferred to the rotary chuck 8 (substrate loading process: step S1). Thus, the substrate W is held horizontally by the rotary chuck 8 (substrate holding process). At this time, the substrate W is held by the rotary chuck 8 such that the main surface on which the organic film is formed becomes the upper surface. The substrate W is continuously held by the rotary chuck 8 until the spin drying process (step S10) ends.

[0148] In a state where the substrate W is held by the rotary chuck 8, the rotation drive mechanism 23 starts the rotation of the substrate W (substrate rotation process). In addition, during the execution of substrate processing, an air flow from above to below is always formed in the internal space 7c of the chamber 7, and the air flow flows into the discharge pipe 32 through the inside of the processing cup 15.

[0149] After the second transfer robot CR retracts from the chamber 7, a substrate heating process for heating the substrate W is performed (step S2). Specifically, an electric current is supplied to the heater 61 by the power supply unit 63, and the temperature rise of the heater 61 starts. Then, the heater drive mechanism 66 moves the substrate heating member 14 from the retracted position to the approaching position. As Figure 6A shown, when the temperature rise of the heater 61 starts and the substrate heating member 14 is arranged at the approaching position, the heating of the substrate W starts (substrate heating start process: step S21).

[0150] And when the detected temperature of the temperature sensor 62 reaches the processing temperature range, a liquid film forming process for forming a liquid film 100 of sulfuric acid-containing liquid on the upper surface of the substrate W (refer to Figure 6C ) is performed (step S3). Specifically, the first nozzle drive mechanism 25 moves the first moving nozzle 9 to the processing position. The processing position is, for example, the central position.

[0151] In a state where the first moving nozzle 9 is located at the processing position, the sulfuric acid-containing liquid valve 50A is opened. Thus, as Figure 6B shown, 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 starts (sulfuric acid-containing liquid supply start process: step S31). The sulfuric acid-containing liquid that lands on the upper surface of the substrate W moves toward the peripheral portion of the upper surface of the substrate W, and the sulfuric acid-containing liquid spreads over the entire upper surface of the substrate W.

[0152] After the supply of the sulfuric acid-containing liquid starts, if a predetermined period elapses, the sulfuric acid-containing liquid valve 50A is closed. Thus, the supply of the sulfuric acid-containing liquid to the upper surface of the substrate W is stopped (sulfuric acid-containing liquid supply stop process: step S32). The discharge period of the sulfuric acid-containing liquid is, for example, about 1 second.

[0153] The sulfuric acid-containing liquid on the upper surface of the substrate W is removed by using 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, so that the sulfuric acid-containing liquid on the upper surface of the substrate W becomes thinner (thin film chemical process). Thus, as Figure 6C shown, a thinner liquid film 100 of the sulfuric acid-containing liquid is formed on the upper surface of the substrate W. The liquid film 100 has a thickness of, for example, 1 μm or more and 2 mm or less.

[0154] At the moment when the discharge of the sulfuric acid-containing liquid stops, the sulfuric acid-containing liquid does not need to spread over the entire upper surface of the substrate W and can spread to the peripheral portion of the upper surface of the substrate W after the supply of the sulfuric acid-containing liquid stops. If the discharge of the sulfuric acid-containing liquid is stopped before the sulfuric acid-containing liquid spreads over the entire substrate W, the supply amount of the sulfuric acid-containing liquid can be further reduced.

[0155] After the discharge of the sulfuric acid-containing liquid is stopped, the first nozzle drive mechanism 25 retracts the first moving nozzle 9. After the discharge of the sulfuric acid-containing liquid is stopped, if a predetermined period elapses, an ozone-containing gas exposure process (step S4) is performed. The ozone-containing gas exposure process is a process 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.

[0156] Specifically, after the discharge of the sulfuric acid-containing liquid is stopped, at the moment when a predetermined period has elapsed, the processing chamber drive mechanism 73 lowers the processing chamber 12 from the non-accommodating position toward the accommodating position. Thus, the substrate W is accommodated in the processing chamber 12 (substrate accommodation process). In a state where the processing chamber 12 is disposed at the accommodating position, the ozone-containing gas valve 55A is opened. Thus, as Figure 6D shown, the ozone-containing gas is supplied into the processing chamber 12 (ozone-containing gas supply start process: 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 process, ozone-containing gas filling process).

[0157] By disposing the substrate W in the processing chamber 12 filled with the 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 process).

[0158] By supplying the ozone-containing gas into the processing chamber 12, the inside of the processing chamber 12 can be pressurized (pressurized supply process). Thus, the pressure inside the processing chamber 12 becomes higher than the pressure outside the processing chamber 12. In the chamber 7, the pressure outside the processing chamber 12 is, for example, atmospheric pressure, about 0.1 MPa. The pressure inside the processing chamber 12 is, for example, 0.1 MPa or more and 0.2 MPa or less. By disposing the substrate W in the processing chamber 12 to narrow the opening 70a, the pressure inside the processing chamber 12 can be easily increased.

[0159] After a predetermined period has elapsed since the supply of the ozone-containing gas 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 toward the non-accommodation position.

[0160] By closing the ozone-containing gas valve 55A, the supply of the ozone-containing gas to the processing chamber 12 is stopped (ozone-containing gas supply stop step: step S42). The processing chamber drive mechanism 73 raises the processing chamber 12 from the accommodation position toward the non-accommodation position. Thereby, the substrate W is detached from the processing chamber 12 (substrate detachment step). By detaching the substrate W from the processing chamber 12, the exposure of the ozone-containing gas to the liquid film 100 on the upper surface of the substrate W can be stopped. Thereby, the ozone-containing gas exposure step (step S4) ends. The substrate detachment step may be performed before the ozone-containing gas valve 55A is closed.

[0161] Strictly speaking, the ozone-containing gas remains in the chamber 7. However, by disposing the processing chamber 12 in the non-accommodation position, the concentration of the ozone gas in the atmosphere in contact with the liquid film 100 on the upper surface of the substrate W can be reduced. In this way, reducing the concentration of the ozone gas in the atmosphere in contact with the liquid film 100 on the upper surface of the substrate W is referred to as the stop of the exposure of the ozone-containing gas.

