Substrate processing method

Abstract

To provide a wafer processing method capable of efficiently removing a removal target substance of an organic material on a wafer while reducing usage of a liquid medicine (especially, sulfuric acid).SOLUTION: A wafer processing method includes: a step of preparing a wafer W comprising on a principal surface a polymer film P containing a polymer including a sulfonic acid group; an oxidant supply step of supplying an oxidant onto the principal surface of the wafer; and an organic material removal step of removing a removal target substance of an organic material existing on the principal surface of the wafer by a reaction product of the sulfonic acid group in the polymer film and the oxidant. The oxidant supply step may also be a liquid-state oxidant supply step or may also be an oxidant steam supply step. The step of preparing the wafer includes: a polymer application step of applying the polymer including the sulfonic acid group onto the principal surface of the wafer; and a bake step of baking the polymer applied onto the principal surface of the wafer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] This invention relates to a substrate processing method for processing a substrate. The substrates to be processed include, for example, semiconductor wafers, substrates for flat panel displays (FPD) such as liquid crystal display devices and organic EL (Electroluminescence) display devices, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates, and the like.

Background Art

[0002] In the manufacturing process of semiconductor devices, a resist (photoresist) is used as a mask for forming patterns on a substrate and for ion implantation into active regions. As a wet process for removing the used resist from the substrate, a process using a sulfuric acid-hydrogen peroxide mixture (SPM) is known. Specifically, as described in Patent Document 1, sulfuric acid and hydrogen peroxide are mixed to generate SPM, and the SPM is supplied to the surface of the substrate, whereby the resist on the substrate is removed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Sulfuric acid is an expensive chemical solution and also a chemical solution with a high environmental impact. Therefore, from the viewpoints of reducing the processing cost and the environmental impact, a reduction in the usage amount is required.

[0005] One embodiment of this invention provides a substrate processing method capable of efficiently removing substances to be removed of organic matter on a substrate while reducing the usage amount of a chemical solution (particularly sulfuric acid).

Means for Solving the Problems

[0006] One embodiment of this invention provides a substrate processing method having the following exemplary features.

[0007] 1. A step of preparing a substrate having a polymer film containing a polymer with sulfonic acid groups as its main surface, An oxidizing agent supply step of supplying an oxidizing agent to the main surface of the substrate, A substrate processing method comprising: an organic matter removal step, which removes organic substances to be removed present on the main surface of the substrate by reaction products of the sulfonic acid groups in the polymer film and the oxidizing agent.

[0008] 2. The substrate processing method according to item 1, wherein the substance to be removed includes at least one of resist and residue after dry etching.

[0009] 3. The substrate processing method according to item 1 or 2, wherein the oxidizing agent supply step involves supplying a liquid or vapor of an oxidizing agent to the main surface of the substrate.

[0010] 4. The substrate treatment method according to any one of items 1 to 3, wherein the oxidizing agent comprises at least one of hydrogen peroxide and ozone.

[0011] 5. The oxidizing agent supply step is: A continuous supply process in which hydrogen peroxide solution or ozonated water is discharged from a nozzle in a continuous flow and supplied to the main surface of the substrate, A mist supply step in which hydrogen peroxide solution, ozonated water, or a mixture of sulfuric acid and hydrogen peroxide solution (SPM) is discharged in a mist form from a nozzle and supplied to the main surface of the substrate, A steam supply step in which hydrogen peroxide or ozone is mixed with water vapor and supplied to the main surface of the substrate, A substrate processing method according to item 1 or 2, comprising at least one of the following:

[0012] 6. Before the commencement of the oxidizing agent supply step, the polymer film is in a solidified state (for example, semi-solid or solid), The substrate processing method according to claim 1 or 2, wherein the oxidizing agent supply step includes a liquid oxidizing agent supply step (continuous flow or mist) of supplying a liquid oxidizing agent to the main surface of the substrate.

[0013] 7. Before the start of the oxidizing agent supply step, the polymer film is in an unsolidified state (for example, in a flow state, liquid state, etc.). The substrate processing method according to claim 1 or 2, wherein the oxidizing agent supply step includes an oxidizing agent vapor supply step of supplying oxidizing agent vapor to the main surface of the substrate.

[0014] 8. A substrate processing method according to any one of claims 1 to 7, further comprising a parallel heating step of heating the substrate in parallel with the oxidizing agent supply step.

[0015] 9. The substrate processing method according to item 8, wherein the parallel heating step is started before the supply of the oxidizing agent is started.

[0016] 10. The process of preparing the substrate is as follows: A polymer coating step in which a polymer containing sulfonic acid groups (typically a polymer solution) is applied to the main surface of the substrate, A substrate processing method according to any one of claims 1 to 9, comprising a baking step of baking a polymer applied to the main surface of the substrate.

[0017] 11. The polymer coating step is performed in the first chamber, The baking process is carried out in a second chamber separate from the first chamber. The substrate processing method according to item 10, wherein the oxidizing agent supply step is performed in a third chamber separate from the first and second chambers.

[0018] 12. The process of preparing the substrate is performed by the first substrate processing apparatus, The substrate processing method according to any one of claims 1 to 11, wherein the oxidizing agent supply step is performed in a second substrate processing apparatus separate from the first substrate processing apparatus.

[0019] 13. The polymer containing the sulfonic acid group includes at least one of vinyl sulfonic acid-vinyl alcohol copolymer (PVS-VA), vinyl sulfonic acid-styrene copolymer (PVS-St), polyvinyl sulfonic acid (PVS), polystyrene sulfonic acid (PSS), polystyrene partial sulfonate (PS-S), ammonium sulfonate salt, and metal sulfonate salt, and the substrate processing method according to any one of items 1 to 12.

Brief Description of Drawings

[0020] [Figure 1] FIG. 1 shows an example of a substrate processing method according to a first embodiment of the present invention. [Figure 2] FIG. 2 shows an example of a substrate processing method according to a second embodiment of the present invention. [Figure 3] FIG. 3 is a schematic plan view for explaining a configuration example of a substrate processing apparatus for executing a substrate processing method according to an embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram for explaining a configuration example of a processing unit provided in the substrate processing apparatus, and shows a configuration example for executing the substrate processing method according to the first embodiment shown in FIG. 1. [Figure 5] FIG. 5 is a schematic diagram for explaining another configuration example of the processing unit provided in the substrate processing apparatus, and shows a configuration example for executing the substrate processing method according to the second embodiment shown in FIG. 2. [Figure 6] FIG. 6 is a block diagram for explaining an electrical configuration of the substrate processing apparatus. [Figure 7] FIG. 7 is a flowchart for explaining an example of substrate processing executed by the substrate processing apparatus. [Figure 8] FIG. 8 is a flowchart for explaining another example of substrate processing executed by the substrate processing apparatus. [Figure 9] FIG. 9 is a schematic plan view showing a schematic configuration of a substrate processing apparatus for executing a substrate processing method according to another embodiment of the present invention.

Embodiments for Carrying Out the Invention

[0021] Hereinafter, embodiments of this invention will be described in detail with reference to the accompanying drawings.

[0022] Figure 1 shows an example of a substrate processing method according to the first embodiment of this invention, and Figure 2 shows an example of a substrate processing method according to the second embodiment of this invention.

[0023] The substrate processing method of the first embodiment (Figure 1) and the second embodiment (Figure 2) includes a step of preparing a substrate W having a polymer film P containing a polymer with sulfonic acid groups on its main surface (Figures 1(b)(c), 2(b)(c)), an oxidizing agent supply step of supplying an oxidizing agent to the main surface of the substrate W (Figures 1(d), 2(d)), and an organic matter removal step of removing organic substances to be removed from the main surface of the substrate W by reaction products between the sulfonic acid groups in the polymer film P and the oxidizing agent (typically removed by a chemical reaction between the reaction products and the organic matter) (Figures 1(d), 2(d)). The organic matter removal step typically proceeds simultaneously with the oxidizing agent supply step.

[0024] The polymer film P is typically a coated film of a polymer material. The polymer film P is typically formed and exposed on the outermost surface of the substrate W so as to come into contact with the oxidizing agent when it is supplied.

[0025] The polymer film P may be a liquid film or a solidified film. A liquid film is typically a film formed by applying a polymer solution, in which a polymer is dissolved in a solvent (an example of a coated film). A solidified film is typically a film formed by solidifying such a liquid film and fixing it to the main surface of the substrate W (another example of a coated film), and is formed, for example, by evaporating the solvent after the liquid film has formed to reduce its fluidity. The solidified film may be a semi-solid film with some fluidity remaining in the solvent, or it may be a solid film in which most of the solvent has been evaporated to solidify it.