[0162] After stopping the exposure of the ozone-containing gas to the liquid film 100 on the upper surface of the substrate W, the heater drive mechanism 66 moves the substrate heating member 14 from the approaching position to the retracted position. By disposing the substrate heating member 14 in the retracted position ( Figure 6E the position shown), the heating of the substrate W is stopped (substrate heating stop step: step S22). Thereby, the substrate heating step (step S2) ends.

[0163] 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 the organic film is removed from the upper surface of the substrate W. Sometimes the organic film is not completely dissolved in the sulfuric acid-containing liquid, but is peeled off from the upper surface of the substrate W due to the liquid flow of the sulfuric acid-containing liquid.

[0164] After the substrate heating step (step S2), the liquid film forming step (step S3), and the ozone-containing gas exposure step (step S4), a first rinsing step (step S5) of cleaning the upper surface of the substrate W by supplying a rinsing liquid to the upper surface of the substrate W is performed.

[0165] Specifically, the second nozzle drive mechanism 26 moves the second moving nozzle 10 to the processing position. The processing position is, for example, the central position. In a state where the second moving nozzle 10 is located at the processing position, the common valve 51 and the rinsing liquid valve 53A are opened. Thereby, as Figure 6EAs shown, the rinsing liquid is discharged from the second moving nozzle 10, and the supply of the rinsing liquid to the upper surface of the substrate W is started (rinsing liquid supply start process, rinsing liquid supply process). The rinsing liquid that has landed on the upper surface of the substrate W moves toward the peripheral portion of the upper surface of the substrate W, and the rinsing liquid spreads over the entire upper surface of the substrate W.

[0166] After the supply of the rinsing liquid is started, if a predetermined period has elapsed, the common valve 51 and the rinsing liquid valve 53A are closed. As a result, the supply of the rinsing liquid to the upper surface of the substrate W is stopped (rinsing liquid supply stop process). As a result, the first rinsing process ends. By the first rinsing process, the sulfuric acid-containing liquid is discharged from the upper surface of the substrate W. Together with the sulfuric acid-containing liquid, the organic film peeled off from the upper surface of the substrate W is removed from the upper surface of the substrate W.

[0167] After the supply of the rinsing liquid to the upper surface of the substrate W is stopped, an ozone-containing gas removal process (step S6) for removing the ozone-containing gas from the processing chamber 12 and the chamber 7 is performed. 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 air supply unit 31 and the discharge flow rate from the discharge pipe 32.

[0168] After the ozone-containing gas removal process (step S6), a chemical liquid supply process (step S7) for supplying the chemical liquid to the upper surface of the substrate W is performed. Specifically, the common valve 51 and the chemical liquid valve 52A are opened in a state where the second moving nozzle 10 is located at the processing position. As a result, the discharge of the rinsing liquid is stopped, and further, a continuous flow of the chemical liquid is discharged (supplied) from the second moving nozzle 10 to the upper surface of the substrate W (chemical liquid discharge process, chemical liquid supply process). As a result, the upper surface of the substrate W is treated with the chemical liquid.

[0169] After the chemical liquid supply process (step S7), a second rinsing process (step S8) for supplying the rinsing liquid to the upper surface of the substrate W and cleaning the upper surface of the substrate W is performed. Specifically, while maintaining the state where the second moving nozzle 10 faces the upper surface of the substrate W and the common valve 51 is open, the chemical liquid valve 52A is closed and the rinsing liquid valve 53A is opened. As a result, the discharge of the chemical liquid from the second moving nozzle 10 is stopped, and further, a continuous flow of the rinsing liquid is discharged (supplied) from the second moving nozzle 10 to the upper surface of the substrate W (rinsing liquid discharge process, rinsing liquid supply process). As a result, the chemical liquid on the upper surface of the substrate W and the rinsing liquid are discharged to the outside of the substrate W together, and the upper surface of the substrate W is cleaned.

[0170] After the second rinsing step (step S8), an organic solvent supply step (step S9) of supplying an organic solvent to the upper surface of the substrate W is performed. 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 opposes the third moving nozzle 11 to the upper surface of the substrate W and opens the organic solvent valve 54A. Thereby, a continuous flow of the organic solvent is discharged (supplied) from the third moving nozzle 11 to the upper surface of the substrate W (organic solvent discharge step, organic solvent supply step). Thereby, the rinsing liquid on the upper surface of the substrate W is replaced with the organic solvent.

[0171] The organic solvent used in the substrate treatment preferably has a higher volatility than the rinsing liquid. If so, by replacing the rinsing liquid with the organic solvent, the substrate W can be dried well in the subsequent spin drying step (step S10). The organic solvent used in the substrate treatment preferably has a lower surface tension than the rinsing liquid. If so, when an uneven pattern is formed on the upper surface of the substrate W, the surface tension acting on the uneven pattern when drying the upper surface of the substrate W can be reduced, and the collapse of the uneven pattern can be suppressed.

[0172] Next, a spin drying step (step S10) of rotating the substrate W at a high speed to dry the upper surface of the substrate W is performed. Specifically, the organic solvent valve 54A is closed to stop supplying the organic solvent to the upper surface of the substrate W. Then, the rotation driving mechanism 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed (for example, 1500 rpm). Thereby, a large centrifugal force acts on the rinsing liquid attached to the substrate W, and the organic solvent is thrown to the periphery of the substrate W.

[0173] After the spin drying step (step S10), the rotation driving mechanism 23 stops the rotation of the substrate W. Thereafter, the second transfer robot CR enters the processing unit 2, receives the processed substrate W from the spin chuck 8, and carries it out of the processing unit 2 (substrate carry-out step: step S11). This substrate W is transferred from the second transfer robot CR to the first transfer robot IR and accommodated in the carrier C by the first transfer robot IR.

[0174] <Functional Configuration of the Controller>

[0175] Figure 7 is a block diagram for explaining the functional configuration of the controller 3. Figure 8 is a flowchart for explaining an example of the organic film removal process performed by the controller 3.

[0176] The controller 3 operates by executing programs stored in the memory 3c (refer to Figure 4 ) to perform various functional processing units. When the controller 3 executes the program, the auxiliary storage device 3e (refer to Figure 4)The program stored in is expanded into the memory 3c.

[0177] Specifically, the controller 3 is configured to function as a temperature determination unit 90, a first start unit 91, a first elapsed time determination unit 92, a first stop unit 93, a second elapsed time determination unit 94, a second start unit 95, a third elapsed time determination unit 96, and a second stop unit 97, and is programmed. By functioning as these functional processing units, the controller 3 executes an organic film removal process for removing the organic film from the upper surface of the substrate W.

[0178] The temperature determination unit 90 determines whether the detected temperature detected by the temperature sensor 62 is within the processing temperature range (step S13). The processing temperature range is, for example, in the range of 50°C or higher and 270°C or lower. The processing temperature range is preferably in the range of 50°C or higher and 270°C or lower, and more preferably in the range of 80°C or higher and 170°C or lower. When the detected 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.

[0179] When the temperature determination unit 90 determines that the detected temperature of the temperature sensor 62 is within the processing temperature range (step S13: Yes), the first start unit 91 outputs a sulfuric acid-containing liquid discharge start command to the first nozzle drive mechanism 25 and the sulfuric acid-containing liquid valve 50A (step S14). As a result, the first moving nozzle 9 moves to the processing position, and the discharge of the sulfuric acid-containing liquid from the first moving nozzle 9 starts. Therefore, the sulfuric acid-containing liquid supplied to the upper surface of the substrate W can be heated quickly.

[0180] The sulfuric acid-containing liquid discharge start command includes, for example: a processing position movement command output to the first nozzle drive mechanism 25 to move the first moving nozzle 9; and a first opening command output to the sulfuric acid-containing liquid valve 50A to open the sulfuric acid-containing liquid valve 50A in a state where the first moving nozzle 9 is disposed at the processing position after the output of the first movement command.

[0181] After the sulfuric acid-containing liquid discharge start command is output, that is, after the discharge of the sulfuric acid-containing liquid from the first moving nozzle 9 starts, the first elapsed time determination unit 92 determines whether the supply stop time has elapsed (step S15). When the supply stop time has not elapsed (step S15: No), the first elapsed time determination unit 92 returns to step S15.

[0182] When it is determined by the determination unit 92 that the supply stop time has elapsed at the first time (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). Thereby, the discharge of the sulfuric acid-containing liquid from the first moving nozzle 9 is stopped, and the first moving nozzle 9 is moved to the retracted position. Therefore, the discharge time of the sulfuric acid-containing liquid can be controlled with high reproducibility. The supply stop time is preset based on the rotation speed of the substrate W and the supply flow rate of the sulfuric acid-containing liquid.

[0183] The sulfuric acid-containing liquid discharge stop command includes, for example: a first closing command that is output to the sulfuric acid-containing liquid valve 50A and closes the sulfuric acid-containing liquid valve 50A; and a retracted position movement command that is output to the first nozzle drive mechanism 25 after the output of the first closing command and moves the first moving nozzle 9.

[0184] After the sulfuric acid-containing liquid discharge stop command is output, that is, after the discharge of the sulfuric acid-containing liquid from the first moving 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 elapsed time since the start of the discharge of the sulfuric acid-containing liquid from the first moving nozzle 9. The liquid film formation time is a time longer than the discharge time. When the liquid film formation time has not elapsed (step S17: No), the second time elapse determination unit 94 returns to step S17.

[0185] When it is determined by the second time elapse determination unit 94 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). Thereby, the processing chamber 12 moves toward the accommodation position, and the discharge of the ozone-containing gas from the ozone-containing gas supply member 13 is started. 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 is quickly started. The second time elapse determination unit 94 is an example of a time elapse determination unit.

[0186] The ozone-containing gas exposure start command includes, for example: an accommodation position movement command that is output to the processing chamber drive mechanism 73 and moves the processing chamber 12 toward the accommodation position; and a second opening command that is output to the ozone-containing gas valve 55A and opens the ozone-containing gas valve 55A when the processing chamber 12 is disposed at the accommodation position after the output of the accommodation position movement command.

[0187] After the instruction to start the exposure to the ozone-containing gas is output, the third elapsed time determination unit 96 determines whether the exposure time has elapsed (step S19). The exposure time is the elapsed time since the ozone-containing gas supply member 13 started discharging the ozone-containing gas. If the exposure time has not elapsed (step S19: no), the third elapsed time determination unit 96 returns to step S19.

[0188] When the third elapsed time determination unit 96 determines that the exposure time has elapsed (step S19: yes), the second stop unit 97 outputs an instruction to stop the exposure to the ozone-containing gas to the processing chamber drive mechanism 73 and the ozone-containing gas valve 55A (step S20). As a result, the processing chamber 12 moves toward the non-accommodating position, and the discharge of the ozone-containing gas from the ozone-containing gas supply member 13 stops. Therefore, an appropriate amount of ozone can be 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.

[0189] The instruction to stop the exposure to the ozone-containing gas includes, for example: a second closing instruction that is output to the ozone-containing gas valve 55A to close the ozone-containing gas valve 55A, and a non-accommodating position movement instruction that is output to the processing chamber drive mechanism 73 after the second closing instruction is output and causes the processing chamber 12 to move toward the non-accommodating position.

[0190] As described above, the controller 3 functions as the above-described functional processing unit, so that the substrate can be processed with high reproducibility. Therefore, the organic film can be removed from the upper surface of the substrate W with high reproducibility.

[0191] <Summary of the First Embodiment>

[0192] According to the first embodiment of the present invention, with the substrate W disposed 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 by filling the processing chamber 12 with the ozone-containing gas. As a result, ozone in the ozone-containing gas can be dissolved in the sulfuric acid-containing liquid constituting the liquid film 100 on the substrate W to form peroxydisulfuric acid in the liquid film 100.

[0193] In addition, the substrate W is heated in a state where the liquid film 100 is formed on the upper surface of the substrate W. That is, the substrate W is heated in a state where peroxydisulfuric acid is formed in the sulfuric acid-containing liquid constituting the liquid film 100 on the upper surface of the substrate W. Therefore, the oxidizing power of peroxydisulfuric acid can be increased.