[0026] Typically, organic substances to be removed exist between the polymer film P and the substrate material (e.g., silicon). Specifically, these substances include at least one of the resist and the residue after dry etching.

[0027] According to this substrate processing method, a reaction product is generated by the reaction between the sulfonic acid groups contained in the polymer in the polymer film P provided on the main surface of the substrate W and an oxidizing agent. Since this reaction product is a caroate-based compound, it chemically reacts with organic matter to decompose it. This decomposition reaction makes it possible to remove organic substances that are the target of removal from the main surface of the substrate W. Because the polymer in the polymer film P contains sulfonic acid groups, organic substances that are the target of removal can be decomposed without supplying sulfuric acid to the main surface of the substrate W, and organic matter removal performance almost equivalent to that achieved when a sulfuric acid-hydrogen peroxide mixture (SPM) is continuously supplied to the substrate W can be achieved.

[0028] Chemical formula 1 below shows an example of a chemical reaction in which a polymer (R-SO3H) having a sulfonic acid group (-SO3H) reacts with an oxidizing agent to produce a reaction product. Chemical formula 2 below shows an example of a chemical reaction in which the reaction product reacts with an organic substance (containing carbon atoms, hydrogen atoms, and oxygen atoms) to decompose the organic substance into a liquid or gas. In these chemical formulas, R represents a substituent such as alkyl or aryl.

[0029] [ka]

[0030] [ka] The oxidizing agent supply step may be a liquid oxidizing agent supply step that supplies a liquid oxidizing agent (liquid oxidizing agent), or an oxidizing agent vapor supply step that supplies oxidizing agent vapor (oxidizing agent vapor) to the main surface of the substrate W (vapor supply step). The liquid oxidizing agent supply step may be a continuous supply step that supplies the liquid oxidizing agent in the form of a continuous flow, or a mist supply step that supplies the liquid oxidizing agent in the form of a mist (spray supply). The oxidizing agent preferably contains at least one of hydrogen peroxide and ozone.

[0031] In the first embodiment shown in Figure 1, the oxidizing agent supply step is a liquid oxidizing agent supply step in which a liquid oxidizing agent (liquid oxidizing agent) is supplied to the main surface of the substrate W (see Figure 1(d)). One example of the liquid oxidizing agent supply step is a continuous supply step in which hydrogen peroxide solution or ozonated water is discharged in a continuous flow from a nozzle (N2) and supplied to the main surface of the substrate W. In this case, without using sulfuric acid, a caroate-based compound can be generated on the substrate W, and organic substances to be removed from the substrate W can be removed. Another example of the liquid oxidizing agent supply step is a mist supply step in which hydrogen peroxide solution, ozonated water, or a sulfuric acid-hydrogen peroxide solution mixture (SPM) is discharged in a mist from a spray nozzle (N2) and supplied to the main surface of the substrate W. In mist discharge from a spray nozzle (N2), the amount of liquid supplied is small, so even when using a sulfuric acid-hydrogen peroxide solution mixture, the amount used is small, and therefore the amount of sulfuric acid used can be suppressed. Therefore, while suppressing the amount of sulfuric acid used, a caroate-based compound can be generated on the substrate W to remove organic substances on the substrate W. When using hydrogen peroxide or ozonated water, there is no need to use sulfuric acid, so a caroate-based compound can be generated on the substrate W without using sulfuric acid to remove organic substances on the substrate W.

[0032] In the second embodiment shown in Figure 2, the oxidizing agent supply step is an oxidizing agent vapor supply step (vapor supply step) in which oxidizing agent vapor (vapor of the oxidizing agent) is supplied from a vapor nozzle (N2) to the main surface of the substrate W (see Figure 2(d)). The oxidizing agent vapor supply step may also be a step in which hydrogen peroxide or ozone is mixed with water vapor and supplied to the main surface of the substrate W. For example, a mixed gas of hydrogen peroxide water and water vapor can be generated by bubbling an inert gas such as nitrogen gas in hydrogen peroxide water. Alternatively, a mixed gas of ozone and water vapor (humid ozone gas) can be generated by bubbling ozone gas in water (typically deionized water). By supplying these mixed gases to the vapor nozzle (N2), a mixed gas of hydrogen peroxide or ozone and water vapor can be supplied from the vapor nozzle (N2) to the main surface of the substrate W.

[0033] If the polymer film P is in a solidified state (semi-solid or solid) before the start of the oxidizing agent supply process, the oxidizing agent supply process may be a liquid oxidizing agent supply process (see Figure 1(d)) in which a liquid oxidizing agent is supplied to the main surface of the substrate W (supplied in the form of a continuous flow or mist). This promotes the elution of the polymer and accelerates the reaction between the sulfonic acid groups in the polymer and the oxidizing agent, thereby promoting the formation of caroic acid-based compounds. This allows for the efficient removal of organic substances on the substrate W while suppressing the amount of sulfuric acid used or eliminating the need for sulfuric acid supply.

[0034] If the polymer film P is in an unsolidified state (flowing state, liquid) before the start of the oxidizing agent supply process, the oxidizing agent supply process is preferably an oxidizing agent vapor supply process (see Figure 2(d)) in which oxidizing agent vapor is supplied to the main surface of the substrate W. This allows for efficient reaction between the sulfonic acid groups in the polymer and the oxidizing agent, while suppressing the outflow (elution) of the polymer film P from the substrate W, thereby generating a caroic acid-based compound. This allows for efficient removal of organic substances on the substrate W without the need to supply sulfuric acid. However, the oxidizing agent vapor supply process may also be applied when the polymer film P is in a solidified state.

[0035] In both the first and second embodiments of the substrate processing method, it is preferable to further perform a parallel heating step in which the substrate W is heated in parallel with the oxidizing agent supply step (see Figures 1(d) and 2(d)). This promotes the reaction between the sulfonic acid groups in the polymer and the oxidizing agent, and further promotes the reaction between the caroic acid-based compound produced by this reaction and the organic substances to be removed. This allows for the efficient removal of the substances to be removed.

[0036] The parallel heating step may be a step of heating the substrate W with a heater unit 14 (typically a hot plate) that is positioned in close proximity to the substrate W, either in contact or not (see Figures 1(d) and 2(d)). Alternatively, the substrate W may be heated with an infrared lamp or a high-temperature inert gas (e.g., high-temperature nitrogen gas or high-temperature clean air). Furthermore, the substrate W may be heated with any combination of two or more of these.

[0037] The parallel heating process is preferably started before the supply of the oxidizing agent. This further promotes the reaction between the oxidizing agent and the sulfonic acid group, and the reaction between the caroic acid-based compound produced by this reaction and the organic matter to be removed.

[0038] The process of preparing the substrate W may include a polymer coating step (see Figures 1(b) and 2(b)) in which a polymer containing sulfonic acid groups is applied to the main surface of the substrate W, and a baking step (see Figures 1(c) and 2(c)) in which the polymer applied to the main surface of the substrate W is baked. In this case, the polymer film P becomes a solidified film (semi-solid or solid). For example, if the baking step (see Figure 2(c)) is omitted, the polymer film P is an unsolidified liquid film before the start of the oxidizing agent supply step. In such cases, an oxidizing agent vapor supply step (see Figure 2(d)) is more suitable than a liquid oxidizing agent supply step (see Figure 1(d)).

[0039] The polymer coating process (see Figures 1(b) and 2(b)), the baking process (see Figures 1(c) and 2(c)), the oxidizing agent supply process (see Figures 1(d) and 2(d)), and the organic matter removal process (see Figures 1(d) and 2(d)) for removing organic substances may be performed within a single chamber. More specifically, the polymer coating process, the baking process, the oxidizing agent supply process, and the organic matter removal process may be performed on a single substrate W while the substrate W is held in a substrate holding unit (substrate holder) (e.g., a spin chuck 8).

[0040] After a substrate loading step (see Figures 1(a) and 2(a)) in which the substrate W is loaded into the spin chuck 8, the following steps may be performed while the substrate W is rotated by the spin chuck 8: polymer coating step (see Figures 1(b) and 2(b)), baking step (see Figures 1(c) and 2(c)), oxidizing agent supply step (see Figures 1(d) and 2(d)), and organic matter removal step (see Figures 1(d) and 2(d)).

[0041] For example, the polymer coating process (see Figures 1(b) and 2(b)) may be a spin coating process in which the polymer solution is supplied to the main surface of the substrate W while the substrate W is rotated by a spin chuck 8 (for example, at a rotation speed of 10 to 3000 rpm), and the polymer solution is spread across the main surface of the substrate W by centrifugal force.