[0194] Furthermore, the substrate W is heated in a state where the processing chamber 12 is filled with the ozone-containing gas. Therefore, even if the solubility of ozone in the sulfuric acid-containing liquid decreases due to heating, the state where the ozone-containing gas containing a sufficient concentration of ozone contacts the sulfuric acid-containing liquid on the upper surface of the substrate W can be maintained. Therefore, the vaporization of ozone in the sulfuric acid-containing liquid can be suppressed.

[0195] As a result, an organic film such as a resist can be quickly and sufficiently removed from the substrate W.

[0196] According to the first embodiment, the heating of the substrate W in the substrate heating step (step S2) starts before the liquid film forming step (step S3) and the ozone-containing gas exposure step (step S4). Therefore, even when the time required for the temperature of the substrate W to rise is longer than the time required for the formation of the liquid film 100 and the time required for filling with the ozone-containing gas, the temperature of the substrate W can be quickly brought into the processing temperature range.

[0197] According to the first embodiment, the ozone-containing gas exposure step (step S4) includes a pressurized supply step of supplying an ozone-containing gas to the processing chamber 12 in such a manner that the pressure in the processing chamber 12 is higher than the pressure outside the processing chamber 12 in a state where a liquid film 100 containing a sulfuric acid-containing liquid is formed on the upper surface of the substrate W. Here, based on 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, if an ozone-containing gas is supplied into the processing chamber 12 to increase 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. Thereby, the concentration of peroxydisulfuric acid in the liquid film 100 can be increased, and thus the organic film can be quickly and sufficiently removed from the upper surface of the substrate W.

[0198] 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 liquid film 100 of the sulfuric acid-containing liquid can be removed from the upper surface of the substrate W by the rinse liquid. Therefore, it is possible to suppress the remaining sulfuric acid on the upper surface of the substrate W after removing the organic film from the upper surface of the substrate W.

[0199] According to the first embodiment, in the liquid film forming step, a sulfuric acid-containing liquid is supplied to the upper surface of the substrate W (sulfuric acid-containing liquid supply step). After stopping the supply of the sulfuric acid-containing liquid to the upper surface of the substrate W, 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).

[0200] Therefore, compared with the case where a continuous flow of the sulfuric acid-containing liquid is supplied to the upper surface of the substrate W while spreading the sulfuric acid-containing liquid over the entire upper surface of the substrate W, the time for supplying the sulfuric acid-containing liquid to the upper surface of the substrate W can be shortened. As described above, the discharge period of the sulfuric acid-containing liquid is about 1 second, for example. Therefore, the usage amount of the sulfuric acid-containing liquid can be reduced.

[0201] Furthermore, compared with the case of supplying a continuous flow of sulfuric acid-containing liquid to the upper surface of the substrate W while spreading the sulfuric acid-containing liquid 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 for heating the liquid film 100 can be reduced, achieving power saving.

[0202] Persulfuric acid generated in the reaction of ozone dissolved in the sulfuric acid-containing liquid from the surface of the liquid film 100 with sulfuric acid diffuses in the liquid film 100 and reaches the upper surface of the substrate W, thereby reacting with the organic film on the upper surface of the substrate W. Therefore, if the liquid film 100 is made thinner, persulfuric acid can easily 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.

[0203] According to the first embodiment, with the substrate W having the liquid film 100 formed thereon disposed in the processing chamber 12, by starting the supply of the ozone-containing gas to the processing chamber 12, the processing chamber 12 is filled with the ozone-containing gas.

[0204] Different from the first embodiment, when the liquid film 100 is formed after the supply of the ozone-containing gas to the processing chamber 12 is ended, since the ozone-containing gas flows out from the processing chamber 12 to the outside, the ozone concentration in the atmosphere in the processing chamber 12 may decrease. 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 in a state where 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.

[0205] According to the first embodiment, the rotary chuck 8 and the processing chamber 12 are accommodated in the chamber 7. The processing chamber 12 moves relative to the rotary chuck 8 in such a manner that the substrate W moves relative to between the inside and the outside of the processing chamber 12. Therefore, the processing chamber 12 can be lowered in the chamber 7 to accommodate the substrate W in the processing chamber 12 (substrate accommodation step), and the processing chamber 12 can be raised in the chamber 7 to remove the substrate W from the processing chamber 12 (substrate removal step).

[0206] Therefore, in a state where the substrate W is disposed in the processing chamber 12 that moves up and down in 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, compared with the case where the chamber 7 is filled with the ozone-containing gas, the ozone-containing gas can be filled quickly.

[0207] According to the first embodiment, when the substrate W is outside the processing chamber 12, after supplying the sulfuric acid-containing liquid from the first moving nozzle 9 to the upper surface of the substrate W to form the liquid film 100 on the upper surface of the substrate W, the substrate W can be disposed in the processing chamber 12. Thus, in the configuration in which the first moving nozzle 9 is separately provided from the processing chamber 12, the ozone-containing gas can be quickly supplied to the liquid film 100 on the upper surface of the substrate W.

[0208] The liquid film 100 of the sulfuric acid-containing liquid has a thickness of 1 μm or more and 2 mm or less, and is thin enough to be quickly heated. Therefore, the temperature of the liquid film 100 can be quickly increased by the heating of the substrate heating member 14. Therefore, in the sulfuric acid-containing liquid supply unit 16, different from the Figure 3 configuration shown, the tank heater 86 and the pipe heater 85 may not be provided.

[0209] <Substrate processing of modified example>

[0210] Figures 9A - 9C is a flowchart for explaining the substrate processing of the modified example.

[0211] Figure 9A The difference between the substrate processing of the first modified example shown and the Figure 5 substrate processing shown is that, in the substrate processing of the first modified example, before the substrate heating start step (step S21), the sulfuric acid-containing liquid discharge start step (step S31) is executed. Specifically, before the substrate heating member 14 reaches the approaching position, the sulfuric acid-containing liquid is started to be discharged from the first moving nozzle 9 to the upper surface of the substrate W.