[0042] The baking process (Figures 1(c) and 2(c)) may be a process of heating the substrate W with the heater unit 14. When the heater unit 14 is in contact with the substrate W, it is preferable that the rotation of the substrate W is stopped. When heating is performed with the heater unit 14 and the substrate W in a non-contact state, the substrate W may be rotating.

[0043] In the oxidizing agent supply step and the organic matter removal step carried out simultaneously (see Figures 1(d) and 2(d)), it is preferable to rotate the substrate W with the spin chuck 8 (for example, at a rotation speed of 10 to 3000 rpm) while simultaneously heating the substrate W with the heater unit 14. In this case, it is preferable that the substrate W and the heater unit are not in contact.

[0044] After the oxidizing agent supply step and the organic matter removal step carried out simultaneously (see Figures 1(d) and 2(d)), it is preferable to perform a rinsing step (see Figures 1(e) and 2(e)) in which a rinsing solution is supplied to the main surface of the substrate W and the processing solution (oxidizing agent, reaction products, etc.) and residues of the substances to be removed are washed away from the main surface of the substrate W. During this rinsing step, it is preferable to rotate the substrate W using a spin chuck 8 (for example, at a rotation speed of 10 to 3000 rpm) and utilize the effect of centrifugal force.

[0045] Furthermore, it is preferable to perform a drying step (see Figures 1(f) and 2(f)) after the rinsing step to remove liquid components from the substrate W. The drying step may be a spin-drying step in which the spin chuck 8 is rotated at a drying rotation speed (for example, 10 to 3000 rpm).

[0046] The polymer containing the sulfonic acid group preferably includes at least one of the following: vinyl sulfonic acid-vinyl alcohol copolymer (PVS-VA), vinyl sulfonic acid-styrene copolymer (PVS-St), polyvinyl sulfonic acid (PVS), polystyrene sulfonic acid (PSS), polystyrene partial sulfonate (PS-S), ammonium sulfonate salt (R-SO3NH4), and metal sulfonate salt (R-SO3M). Here, M represents a metal, typically one of Li, Na, or K. By using these polymers, caroate-based compounds can be produced by reaction with an oxidizing agent.

[0047] A portion of the above polymer (R-SO3H) is shown in chemical formula 3 below.

[0048] [ka] Ammonium sulfonate salt (R-SO3NH4) is R-SO3 in aqueous solution, as shown in chemical formula 4 below. - and NH4 + It ionizes and, under heating conditions, generates NH3 (ammonia gas) to produce R-SO3H. The metal sulfonic acid salt (R-SO3M) is R-SO3 in aqueous solution, as shown in chemical formula 5 below. - and M + It ionizes.

[0049] [ka]

[0050] [ka] Therefore, by supplying an oxidizing agent, a caroic acid-based reaction product can be produced by the reaction shown in chemical formula 6 below.

[0051] [ka] Furthermore, in processes where metal contamination is a concern, it is preferable to avoid using metal sulfonates.

[0052] The polymer coating process (see Figures 1(b) and 2(b)), the baking process (see Figures 1(c) and 2(c)), and the oxidizing agent supply process (see Figures 1(d) and 2(d)) may be performed within a single chamber. Alternatively, the polymer coating process (see Figures 1(b) and 2(b)) may be performed in a first chamber, the baking process (see Figures 1(c) and 2(c)) may be performed in a second chamber separate from the first chamber, and the oxidizing agent supply process (see Figures 1(d) and 2(d)) may be performed in a third chamber separate from the first and second chambers.

[0053] Furthermore, the process of preparing the substrate W (see Figures 1(b)(c) and 2(b)(c)) may be performed by a first substrate processing apparatus, and the oxidizing agent supply process (see Figures 1(d) and 2(d)) may be performed by a second substrate processing apparatus separate from the first substrate processing apparatus.

[0054] Figure 3 is a schematic plan view illustrating an example of the configuration of a substrate processing apparatus 1 for carrying out a substrate processing method according to one embodiment of the present invention. The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates W one at a time. In this embodiment, the substrate W has a disc shape. The substrate W is a substrate such as a silicon wafer and has a pair of main surfaces.

[0055] The substrate processing apparatus 1 includes a plurality of processing units 2 for processing substrates W, a load port LP (carrier holding unit) on which carriers C (carriers) for accommodating the plurality of substrates W processed by the processing units 2 are placed, a transport robot (in this example, a first transport robot IR and a second transport robot CR) for transporting the substrates W between the load port LP and the processing units 2, and a controller 3 for controlling each component provided in the substrate processing apparatus 1.

[0056] The first transport robot IR transports the substrate W between the carrier C and the second transport robot CR. The second transport robot CR transports the substrate W between the first transport robot IR and the processing unit 2. Each transport robot is, for example, an articulated arm robot.

[0057] Multiple processing units 2 are arranged on both sides of the transport path TR along which the substrate W is transported by the second transport robot CR, and are stacked vertically. Multiple processing units 2 have, for example, similar configurations.

[0058] Multiple processing units 2 form four processing towers TW, each positioned at four horizontally separated locations. Each processing tower TW contains multiple processing units 2 stacked vertically. The four processing towers TW are arranged in pairs on each side of the transport path TR, which extends from the load port LP towards the second transport robot CR.

[0059] The substrate processing apparatus 1 includes a plurality of fluid boxes 4 that house valves, piping, etc., and a storage box 5 that houses tanks for storing chemicals, rinsing solutions, organic solvents, or raw materials thereof. The processing unit 2 and the fluid boxes 4 are arranged inside a frame 6 that is roughly rectangular in plan view.

[0060] The processing unit 2 has a chamber 7 for housing the substrate W during substrate processing. The chamber 7 includes an entrance / exit (not shown) for loading the substrate W into and out of the chamber 7 by the second transport robot CR, and a shutter unit (not shown) for opening and closing the entrance / exit. The processing liquid supplied to the substrate W in the chamber 7 may include chemicals, rinsing solutions, organic solvents, etc., as will be described in more detail later.

[0061] Figure 4 is a schematic diagram illustrating an example of the configuration of the processing unit 2, and shows an example of the configuration for carrying out the substrate processing method according to the first embodiment shown in Figure 1. The processing unit 2 includes a spin chuck 8 that rotates the substrate W around the rotation axis A1 while holding the substrate W in a predetermined processing position, and a plurality of nozzles (first moving nozzle N1, second moving nozzle N2, third moving nozzle N3, fourth moving nozzle N4) that discharge processing liquid toward the substrate W.

[0062] The processing unit 2 further includes a heater unit 14 for heating the substrate W held in the spin chuck 8, and a processing cup 15 for receiving the processing liquid splashed from the substrate W held in the spin chuck 8.

[0063] The spin chuck 8, multiple moving nozzles, heater unit 14, and processing cup 15 are located inside the chamber 7.

[0064] The rotation axis A1 passes through the center of the substrate W and is perpendicular to each main surface of the substrate W held in the processing position. The processing position is, for example, the position of the substrate W shown in Figure 4, which is a horizontal position where the main surface of the substrate W is on the horizontal plane, but it is not limited to the horizontal position. That is, the processing position may be different from that in Figure 4, where the main surface of the substrate W is inclined with respect to the horizontal plane. When the processing position is horizontal, the rotation axis A1 extends vertically.

[0065] The spin chuck 8 is an example of a substrate holding member (substrate holding unit, substrate holder) that holds the substrate W in a processing position, and is also an example of a rotational holding member that rotates the substrate W around the rotation axis A1 while holding the substrate W in a processing position.

[0066] The spin chuck 8 includes a spin base 21 having a disk shape aligned horizontally, a plurality of gripping pins 20 that grip the substrate W above the spin base 21 and grip the peripheral edge of the substrate W above the spin base 21, a rotation shaft 22 connected to the spin base 21 and extending vertically, and a rotation drive mechanism 23 that rotates the rotation shaft 22 around its central axis (rotation axis A1). The spin base 21 is an example of a disk-shaped base.

[0067] Multiple gripping pins 20 are arranged on the upper surface of the spin base 21 at intervals in the circumferential direction of the spin base 21. The rotational drive mechanism 23 includes an actuator, such as an electric motor. The rotational drive mechanism 23 rotates the spin base 21 and the multiple gripping pins 20 around the rotation axis A1 by rotating the rotation shaft 22. As a result, the substrate W is rotated around the rotation axis A1 together with the spin base 21 and the multiple gripping pins 20.

[0068] Multiple gripping pins 20 are movable between a closed position in which they contact the peripheral edge of the substrate W and grip the substrate W, and an open position in which they release the grip on the substrate W. The multiple gripping pins 20 are moved by an opening / closing mechanism (not shown).