[0212] Figure 9B The difference between the substrate processing of the second modified example shown and the Figure 5 substrate processing shown is that, after the ozone-containing gas supply start step (step S41), the substrate heating start step (step S21) is executed. Specifically, before the substrate heating member 14 reaches the approaching position, the liquid film of the sulfuric acid-containing liquid is formed, and the ozone-containing gas is started to be supplied to the processing chamber 12.

[0213] If the processing chamber 12 is disposed at the accommodation position, different from the Figure 9B substrate processing shown, the ozone-containing gas supply stop step (step S42) may also be executed before the substrate heating start step (step S21). Specifically, before the substrate heating member 14 reaches the approaching position, the supply of the ozone-containing gas to the processing chamber 12 may also be stopped.

[0214] On the other hand, the heating of the substrate W does not necessarily need to start in a state where the processing chamber 12 is filled with the ozone-containing gas and the liquid film 100 is formed on the upper surface of the substrate W. That is, it may be as Figure 5In the substrate processing as described above, with the processing chamber 12 containing the substrate W filled with an ozone-containing gas and a liquid film 100 formed on the upper surface of the substrate W, heating of the substrate W is performed. That is, regardless of the timing of starting the heating of the substrate W, as long as the processing chamber 12 containing 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, the organic film can be rapidly and sufficiently removed from the upper surface of the substrate W.

[0215] Figure 9C The difference between the substrate processing of the third modification shown in Figure 5 and the substrate processing shown in is that a hydrophilic treatment process (step S12) for hydrophilizing the upper surface of the substrate W is performed before the liquid film 100 containing sulfuric acid liquid is formed on the upper surface of the substrate W.

[0216] Specifically, after the substrate heating member 14 starts heating the substrate W, the processing chamber drive mechanism 73 moves the processing chamber 12 from the non-accommodating position toward the accommodating position. Then, the ozone-containing gas valve 55A is opened. Thus, in a state where the substrate W is disposed in the processing chamber 12, supply of the ozone-containing gas into the processing chamber 12 is started (ozone-containing gas supply start process: 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 process, ozone-containing gas filling process). 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 exposure process).

[0217] After the upper surface of the substrate W is exposed to the ozone-containing gas for a specified period, the ozone-containing gas valve 55A is closed. Then, in a state where the ozone-containing gas valve 55A is closed, the processing chamber drive mechanism 73 moves the processing chamber 12 from the accommodating position toward the non-accommodating position. Thus, supply of the ozone-containing gas into the processing chamber 12 is stopped (ozone-containing gas supply stop process: step S122), and the exposure of the upper surface of the substrate W to the ozone-containing gas is stopped.

[0218] In the substrate processing of the third modification, before the liquid film 100 containing sulfuric acid liquid is formed on the upper surface of the substrate W, the upper surface of the substrate W is hydrophilized. Specifically, the upper surface of the substrate W is oxidized by the ozone-containing gas, whereby the hydrophilicity of the upper surface of the substrate W becomes higher (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 liquid is likely to spread on the upper surface of the substrate W. Therefore, thinning of the liquid film 100 of the sulfuric acid liquid can be achieved. Furthermore, by thinning the liquid film 100, ozone can easily reach the upper surface of the substrate W, and the organic film can be rapidly and sufficiently removed from the upper surface of the substrate W.

[0219] In the substrate processing of the third modification example, the upper surface of the substrate W can be hydrophilized by supplying an ozone-containing gas. Therefore, the ozone-containing gas can be used for both hydrophilization of the upper surface of the substrate W and removal of the organic film from the upper surface of the substrate W. Therefore, compared with the case where the upper surface of the substrate W is hydrophilized by a method different from the supply of the ozone-containing gas, the equipment required for substrate processing can be simplified.

[0220] In Figure 9C In the substrate processing of the third modification example shown, after the substrate heating start step (step S21), an ozone-containing gas supply start step (step S121) is executed. Although not shown, different from the substrate processing of the third modification example shown in Figure 9C , the ozone hydrophilization start step (step S121) may also be started before the substrate start step (step S21).

[0221] <Substrate Processing Apparatus of the Second Embodiment>

[0222] Figure 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 included in the substrate processing apparatus 1A of the second embodiment. In Figure 10 , for the configurations that are the same as those shown in the above Figures 1 - 9C , the same reference numerals as Figure 1 etc. are assigned and their descriptions are omitted.

[0223] The main difference between the substrate processing apparatus 1A of the second embodiment and the substrate processing apparatus 1 of the first embodiment is that the substrate processing apparatus 1A further includes a sulfuric acid-containing liquid recovery unit 17 for recovering the sulfuric acid-containing liquid discharged from the upper surface of the substrate W.

[0224] The sulfuric acid-containing liquid recovery unit 17 includes: a plurality of (two in the example shown in Figure 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 supply pipe 112 for transporting the sulfuric acid-containing liquid from the plurality of recovery tanks 110 to the storage tank 80.

[0225] The recovery tank 110 is a tank with a closed upper part, and the 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 in contact with the liquid level of the sulfuric acid-containing liquid in the recovery tank 110. The exhaust pipe 117 exhausts the internal space SP of the recovery tank 110.

[0226] 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 branched from the upstream recovery pipe 126 and respectively connected to a plurality of recovery tanks 110.

[0227] 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 respectively connected to a plurality of recovery tanks 110.

[0228] 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, which is upstream of the connection between the upstream recovery pipe 126 and the upstream recovery valve 113, and discharges the sulfuric acid-containing liquid in the upstream recovery pipe 126; and a waste valve 115 provided in the waste pipe 114.

[0229] 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 supply filter 121, a liquid supply pump 122, an upstream liquid supply valve 123, a liquid supply circulation pipe 124, and a liquid supply circulation valve 125. One of each of these components is provided in each recovery tank 110.

[0230] 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.

[0231] The ozone concentration meter 118 includes, for example: a detector main body; and a gas supply pipe having a front end located in the internal space SP of the recovery tank 110, and conveying the gas in the internal space SP of the recovery tank 110 to the detector main body.