[0069] When the multiple gripping pins 20 are in the closed position, they grip the peripheral edge of the substrate W and hold the substrate W horizontally. When the multiple gripping pins 20 are in the open position, they release their grip on the substrate W while supporting the peripheral edge of the substrate W from below. The opening and closing mechanism includes, for example, a link mechanism and an actuator that provides driving force to the link mechanism.

[0070] The multiple moving nozzles include a first moving nozzle N1 that discharges a polymer solution toward the upper surface (upper main surface) of the substrate W held in the spin chuck 8, a second moving nozzle N2 that discharges a liquid oxidizing agent toward the upper surface of the substrate W held in the spin chuck 8, a third moving nozzle N3 that selectively discharges a continuous flow of chemical solution and a continuous flow of rinsing solution toward the upper surface of the substrate W held in the spin chuck 8, and a fourth moving nozzle N4 that discharges an organic solvent toward the upper surface of the substrate W held in the spin chuck 8.

[0071] The first moving nozzle N1 is an example of a polymer solution nozzle that supplies a polymer solution toward the main surface (top surface) of the substrate W held in the spin chuck 8. The second moving nozzle N2 is an example of a liquid oxidizing agent nozzle that discharges a liquid oxidizing agent toward the main surface (top surface) of the substrate W held in the spin chuck 8. The second moving nozzle N2 may be a straight nozzle that discharges the liquid oxidizing agent in a continuous flow, or it may be a spray nozzle that discharges the liquid oxidizing agent in a mist (i.e., droplet state). The spray nozzle may be a two-fluid nozzle that discharges a mixture of liquid oxidizing agent and an inert gas (nitrogen gas or clean air). The third moving nozzle N3 is an example of a chemical solution nozzle that discharges a chemical solution toward the main surface (top surface) of the substrate W held in the spin chuck 8, and is also an example of a rinsing solution nozzle that discharges a rinsing solution toward the main surface (top surface) of the substrate W held in the spin chuck 8. The fourth moving nozzle N4 is an example of an organic solvent nozzle that discharges an organic solvent toward the main surface (top surface) of the substrate W held by the spin chuck 8.

[0072] Multiple movable nozzles are moved horizontally by multiple nozzle drive mechanisms (first nozzle drive mechanism 24, second nozzle drive mechanism 25, third nozzle drive mechanism 26, and fourth nozzle drive mechanism 27).

[0073] Each nozzle drive mechanism can move the corresponding movable nozzle between a processing position and a retracted position. The processing position is typically a central position where the movable nozzle faces the central region of the upper surface of the substrate W. The central region of the upper surface of the substrate W is the region on the upper surface of the substrate W that includes the center of rotation (central part) and the part surrounding the center of rotation. The retracted position is a position where the movable nozzle does not face the upper surface of the substrate W and is outside the processing cup 15.

[0074] Each nozzle drive mechanism includes an arm (first arm 24a, second arm 25a, third arm 26a, and fourth arm 27a) that supports the corresponding moving nozzle, and an arm drive mechanism (first arm drive mechanism 24b, second arm drive mechanism 25b, third arm drive mechanism 26b, and fourth arm drive mechanism 27b) that moves the corresponding arm horizontally. Each arm drive mechanism includes an actuator such as an electric motor or an air cylinder.

[0075] The movable nozzle may be a rotary nozzle that rotates around a predetermined pivot axis, or a linear nozzle that moves linearly in the direction in which the corresponding arm extends. The movable nozzle may also be configured to move in the vertical direction.

[0076] The processing unit 2 includes a polymer solution supply unit 9 that supplies a polymer solution to a substrate W held in a spin chuck 8. The polymer solution supply unit 9 includes a first moving nozzle N1, a polymer solution piping 40, a polymer solution valve 50A, and a polymer solution flow rate adjustment valve 50B.

[0077] The polymer solution piping 40 is connected to a polymer solution supply source and a first mobile nozzle N1, and guides the polymer solution from the polymer solution supply source to the first mobile nozzle N1. A polymer solution valve 50A and a polymer solution flow rate adjustment valve 50B are provided in the polymer solution piping 40.

[0078] The statement that the polymer solution valve 50A is provided in the polymer solution piping 40 may also mean that the polymer solution valve 50A is interposed in the polymer solution piping 40. The same applies to the other valves described below.

[0079] The polymer solution valve 50A opens and closes the flow path in the polymer solution piping 40. The polymer solution flow rate adjustment valve 50B adjusts the flow rate of the polymer solution flowing through the flow path in the polymer solution piping 40. When the polymer solution valve 50A is opened, the polymer solution is supplied to the first moving nozzle N1 at the flow rate adjusted by the polymer solution flow rate adjustment valve 50B.

[0080] Although not shown in the diagram, the polymer solution valve 50A includes a valve body with a valve seat inside, a valve element that opens and closes the valve seat, and an actuator that moves the valve element between an open position and a closed position. Other valves have a similar configuration.

[0081] The processing unit 2 further includes a liquid oxidizing agent supply unit 10 (an example of an oxidizing agent supply unit) that supplies a liquid oxidizing agent to the substrate W held in the spin chuck 8. The liquid oxidizing agent supply unit 10 includes a second moving nozzle N2, a liquid oxidizing agent piping 45, a liquid oxidizing agent valve 55A, and a liquid oxidizing agent flow rate adjustment valve 55B.

[0082] The liquid oxidizer piping 45 is connected to a liquid oxidizer supply source and a second mobile nozzle N2, and guides the liquid oxidizer from the liquid oxidizer supply source to the second mobile nozzle N2. A liquid oxidizer valve 55A and a liquid oxidizer flow rate adjustment valve 55B are provided in the liquid oxidizer piping 45. The liquid oxidizer valve 55A opens and closes the flow path in the liquid oxidizer piping 45. The liquid oxidizer flow rate adjustment valve 55B adjusts the flow rate of the liquid oxidizer flowing through the flow path in the liquid oxidizer piping 45. When the liquid oxidizer valve 55A is opened, the liquid oxidizer is supplied to the second mobile nozzle N2 at the flow rate adjusted by the liquid oxidizer flow rate adjustment valve 55B.

[0083] The chemical solution discharged from the third mobile nozzle N3 may be, for example, APM solution (ammonia-hydrogen peroxide mixture; more specifically, so-called SC1). In addition, chemical solutions containing hydrofluoric acid (HF), dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrochloric acid (HCl), HPM solution (hydrochloric acid-hydrogen peroxide mixture), ammonia water, TMAH solution (Tetramethylammonium hydroxide solution), or hydrogen peroxide water (H2O2) may be discharged from the third mobile nozzle N3.

[0084] The rinsing solution discharged from the third mobile nozzle N3 is, for example, water such as deionized water (DIW). However, the rinsing solution is not limited to deionized water, and may be deionized water, carbonated water, electrolyzed ionized water, hydrochloric acid water at a dilution concentration (for example, 1 ppm or more and 100 ppm or less), ammonia water at a dilution concentration (for example, 1 ppm or more and 100 ppm or less), reduced water (hydrogen water), or a mixture containing at least two of these.

[0085] The third mobile nozzle N3 is connected to a common pipe 41 that guides fluid to the third mobile nozzle N3. The common pipe 41 is connected to a chemical pipe 42 that supplies chemical solution to the common pipe 41, and a rinse liquid pipe 43 that supplies rinse liquid to the common pipe 41. The common pipe 41 may be connected to the chemical pipe 42 and the rinse liquid pipe 43 via a mixing valve (not shown).

[0086] The common piping 41 is equipped with a common valve 51 for opening and closing the common piping 41. The chemical piping 42 is equipped with a chemical valve 52A for opening and closing the chemical piping 42, and a chemical flow rate adjustment valve 52B for adjusting the flow rate of the chemical piping 42. The rinse liquid piping 43 is equipped with a rinse liquid valve 53A for opening and closing the rinse liquid piping 43, and a rinse liquid flow rate adjustment valve 53B for adjusting the flow rate of the rinse liquid piping 43.

[0087] When the chemical valve 52A and the common valve 51 are opened, a continuous flow of chemical solution is discharged from the third movable nozzle N3. The third movable nozzle N3, which acts as a chemical solution nozzle, the chemical solution piping 42, the chemical solution valve 52A, the chemical solution flow rate adjustment valve 52B, the common valve 51, etc. constitute a chemical solution supply unit that supplies chemical solution from a chemical solution supply source to the substrate W held in the spin chuck 8.