[0232] As Figure 10 shown, the recovery tank heater 119 is, for example, a heater mounted on the wall portion of the recovery tank 110 from the outer side. Different from Figure 10 , it can be mounted on the lower side of the bottom wall of the recovery tank 110, or on both the bottom wall and the side wall. The recovery tank heater 119 can also be a heater immersed in the sulfuric acid-containing liquid in the recovery tank 110.

[0233] The liquid supply filter 121 removes impurities from the sulfuric acid-containing liquid passing through the upstream liquid supply pipe 129. The liquid supply pump 122 is provided on the downstream side of the liquid supply filter 121 in the upstream liquid supply pipe 129, and sends the sulfuric acid-containing liquid in the upstream liquid supply pipe 129 to the storage tank 80.

[0234] The upstream liquid supply valve 123 is provided on the downstream side of the liquid supply pump 122 in the upstream liquid supply pipe 129 and opens and closes the upstream liquid supply pipe 129. The liquid supply circulation pipe 124 is connected in the upstream liquid supply pipe 129 at a position downstream of the liquid supply pump 122 and upstream of the upstream liquid supply valve 123. The liquid supply circulation valve 125 opens and closes the liquid supply circulation pipe 124.

[0235] According to the second embodiment, it is possible to recover the sulfuric acid-containing liquid supplied from the first moving nozzle 9 to the upper surface of the substrate W and reuse the sulfuric acid-containing liquid. Thereby, the amount of sulfuric acid to be discarded can be reduced. 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 removing the ozone by vaporizing it from the sulfuric acid-containing liquid, the sulfuric acid-containing liquid from which the ozone has been sufficiently removed can be reused. Therefore, it is 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.

[0236] In addition, since a plurality of recovery tanks 110 are provided, even if any one of the recovery tanks 110 is not ready, it is possible to supply the sulfuric acid-containing liquid from the other recovery tanks 110 to the storage tank 80. The recovery tank 110 not being ready means a case where the amount of the sulfuric acid-containing liquid in the recovery tank 110 is insufficient or a case where the ozone cannot be sufficiently removed from the sulfuric acid-containing liquid in the recovery tank 110.

[0237] <Substrate processing apparatus of the third embodiment>

[0238] Figure 11 It is a schematic diagram for explaining the configuration of the processing unit 2 included in the substrate processing apparatus 1B of the third embodiment. In Figure 11 For the components having the same configuration as those shown in the above Figures 1 - 10 the same reference numerals as those in Figure 1 etc. are given and their descriptions are omitted. The same applies to the following Figure 12 .

[0239] The main difference between the processing unit 2 of the third embodiment and the processing unit 2 of the first embodiment is that the processing chamber 12 is not provided in the processing unit 2 of the third embodiment.

[0240] Specifically, the ozone-containing gas supply member 13 included in the processing unit 2 of the third embodiment supplies the 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. The ozone-containing gas nozzle 130 is connected to the ozone-containing gas pipe 45. By opening the ozone-containing gas valve 55A, it is possible to start supplying the ozone-containing gas to the internal space 7c of the chamber 7. In the third embodiment, the chamber 7 functions as a processing chamber.

[0241] Unlike Figure 11 the ozone-containing gas supply member 13 may also have a discharge port that opens to the side wall 7b of the chamber 7.

[0242] In the third embodiment, the substrate processing ( Figure 5 , Figures 9A - 9C ) identical to that of the first embodiment can also be performed.

[0243] In the third embodiment, the substrate processing Figure 12 shown can also be performed. Figure 12 is a flowchart for explaining an example of the substrate processing performed by the substrate processing apparatus 1B. In the Figure 12 substrate processing shown, unlike the Figure 9C substrate processing shown, the supply of the ozone-containing gas to the processing chamber 12 starts before the liquid film forming step (step S3) and stops after the liquid film forming step (step S3) ends.

[0244] Specifically, an electric current is supplied to the heater 61 by the energization unit 63, and the temperature rise of the heater 61 starts. Then, the heater drive mechanism 66 moves the substrate heating member 14 from the retracted position to the approaching position. The temperature rise of the heater 61 starts and the substrate heating member 14 is disposed at the approaching position, thereby starting the heating of the substrate W (substrate heating start step: step S21). Thereby, the substrate heating step (step S2) is performed.

[0245] Before starting to discharge the sulfuric acid-containing liquid onto the upper surface of the substrate W, the ozone-containing gas valve 55A is opened. Thereby, the supply of the ozone-containing gas from the ozone-containing gas supply member 13 to the internal space 7c of the chamber 7 starts (ozone-containing gas supply start step: step S121). By continuing to supply the ozone-containing gas to the internal space 7c of the chamber 7, the chamber 7 can be filled with the ozone-containing gas (ozone-containing gas supply step, ozone-containing gas filling step).

[0246] By filling the chamber 7 with the ozone-containing gas, the upper surface of the substrate W held by the rotating chuck 8 is exposed to the ozone-containing gas (substrate upper surface exposure step). The upper surface of the substrate W is hydrophilized by exposing the upper surface of the substrate W to the ozone-containing gas (ozone hydrophilization step, hydrophilization step: step S12).

[0247] After that, the liquid film forming step (step S3) is performed. In a state where the liquid film 100 of the sulfuric acid-containing liquid is formed on the upper surface of the substrate W, the chamber 7 can be pressurized by supplying the ozone-containing gas into the chamber 7 (pressurized supply step).

[0248] After the liquid film formation process (step S3), the ozone-containing gas valve 55A is closed. Thereby, the supply of the ozone-containing gas from the ozone-containing gas supply member 13 to the internal space 7c of the chamber 7 is stopped (ozone-containing gas supply stop process: step S41). By discharging the ozone-containing gas from the internal space 7c of the chamber 7 via the discharge pipe 32 in a state where the supply of the ozone-containing gas is stopped, the exposure of the ozone-containing gas to the upper surface of the substrate W can be stopped.

[0249] Thereafter, the heater drive mechanism 66 moves the substrate heating member 14 from the approaching position to the retracted position. By disposing the substrate heating member 14 at the retracted position, the heating of the substrate W is stopped (substrate heating stop process: step S22). Thereby, the substrate heating process (step S2) ends.