[0088] When the rinse liquid valve 53A and the common valve 51 are opened, a continuous flow of rinse liquid is discharged from the third movable nozzle N3. The third movable nozzle N3, which acts as a rinse liquid nozzle, the rinse liquid piping 43, the rinse liquid valve 53A, the rinse liquid flow rate adjustment valve 53B, the common valve 51, etc. constitute a rinse liquid supply unit that supplies rinse liquid from a rinse liquid supply source to the substrate W held in the spin chuck 8.

[0089] The organic solvent discharged from the fourth mobile nozzle N4 contains at least one of the following: alcohols such as ethanol (EtOH) and isopropanol (IPA); ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE); lactic acid esters such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as toluene and xylene; and ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone.

[0090] The fourth movable nozzle N4 is connected to an organic solvent pipe 44 that guides the organic solvent to the fourth movable nozzle N4. The organic solvent pipe 44 is equipped with an organic solvent valve 54A for opening and closing the organic solvent pipe 44, and an organic solvent flow rate adjustment valve 54B for adjusting the flow rate of the organic solvent in the organic solvent pipe 44. The fourth movable nozzle N4 as an organic solvent nozzle, the organic solvent pipe 44, the organic solvent valve 54A, the organic solvent flow rate adjustment valve 54B, etc. constitute an organic solvent supply unit that supplies organic solvent from an organic solvent supply source to the substrate W held in the spin chuck 8.

[0091] The processing cup 15 includes a plurality of guards 28 (three in Figure 4) that receive processing liquid splashed outward from the substrate W held by the spin chuck 8, a plurality of cups 29 (three in Figure 4) that each receive the processing liquid guided downward by the plurality of guards 28, and a cylindrical outer wall member 30 that surrounds the plurality of guards 28 and the plurality of cups 29.

[0092] Each guard 28 has a cylindrical shape that surrounds the spin chuck 8 in a plan view. The upper end of each guard 28 is inclined inward toward the center of the guard 28. Each cup 29 has an annular groove shape that is open upward. Multiple guards 28 and multiple cups 29 are arranged coaxially.

[0093] Multiple guards 28 are individually raised and lowered by a guard lifting drive mechanism (not shown). The guard lifting drive mechanism includes, for example, multiple actuators that drive each of the multiple guards 28 to raise or lower. The multiple actuators include at least one of an electric motor and an air cylinder.

[0094] The processing unit 2 includes a blowing unit 31, such as an FFU (fan filter unit), that sends inert gas from outside the chamber 7 into the chamber 7, and a discharge pipe 32 that exhausts gas from inside the chamber 7. The blowing unit 31 is located on the upper wall 7a of the chamber 7. The discharge pipe 32 is connected to the outer wall member 30. The inert gas sent to the chamber 7 by the blowing unit 31 may be, for example, nitrogen gas, a noble gas, or a mixture thereof. The noble gas is, for example, argon gas.

[0095] The discharge pipe 32 is connected to an exhaust duct (not shown). The atmosphere inside the exhaust duct is drawn in by a suction device (not shown). The atmosphere inside the chamber 7 is exhausted into the exhaust duct via the discharge pipe 32. The suction device includes a suction pump, etc., for drawing in the exhaust duct. The suction device is interposed in or connected to the exhaust duct. The discharge duct and suction device are located in the cleanroom where the substrate processing apparatus 1 is installed or in facilities associated with the cleanroom. The exhaust duct and suction device may be part of the substrate processing apparatus 1.

[0096] The blower unit 31 and the discharge pipe 32 work together to create an airflow in the internal space 7c of the chamber 7 that flows from top to bottom. The airflow passes through the inside of the processing cup 15 and flows into the discharge pipe 32.

[0097] The processing liquid supplied to the substrate W splashes from the periphery of the substrate W and is received by one of the guards 28. The processing liquid received by the guard 28 is guided to the corresponding cup 29 and is collected or discarded through the drain pipe 35 corresponding to each cup 29.

[0098] In this embodiment, the heater unit 14 has the form of a disc-shaped hot plate that heats the substrate W from below. The heater unit 14 is positioned between the upper surface of the spin base 21 and the lower surface of the substrate W. The heater unit 14 has a heating surface 14a that faces the lower surface of the substrate W from below.

[0099] The heater unit 14 includes a plate body 60 and a heater 61. In a plan view, 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 may be a resistor built into the plate body 60. By energizing the heater 61, the heating surface 14a is heated.

[0100] The heater 61 is configured to heat the substrate W to a temperature above room temperature (for example, 5°C or higher and 25°C or lower) and within a temperature range of, for example, 400°C or lower.

[0101] The processing unit 2 further includes a temperature sensor 62 for detecting the temperature of the heater unit 14. In the example shown in Figure 4, the temperature sensor 62 is built into the plate body 60, but the arrangement of the temperature sensor 62 is not particularly limited. The temperature sensor 62 may, for example, be attached to the plate body 60 from the outside.

[0102] A power supply unit 63 is connected to the heater 61 via a power supply line 64. The temperature of the heater 61 is adjusted by adjusting the current supplied from the power supply unit 63 to the heater 61. For example, the current supplied from the power supply unit 63 to the heater 61 is adjusted based on the temperature detected by the temperature sensor 62.

[0103] A heater lifting shaft 65 is connected to the lower surface of the heater unit 14. The heater lifting shaft 65 is inserted into the through hole 21a formed in the center of the spin base 21 and the internal space of the rotating shaft 22.

[0104] The processing unit 2 further includes a heater drive mechanism 66 that drives the movement of the heater unit 14 in the vertical direction. The heater drive mechanism 66 includes, for example, a heater actuator (not shown) that drives the movement of the heater lifting shaft 65 in the vertical direction. The heater actuator includes, for example, at least one of an electric motor and an air cylinder. The heater drive mechanism 66 moves the heater unit 14 in the vertical direction via the heater lifting shaft 65. The heater unit 14 is movable in the vertical direction between the lower surface of the substrate W and the upper surface of the spin base 21.

[0105] The heater unit 14 can receive the substrate W from multiple gripping pins 20 located in the open position as it rises. The heater unit 14 can heat the substrate W by being positioned either at a contact position where the heating surface 14a contacts the lower surface of the substrate W, or at a proximity position where it is close to the lower surface of the substrate W without contact. The position where the heater unit 14 is sufficiently retracted from the lower surface of the substrate W to the extent that the heating of the substrate W by the heater unit 14 is mitigated is called the retracted position. Sufficiently mitigating the heating of the substrate W can be rephrased as stopping the heating of the substrate W.

[0106] The amount of heat transferred from the heater unit 14 to the substrate W when the heater unit 14 is in the retracted position is less than the amount of heat transferred from the heater unit 14 to the substrate W when the heater unit 14 is in the proximity position. The contact position and proximity position are also called heating positions. The retracted position is also called a heating relaxation position or a heating stop position.

[0107] Figure 5 is a schematic diagram illustrating another configuration example of the processing unit 2, showing a configuration example for carrying out the substrate processing method according to the second embodiment shown in Figure 2. In Figure 5, the corresponding parts shown in Figure 4 are denoted by the same reference numerals and their descriptions are omitted.

[0108] This configuration example includes an oxidant vapor supply unit 110 that supplies oxidant vapor (oxidant vapor) instead of the liquid oxidant supply unit 10 (see Figure 4). In this configuration example, the second moving nozzle N2 is an example of an oxidant vapor nozzle that supplies oxidant vapor to the main surface of the substrate W held in the spin chuck 8. The oxidant vapor supply unit 110 (an example of an oxidant supply unit) supplies oxidant vapor from the oxidant vapor supply source to the main surface of the substrate W. The oxidant vapor supply unit 110 includes an oxidant vapor pipe 145 connected to the oxidant vapor supply source and the second moving nozzle N2, and an oxidant vapor valve 155A and an oxidant vapor flow rate adjustment valve 155B provided in the oxidant vapor pipe 145. The oxidant vapor valve 155A opens and closes the flow path in the oxidant vapor pipe 145. The oxidant vapor flow rate adjustment valve 155B adjusts the flow rate of oxidant vapor flowing through the oxidant vapor pipe. By opening the oxidizer vapor valve 155A, oxidizer vapor is discharged from the second moving nozzle N2 at a flow rate adjusted by the oxidizer vapor flow rate adjustment valve 155B. The opening and closing of the oxidizer vapor valve 155A and the degree of opening of the oxidizer vapor flow rate adjustment valve 155B are controlled by the controller 3 (see Figure 6).

[0109] The oxidizer vapor source may be configured to supply, for example, a mixed gas of an oxidizer and water vapor as oxidizer vapor. The oxidizer may include, for example, hydrogen peroxide or ozone, and may contain two or more oxidizers.

[0110] For example, the oxidizing agent source may include a tank for storing hydrogen peroxide solution and a nitrogen gas pipe for supplying an inert gas (e.g., nitrogen gas, clean air, etc.) to the hydrogen peroxide solution stored in the tank, and may be configured to bubble the inert gas flowing out of the nitrogen gas pipe into the hydrogen peroxide solution. With this configuration, an oxidizing agent vapor consisting of a mixture of hydrogen peroxide and water vapor is generated in the space above the liquid surface of the hydrogen peroxide solution. Therefore, by configuring the tank as a sealed container and connecting the space above the liquid surface of the hydrogen peroxide solution within the tank to the oxidizing agent vapor pipe 145, an oxidizing agent vapor consisting of a mixture of hydrogen peroxide solution and water vapor can be supplied. Alternatively, a mixture of hydrogen peroxide and water vapor can also be generated above the liquid surface of the hydrogen peroxide solution by heating the hydrogen peroxide solution stored in the tank.

[0111] Furthermore, the oxidizer supply source may include a tank for storing water (typically deionized water) and an ozone gas piping for supplying ozone gas to the water stored in the tank, and may be configured to bubble the ozone gas flowing out of the ozone gas piping in the water. With this configuration, oxidizer vapor consisting of moist ozone gas, which is a mixture of ozone and water vapor, is generated in the space above the water surface. Therefore, by configuring the tank as a sealed container and connecting the space above the water surface within the tank to the oxidizer vapor piping 145, oxidizer vapor consisting of moist ozone gas can be supplied.

[0112] An ozone removal device 33 (ozone abater) is provided between the exhaust pipe 32 and the exhaust duct, or in the exhaust pipe 32. The ozone gas contained in the atmosphere discharged from the chamber 7 is decomposed as it passes through the ozone removal device 33.

[0113] Figure 6 is a block diagram illustrating the electrical configuration of the substrate processing apparatus 1. The controller 3 is a computer that includes a computer body 3a and peripheral devices 3d connected to the computer body 3a. The computer body 3a includes a processor (CPU) 3b that executes various instructions and a memory 3c that stores information.

[0114] The peripheral device 3d includes an auxiliary storage device 3e for storing information such as programs, a reading device 3f for reading information from removable media (not shown), and a communication device 3g for communicating with other devices such as a host computer (not shown).

[0115] Controller 3 is connected to input device 3A, display device 3B, and alarm device 3C. Input device 3A is operated when an operator, such as a user or maintenance personnel, inputs information into the board processing device 1. The information is displayed on the screen of display device 3B. Input device 3A may be a keyboard, a pointing device, a touch panel, or any other device. A touch panel display that serves as both input device 3A and display device 3B may be provided in the board processing device 1. Alarm device 3C issues an alarm using one or more of the following: light, sound, characters, and graphics. If input device 3A is a touch panel display, input device 3A may also serve as alarm device 3C.

[0116] The auxiliary storage device 3e is a non-volatile memory that retains data even when power is not supplied. The auxiliary storage device 3e is, for example, a magnetic storage device such as a hard disk drive.

[0117] The auxiliary storage device 3e stores multiple recipes. A recipe is information that defines the processing content, processing conditions, and processing procedure for the substrate W. The multiple recipes differ from each other in at least one of the processing content, processing conditions, and processing procedure for the substrate W.

[0118] The controller 3 controls each component of the substrate processing device 1 so that the substrate W is processed according to a recipe specified by an external device such as a host computer.

[0119] The devices controlled by the controller 3 include the first transport robot IR, the second transport robot CR, the rotary drive mechanism 23, the first nozzle drive mechanism 24, the second nozzle drive mechanism 25, the third nozzle drive mechanism 26, the fourth nozzle drive mechanism 27, the heater drive mechanism 66, the energizing unit 63, the blower unit 31, the temperature sensor 62, the heater 61, the polymer solution valve 50A, the polymer solution flow rate adjustment valve 50B, the common valve 51, the chemical solution valve 52A, the chemical solution flow rate adjustment valve 52B, the rinse solution valve 53A, the rinse solution flow rate adjustment valve 53B, the organic solvent valve 54A, the organic solvent flow rate adjustment valve 54B, and the like. When the configuration example in Figure 4 is applied, the devices controlled by the controller 3 further include the liquid oxidizer valve 55A and the liquid oxidizer flow rate adjustment valve 55B. When the configuration example in Figure 5 is applied, the devices controlled by the controller 3 further include the oxidizer vapor valve 155A and the oxidizer vapor flow rate adjustment valve 155B.

[0120] Furthermore, while Figure 6 shows representative components, this does not mean that components not shown are not controlled by the controller 3. The controller 3 can appropriately control each component provided in the substrate processing apparatus 1.

[0121] Each step described with reference to Figures 7 and 8 below is performed by the controller 3 controlling the substrate processing apparatus 1. In other words, the controller 3 is programmed to perform the following steps.

[0122] Figure 7 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus 1. This substrate processing is an example using the processing unit 2 shown in the configuration example in Figure 4, and is an example of substrate processing according to the second embodiment shown in Figure 2. The example of substrate processing will be explained with reference to Figure 1 mentioned above.

[0123] A resist (typically a film-like resist) is formed on at least one of the pair of main surfaces of the substrate W used for substrate processing. The resist is typically an organic material and may be a resist that has been used as a mask for pattern formation processing (dry etching or wet etching) or ion implantation processing. This resist is an example of an organic substance to be removed from the main surface of the substrate W. The main surface of the substrate W may also contain polymer residue, which is the residue after dry etching, in addition to or in addition to the resist. Polymer residue is another example of an organic substance to be removed from the main surface of the substrate W.

[0124] In the substrate processing using the substrate processing apparatus 1, for example, the following steps are performed: substrate loading (step S1), polymer coating (step S2), baking (step S3), liquid oxidizing agent supply (step S4A), parallel heating (step S5), rinsing (step S6), organic solvent supply (step S7), drying (step S8), and substrate unloading (step S9).

[0125] The untreated substrate W is transported from the carrier C to the processing unit 2 by the transport robots IR and CR (see Figure 3), and then passed to the spin chuck 8 as shown in Figure 1(a) (substrate loading process: step S1). The substrate W is then held horizontally by the spin chuck 8 (substrate holding process). At this time, the substrate W is held in the spin chuck 8 with the main surface where the resist is formed (the main surface where the organic material to be removed is formed) facing upwards. The substrate W continues to be held by the spin chuck 8 until the drying process (step S8) is completed.

[0126] With the substrate W held in the spin chuck 8, the rotation drive mechanism 23 starts rotating the substrate W (substrate rotation process). During the substrate processing, an airflow is constantly formed in the internal space 7c of the chamber 7, flowing from top to bottom. This airflow passes through the inside of the processing cup 15 and flows into the discharge pipe 32.

[0127] Meanwhile, the first nozzle drive mechanism 24 moves the first movable nozzle N1 to a processing position (for example, the central position). The processing position is a position where the first movable nozzle N1 faces the main surface of the substrate W (the main surface on which the resist is formed) and can supply the polymer solution to the main surface of the substrate W.

[0128] With the first moving nozzle N1 in the processing position, the polymer solution valve 50A is opened, thereby starting the supply of polymer solution to the first moving nozzle N1. As a result, the polymer solution is discharged from the first moving nozzle N1 and supplied to the upper surface of the rotating substrate W. As a result, as shown in Figure 1(b), the polymer solution is applied to the upper surface of the substrate W (the main surface on which the resist is formed), and a liquid film of polymer solution (polymer film P) is formed on the upper surface of the substrate W (step S2). The liquid film of polymer solution is in direct contact with the resist formed on the main surface of the substrate W.

[0129] During the polymer coating process (step S2), the first nozzle drive mechanism 24 typically holds the first movable nozzle N1 stationary at the position (center position) where the polymer solution lands on the rotational center of the substrate W. However, if necessary, the first nozzle drive mechanism 24 may move the first movable nozzle N1 in the radial direction of rotation, thereby moving the landing point of the polymer solution on the upper surface of the substrate W in the radial direction of the substrate W.

[0130] After a predetermined time has elapsed since the supply of the polymer solution was started, the polymer solution valve 50A is closed, and the supply of the polymer solution from the first moving nozzle N1 to the upper surface of the substrate W is stopped.

[0131] After the dispensing of the polymer solution is stopped, the first nozzle drive mechanism 24 retracts the first movable nozzle N1 to a retracted position set outside the substrate W. Meanwhile, a baking process (step S3) is performed in which the substrate W is heated to bake the polymer, i.e., the liquid film of the polymer solution, applied to the main surface of the substrate W.