[0250] Then, the first rinsing process (step S5) to the substrate unloading process (step S11) are sequentially executed.

[0251] Thus, by using the substrate processing apparatus 1B of the third embodiment, the supply of the ozone-containing gas can be started earlier than the discharge of the sulfuric acid-containing liquid. Therefore, compared with the substrate processing apparatus 1 of the first embodiment, various substrate processes can be executed. According to the substrate processing apparatus 1B of the third embodiment, the same effects as those of the substrate processing apparatus 1 of the first embodiment are achieved.

[0252] In the case of performing Figure 12 the substrate process shown, in the substrate process in which the supply of the ozone-containing gas is started earlier, the supply of the ozone-containing gas may also be started based on the detected temperature of the temperature sensor 62. Specifically, the first start unit 91 starts the supply of the ozone-containing gas from the ozone-containing gas supply member 13 when the temperature determination unit 90 determines that the detected temperature of the temperature sensor 62 is within the processing temperature range. Therefore, in a state where the substrate W is heated to a sufficiently high temperature, the supply of the ozone-containing gas from the ozone-containing gas supply member 13 is started. Therefore, the removal of the organic film from the upper surface of the substrate W can be started promptly.

[0253] <Other Embodiments>

[0254] The present invention is not limited to the embodiments described above and can be implemented in other ways.

[0255] (1) In each of the above embodiments, it is configured to discharge the processing liquid from a plurality of moving nozzles. However, different from the above embodiments, it may be configured to discharge the processing liquid from a fixed nozzle whose position in the horizontal direction is fixed, or it may be configured to discharge all of the processing liquid from a single nozzle.

[0256] For example, different from the first embodiment, the first moving nozzle 9 may not be provided, and a sulfuric acid-containing liquid nozzle including a discharge port where a sulfuric acid-containing liquid supply member exposes from the housing 71 of the processing chamber 12 may be included. In this case, the same substrate processing as that of the third embodiment can be performed (for example, refer to Figure 12 ).

[0257] (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 expanded 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 coating the sulfuric acid-containing liquid. Specifically, the liquid film 100 may be formed while bringing a strip-shaped coating member on which the sulfuric acid-containing liquid adheres into contact with the upper surface of the substrate W and moving it along the upper surface of the substrate W. Alternatively, after supplying a continuous flow of the sulfuric acid-containing liquid to the upper surface of the substrate W, the liquid film 100 may be formed by spreading it over the entire upper surface of the substrate W using a rod-shaped coating member.

[0258] (3) As an example of the substrate processing, Figure 5 , Figures 9A - 9C , Figure 12 are shown. However, as an example of the substrate processing, it is not limited to the above examples. For example, after the supply of the ozone-containing gas to the processing chamber 12 is completed, the processing chamber 12 may be moved to the accommodation position so that the liquid film 100 is exposed to the ozone-containing gas. In addition, the discharge of the sulfuric acid-containing liquid and the supply of the ozone-containing gas may be started simultaneously. In addition, the substrate heating stop process (step S22) may also be stopped during the execution of the first rinsing process (step S5). In addition, the chemical liquid supply process (step S7) to the organic solvent supply process (step S9) may be appropriately omitted.

[0259] In the case where the discharge of the sulfuric acid-containing liquid and the supply of the ozone-containing gas are started simultaneously, the discharge of the sulfuric acid-containing liquid and the supply of the ozone-containing gas may also be started based on the detected temperature of the temperature sensor 62. Specifically, the first start unit 91 may start both the supply of the ozone-containing gas and the discharge of the sulfuric acid-containing liquid when the temperature determination unit 90 determines that the detected temperature of the temperature sensor 62 is within the temperature range of the processing temperature.

[0260] (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 opposed to the upper surface of the substrate W, or may include a heater opposed to 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 or warm water to the lower surface of the substrate W. The substrate heating member may also be configured to heat the plate body 60 by circulating the heating fluid within the plate body 60. In the case of using a heating fluid, adjustment of the temperature of the substrate W is performed by adjusting the opening degree of a valve that controls the flow rate of the heating fluid.

[0261] (5) In the substrate processing apparatus 1, a cooling plate (not shown) for cooling the substrate W may also be provided. The substrate W may also be cooled to room temperature by the cooling plate after the substrate heating stop step (step S22).

[0262] (6) In each of the above-described embodiments, the rotary chuck 8 is a holding-type rotary chuck that holds the periphery of the substrate W by a plurality of holding pins 20, but the rotary chuck 8 is not limited to a holding-type rotary chuck. For example, the rotary chuck 8 may also be a vacuum adsorption-type rotary chuck that adsorbs the substrate W to the rotary base 21.

[0263] (7) The configuration of the processing chamber 12 is not limited to Figure 2 the configuration shown. For example, an openable and closable processing chamber may also be provided within the chamber 7.

[0264] In addition, the rotary base 21 may also be configured to move up and down. Accordingly, the substrate accommodation step may be a step of raising (moving) the substrate W within the chamber 7 to accommodate the substrate W in the processing chamber 12, and the substrate detachment step may be a step of lowering (moving) the substrate W within the chamber 7 to detach the substrate W from the processing chamber 12. In short, the substrate accommodation step may be any step of relatively moving the processing chamber 12 with respect to the substrate W within the chamber 7 to accommodate the substrate W in the processing chamber 12. Similarly, the substrate detachment step may be any step of relatively moving the processing chamber 12 with respect to the substrate W within the chamber 7 to detach the substrate W from the processing chamber 12.

[0265] (8) Hydrophilic treatment of the upper surface of the substrate W may also be performed by a method other than oxidation based on an ozone-containing gas. For example, the upper surface of the substrate W may be made hydrophilic by irradiating ultraviolet rays to the upper surface of the substrate W.

[0266] (9) In each of the above-described embodiments, the controller 3 controls the entirety of the substrate processing apparatus 1. However, controllers that control the respective components of the substrate processing apparatus 1 may also be dispersed in multiple locations. In addition, the controller 3 does not need to directly control each component, and signals output from the controller 3 may also be received by slave controllers that control the respective components of the substrate processing apparatus 1.