[0132] Specifically, the power supply unit 63 supplies current to the heater 61, and the temperature of the heater 61 begins to rise. Then, the heater drive mechanism 66 moves the heater unit 14 from the retracted position to the bake processing position. For example, the bake processing position may be a contact position where the heating surface 14a of the heater unit 14 is in contact with the lower surface of the substrate W (the main surface opposite to the main surface on which the resist is formed). In this case, the rotation of the substrate W is stopped, and contact heating is performed by bringing the heater unit 14 into contact with the substrate W in its stopped state to transfer heat. Alternatively, the bake processing position may be a proximity position where the heating surface 14a of the heater unit 14 is located below the lower surface of the substrate W at a small distance. In this case, while the substrate W continues to rotate, non-contact heating (heating by convection and radiant heat of the surrounding atmosphere) can be performed on the rotating substrate W by the heater unit 14.

[0133] During the baking process for a predetermined time, the solvent in the polymer liquid film evaporates, and a polymer film P (solidified film; see Figure 1(c)) is formed on the main surface of the substrate W. This polymer film P is in contact with the resist formed on the main surface of the substrate W. As mentioned above, the polymer film P may be semi-solid or solid.

[0134] After the baking process (step S3), a liquid oxidizing agent supply process (step S4A: oxidizing agent supply process) is performed, which supplies a liquid oxidizing agent to the main surface of the substrate W. Specifically, the substrate W is rotated, and the second moving nozzle N2 is positioned at a processing position (for example, the central position) facing the upper surface of the substrate W. If the baking processing position of the heater unit 14 is a contact position that is in contact with the substrate W, the heater unit 14 is lowered to a close position spaced downward from the lower surface of the substrate W before the rotation of the substrate W begins. In parallel with the liquid oxidizing agent supply process (step S4A), the substrate W is heated by the heater unit 14 positioned at the close position (step S5: parallel heating process). Since the power supply to the heater unit 14 continues from the baking process, the parallel heating process starts before the start of the liquid oxidizing agent supply process.

[0135] While the substrate W is rotated and heated in this manner, liquid oxidizing agent is discharged from the second moving nozzle N2 toward the upper surface of the substrate W (the main surface on which the resist is formed). Specifically, when the liquid oxidizing agent valve 55A is opened, liquid oxidizing agent is discharged from the second moving nozzle N2 at a predetermined flow rate.

[0136] The liquid oxidizing agent comes into contact with the solidified polymer film P on the substrate W. A caroic acid-based compound is then generated by the reaction shown in chemical formula 1. This compound decomposes the resist by the reaction shown in chemical formula 2. Therefore, during the liquid oxidizing agent supply step (step S4A), an organic matter removal step that decomposes and removes the resist on the substrate W proceeds simultaneously.

[0137] During the liquid oxidizing agent supply process (step S4A), the second nozzle drive mechanism 25 typically holds the second movable nozzle N2 stationary at the position (center position) where the liquid oxidizing agent lands on the rotational center of the substrate W. However, if necessary, the second nozzle drive mechanism 25 may move the second movable nozzle N2 in the radial direction of rotation, thereby moving the landing point of the liquid oxidizing agent on the upper surface of the substrate W in the radial direction of the substrate W.

[0138] After a predetermined time for supplying the liquid oxidizer (step S4A), the liquid oxidizer valve 55A is closed, and the supply of the liquid oxidizer is stopped (end of the liquid oxidizer supply process). The second moving nozzle N2 is then moved to the retracted position. The heater drive mechanism 66 also moves the heater unit 14 from the proximity position to the retracted position. By positioning the heater unit 14 in the retracted position (the position shown in Figure 1(e)), heating of the substrate W is stopped (end of the parallel heating process).

[0139] Next, a rinsing step (step S6) is performed to clean the upper surface of the substrate W. Specifically, the third nozzle drive mechanism 26 moves the third movable nozzle N3 to the processing position. The processing position is, for example, the central position. With the third movable nozzle N3 in the processing position, the common valve 51 and the rinsing liquid valve 53A are opened. As a result, as shown in Figure 1(e), rinsing liquid is discharged from the third movable nozzle N3, and the supply of rinsing liquid to the upper surface of the substrate W begins (rinsing liquid supply step). The rinsing liquid that has landed on the upper surface of the substrate W moves toward the peripheral edge of the upper surface of the substrate W, and the rinsing liquid spreads across the entire upper surface of the substrate W. As a result, the liquid oxidizing agent on the substrate W is replaced by the rinsing liquid, and any residue on the substrate W is washed away by the flow of the rinsing liquid.

[0140] After a predetermined time has elapsed since the start of the rinse solution supply, the common valve 51 and the rinse solution valve 53A are closed. This stops the supply of rinse solution to the upper surface of the substrate W. This completes the rinsing process. Through the rinsing process, the liquid oxidizing agent on the upper surface of the substrate W is replaced by the rinse solution, and any resist and its residue that have been peeled off the upper surface of the substrate W are washed away and removed from the upper surface of the substrate W to the outside of the substrate W.

[0141] The rinsing process (step S6) may include chemical treatment using a chemical solution. For example, the rinsing process may include a first rinsing liquid supply process (step S61), a chemical solution supply process (step S62), and a second rinsing liquid supply process (step S62), which are performed in sequence. Specifically, the common valve 51 and the rinsing liquid valve 53A are opened, and rinsing liquid is discharged from the third movable nozzle N3 to perform the first rinsing liquid supply process (step S61). After a predetermined time has elapsed, the rinsing liquid valve 53A is closed, the chemical solution valve 52A is opened, and a chemical solution (for example, SC1) is discharged from the third movable nozzle N3 to perform the chemical solution supply process (step S62). After a predetermined time, the chemical solution valve 52A is closed, the rinsing liquid valve 53A is opened, and rinsing liquid is discharged from the third movable nozzle N3 to perform the second rinsing liquid supply process (step S63). The rinsing process is terminated by closing the rinsing liquid valve 53A and the common valve 51 after a predetermined time. Subsequently, the third movable nozzle N3 is moved to the retracted position. The rinsing process, including chemical treatment, has the advantage of efficiently removing residue from the substrate W.

[0142] During the rinsing process (step S6), the third nozzle drive mechanism 26 typically holds the third movable nozzle N3 stationary at the center of rotation of the substrate W, where the rinsing liquid / chemical solution lands (center position). However, if necessary, the third nozzle drive mechanism 26 may move the third movable nozzle N3 in the radial direction of rotation, thereby moving the landing point of the rinsing liquid / chemical solution on the upper surface of the substrate W in the radial direction of the substrate W.

[0143] After the rinsing process (step S6), an organic solvent supply process (step S7) is performed, in which an organic solvent is supplied to the upper surface of the substrate W. Specifically, the fourth nozzle drive mechanism 27 positions the fourth movable nozzle N4 to a processing position (for example, the central position) facing the upper surface of the substrate W, and in this state, the organic solvent valve 54A is opened. As a result, a continuous flow of organic solvent is discharged (supplied) from the fourth movable nozzle N4 toward the upper surface of the substrate W (step S7, organic solvent supply process). As a result, the rinsing liquid on the upper surface of the substrate W is replaced with the organic solvent.

[0144] During the organic solvent supply process, the fourth nozzle drive mechanism 27 typically holds the fourth movable nozzle N4 stationary at a position (center position) where the organic solvent lands on the rotation center of the substrate W. However, if necessary, the fourth nozzle drive mechanism 27 may move the fourth movable nozzle N4 in the radial direction of rotation, thereby moving the landing point of the organic solvent on the upper surface of the substrate W in the radial direction of the substrate W.

[0145] It is preferable that the organic solvent used for substrate processing has higher volatility than the rinsing solution. If so, replacing the rinsing solution with the organic solvent allows for better drying of the substrate W in the subsequent drying process (step S8). It is preferable that the organic solvent used for substrate processing has lower surface tension than the rinsing solution. 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, thereby suppressing the collapse of the uneven pattern.

[0146] Next, a drying process (step S8, spin-drying process) is performed in which the substrate W is rotated at high speed to dry the upper surface of the substrate W (see Figure 1(f)). Specifically, the organic solvent valve 54A is closed to stop the supply of organic solvent to the upper surface of the substrate W. Then, the rotation drive mechanism 23 accelerates the rotation of the substrate W, causing it to rotate at high speed (for example, 1500 rpm). As a result, a large centrifugal force acts on the rinsing liquid adhering to the substrate W, causing the organic solvent to be swept away around the substrate W.