[0267] (10) Further, in the above-described embodiments, the substrate processing apparatuses 1, 1A, and 1B include a transfer robot (first transfer robot IR and second transfer robot CR), a plurality of processing units 2, and a controller 3. However, the substrate processing apparatuses 1, 1A, and 1B may be composed of a single processing unit 2 and a controller 3, and may not include a transfer robot. Alternatively, the substrate processing apparatuses 1, 1A, and 1B may also be composed of only a single processing unit 2. In other words, the processing unit 2 may also be an example of a substrate processing apparatus.

[0268] (11) In the above-described embodiments, expressions such as "along", "horizontal", "vertical", and "cylindrical" are used. However, each of these expressions does not necessarily have to be strictly "along", "horizontal", "vertical", or "cylindrical". That is, each of these expressions allows for deviations in manufacturing accuracy, setting accuracy, and the like.

[0269] (12) Further, each configuration is sometimes schematically shown in a block diagram, but the shape, size, and positional relationship of the block diagram do not represent the shape, size, and positional relationship of each configuration.

[0270] The embodiments of the present invention have been described in detail, but these are merely specific examples used to clarify the technical content of the present invention. The present invention is not construed as being limited to these specific examples, and the scope of the present invention is defined only by the scope of the appended claims.

Claims

1. A substrate processing method, wherein an organic film is formed on a main surface of the substrate, and the substrate processing method includes: A liquid film forming step of forming a liquid film containing a sulfuric acid liquid on the main surface of the substrate; An ozone-containing gas exposure step of filling a processing chamber capable of accommodating the substrate with an ozone-containing gas to expose the liquid film to the ozone-containing gas, enabling ozone in the ozone-containing gas to dissolve in the sulfuric acid liquid constituting the liquid film to form peroxydisulfuric acid in the liquid film; And A substrate heating step of heating the substrate in a state where the substrate is disposed in the processing chamber filled with the ozone-containing gas, a liquid film is formed on the main surface of the substrate, and peroxydisulfuric acid is formed in the liquid film.

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

3. The substrate processing method according to claim 1, wherein, The ozone-containing gas exposure step includes a pressurized supply step of supplying the ozone-containing gas to the processing chamber in such a manner that the pressure in the processing chamber is higher than the pressure outside the processing chamber.

4. The substrate processing method according to claim 1 further includes: After the substrate heating step, a rinse liquid supply step of supplying a rinse liquid to the main surface of the substrate.

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

6. The substrate processing method according to claim 1, wherein, The ozone-containing gas exposure step includes a step of starting to supply an ozone-containing gas to the processing chamber in a state where the substrate having the liquid film formed on the main surface is disposed in the processing chamber, so that the processing chamber is filled with the ozone-containing gas.

7. The substrate processing method according to claim 1 further includes: A hydrophilic treatment step of hydrophilizing the main surface of the substrate before the start of the formation of the liquid film in the liquid film forming step.

8. The substrate processing method according to claim 7, wherein, The hydrophilic treatment step includes an ozone hydrophilic treatment step of supplying an ozone-containing gas to the processing chamber in a state where the substrate is disposed in the processing chamber before the start of the formation of the liquid film in the liquid film forming step, so that the main surface of the substrate is exposed to the ozone-containing gas.

9. The substrate processing method according to any one of claims 1 to 8 further includes: A substrate holding step of holding the substrate on a substrate holding member disposed in a chamber, The ozone-containing gas exposure step includes a substrate accommodating step of relatively moving the processing chamber with respect to the substrate held on the substrate holding member in the chamber to accommodate the substrate held on the substrate holding member in the processing chamber; an ozone-containing gas supply step of supplying an ozone-containing gas to the processing chamber in a state where the substrate is accommodated in the processing chamber; and a substrate detaching step of relatively moving the processing chamber with respect to the substrate held on the substrate holding member in the chamber after the ozone-containing gas supply step to detach the substrate held on the substrate holding member from the processing chamber.

10. A substrate processing apparatus, which includes: A substrate holding member that holds a substrate having an organic film formed on a main surface in a predetermined processing posture; A processing chamber capable of accommodating a 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 ozone-containing gas into the processing chamber; A sulfuric acid-containing liquid discharge member for discharging sulfuric acid-containing liquid toward the main surface of the substrate held by the substrate holding member; And A controller for controlling the substrate heating member, the ozone-containing gas supply member, and the sulfuric acid-containing liquid discharge member, The controller is programmed to: when the substrate held by the substrate holding member is disposed in the processing chamber and the substrate is heated by the substrate heating member, discharge 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 sulfuric acid-containing liquid on the main surface of the substrate, and supply ozone-containing gas from the ozone-containing gas supply member into the processing chamber to expose the liquid film to the ozone-containing gas, enabling ozone in the ozone-containing gas to dissolve in the sulfuric acid-containing liquid constituting the liquid film to form peroxydisulfuric acid in the liquid film, and heating the substrate in a state where peroxydisulfuric acid is formed in the liquid film.

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

12. The substrate processing apparatus according to claim 11, wherein The first start unit starts the discharge of sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member when the temperature determination unit determines that the detected temperature of the temperature sensor is within the temperature range of the processing temperature. The controller is programmed to further execute the functions of a time elapse determination unit and a second start unit. The time elapse determination unit determines whether the liquid film formation time has elapsed after starting the discharge of sulfuric acid-containing liquid from the sulfuric acid-containing liquid discharge member. The second start unit starts the supply of 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. The substrate processing apparatus according to claim 10, further comprising: A chamber for accommodating the substrate holding member and the processing chamber; And A processing chamber drive mechanism for relatively moving the processing chamber with respect to the substrate holding member in such a manner that the substrate held by the substrate holding member moves relatively between inside and outside the processing chamber.

14. The substrate processing apparatus according to claim 13, wherein The sulfuric acid-containing liquid discharging member includes a sulfuric acid-containing liquid nozzle for discharging the sulfuric acid-containing liquid. The substrate processing apparatus further includes 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 in a state where the substrate held by the substrate holding member is outside the processing chamber.

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

16. The substrate processing apparatus according to any one of claims 10 to 15, further comprising: 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 discharging member.

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