[0147] After the drying process (step S8), the rotary drive mechanism 23 stops the rotation of the substrate W. Then, the second transport robot CR enters the processing unit 2, receives the processed substrate W from the spin chuck 8, and transports it out of the processing unit 2 (substrate transport process: step S9). The substrate W is then passed from the second transport robot CR to the first transport robot IR, which places it into the carrier C.

[0148] Figure 8 is a flowchart illustrating another example of substrate processing performed by the substrate processing apparatus 1. This substrate processing is another example using the processing unit 2 of the configuration example shown in Figure 5, and is an example of the substrate processing of the second embodiment shown in Figure 2 above. In Figure 8, steps in which substantially the same processing as in Figure 7 is performed are indicated by the same reference numerals.

[0149] The substrate W to be processed is the same as the substrate processing shown in Figure 7. The substrate loading process (step S1, see Figure 2(a)), polymer coating process (step S2, see Figure 2(b)), baking process (step S3, see Figure 2(c)), parallel heating process (step S5, see Figure 2(d)), rinsing process (step S6, see Figure 2(e)), organic solvent supply process (step S7), drying process (step S8, see Figure 2(f)), and substrate unloading process (step S9) are substantially the same as in the substrate processing shown in Figure 7.

[0150] On the other hand, in the substrate processing shown in Figure 7, the oxidizing agent supply step is the step of supplying a liquid oxidizing agent (step S4A), whereas in the substrate processing shown in Figure 8, it is the oxidizing agent vapor supply step (step S4B; see Figure 2(d)) in which oxidizing agent vapor is supplied to the main surface of the substrate W.

[0151] Specifically, after the baking process, an oxidant vapor supply process (step S4B) is performed, in which oxidant vapor is supplied to the main surface of the substrate W. More specifically, the substrate W is rotated, and the second moving nozzle N2 (oxidant vapor nozzle) is positioned at a processing position (for example, the central position) facing the upper surface of the substrate W. If the baking processing position of the heater unit 14 is a contact position that is in contact with the substrate W, the heater unit 14 is lowered to a close position spaced downward from the lower surface of the substrate W before the rotation of the substrate W begins. In parallel with the oxidant vapor supply process (step S4B), the substrate W is heated by the heater unit 14 positioned at the close position (step S5: parallel heating process). While the substrate W is rotating and heated in this way, oxidant vapor is discharged from the second moving nozzle N2 toward the upper surface of the substrate W (the main surface on which the resist is formed). Specifically, the oxidant vapor valve 155A is opened, causing oxidant vapor to be discharged from the second moving nozzle N2 at a predetermined flow rate. Since power is supplied to the heater unit 14 from the bake process, the parallel heating process starts before the oxidizer vapor supply process begins.

[0152] The oxidizing agent vapor comes into contact with the solidified polymer film P on the substrate W. This generates a caroic acid-based compound through the reaction shown in chemical formula 1. This compound decomposes the resist through the reaction shown in chemical formula 2. Therefore, during the oxidizing agent vapor supply step (step S4B), an organic matter removal step that decomposes and removes the resist on the substrate W proceeds simultaneously.

[0153] During the oxidizing vapor supply process (step S4B), the second nozzle drive mechanism 25 typically holds the second movable nozzle N2 stationary at a position (central position) where oxidizing vapor is discharged toward the rotational center of the substrate W. However, if necessary, the second nozzle drive mechanism 25 may move the second movable nozzle N2 in the radial direction of rotation, thereby moving the target discharge position of the oxidizing vapor on the upper surface of the substrate W in the radial direction of the substrate W.

[0154] After the oxidizer vapor supply process (step S4B) for a predetermined time, the oxidizer vapor valve 155A is closed and the supply of oxidizer vapor is stopped (end of oxidizer vapor supply process). The second movable nozzle N2 is then moved to the retracted position. The heater drive mechanism 66 also moves the heater unit 14 from the proximity position to the retracted position. By placing the heater unit 14 in the retracted position (position shown in Figure 2(e)), heating of the substrate W is stopped (end of parallel heating process).

[0155] In the substrate processing example shown in Figure 8, the bake step (step S3; see Figure 2(c)) may be omitted. In this case, although the polymer film P is an unsolidified liquid film, the oxidizing agent is supplied in the form of vapor, which suppresses the outflow of the polymer film P from the substrate W while efficiently generating a caroate-based compound on the substrate W, thereby efficiently removing organic matter from the substrate W.

[0156] Furthermore, in both the substrate processing examples in Figure 7 and Figure 8, the organic solvent supply step (S7) may be omitted. In addition, in both the substrate processing examples in Figure 7 and Figure 8, steps S2 to S8 may be repeated two or more times as needed. This ensures that the resist on the substrate W is sufficiently removed.

[0157] Figure 9 is a schematic plan view showing the general configuration of a substrate processing apparatus 1 for carrying out a substrate processing method according to another embodiment of the present invention. In Figure 9, the corresponding parts shown in Figure 3 are denoted by the same reference numerals.

[0158] In this embodiment, the multiple processing units 2 include coating units 2C, baking units 2B, and liquid processing units 2L. In this example, multiple coating units 2C are stacked vertically in one processing tower TW, and multiple liquid processing units 2L are stacked vertically in another processing tower TW. Furthermore, multiple baking units 2B are stacked vertically in two other processing towers TW.

[0159] The coating unit 2C performs a polymer coating process in which a polymer solution is applied to the main surface of the substrate W. Specifically, the coating unit 2C is equipped with a spin chuck 70 and a polymer solution nozzle 71 in the chamber 7. The coating unit 2C is a spin coating unit that holds a single substrate W in the spin chuck 70 and rotates it while supplying a polymer solution from the polymer solution nozzle 71 to the main surface (top surface) of the substrate W, and spreading a coating film (liquid film) of the polymer solution over the entire main surface of the substrate W by centrifugal force.

[0160] The bake unit 2B includes a hot plate 80 on which the substrate W is placed, a cool plate 81 which also serves as a transfer platform for the substrate W, and a local transport robot 82, all located within a chamber 7. The local transport robot 82 transports the substrate W between the hot plate 80 and the cool plate 81 within the chamber 7 of the bake unit 2B. Transfer of the substrate W to the second transport robot CR takes place on the cool plate 81. The substrate W, once placed on the cool plate 81, is transported to the hot plate 80 by the local transport robot 82. The hot plate 80 heats the substrate W from the bottom side, heating the polymer solution coating film formed on its main surface (top surface in this example), evaporating the solvent in the coating film, solidifying the polymer solution, and performing a bake treatment to create a solidified (semi-solid or solid) polymer film P. After this bake treatment, the substrate W is transported to the cool plate 81 by the local transport robot 82 and cooled (for example, to room temperature). After cooling, the processed substrate W is removed from the cool plate 81 by the second transport robot CR. In this way, the bake unit 2B performs the bake process.

[0161] The liquid treatment unit 2L performs an oxidizing agent supply step, a parallel heating step, and a drying step (spin-drying step). The liquid treatment unit 2L may also perform an organic solvent supply step as needed. The liquid treatment unit 2L comprises a spin chuck 90, an oxidizing agent nozzle 91, a parallel heating unit 92, and a rinse liquid nozzle 93 in the chamber 7, and an organic solvent nozzle 94 as needed. The oxidizing agent nozzle 91 may be a liquid oxidizing agent nozzle that discharges a liquid oxidizing agent (a nozzle that discharges a liquid oxidizing agent in the form of a continuous flow or mist), or a vapor nozzle that discharges an oxidizing agent vapor. The parallel heating unit 92 may be a lamp heater that heats the substrate W from the top side, a hot plate that heats the substrate W from the bottom side, or a high-temperature inert gas nozzle that supplies heated inert gas (typically nitrogen gas or clean air) toward the top or bottom surface of the substrate W.

[0162] The liquid processing unit 2L holds a single substrate W in a spin chuck 90 and rotates it while supplying an oxidizing agent (liquid oxidizing agent or oxidizing agent vapor) from an oxidizing agent nozzle 91 to the main surface (top surface) of the substrate W. In parallel with this, the substrate W is heated by a parallel heating unit 92. This causes a reaction between the oxidizing agent and the sulfonic acid groups in the polymer film P to generate a caroic acid-based compound, which then reacts with the resist to decompose the resist. Subsequently, a rinsing process is performed by discharging a rinsing solution (and additional chemicals if necessary) from a rinsing solution nozzle 93 toward the main surface of the substrate W. After the rinsing process, a drying process (spin-drying process) is performed by rotating the spin chuck 90 at high speed to shake off any remaining liquid components on the substrate W. Between the rinsing and drying processes, an organic solvent supply process may be performed, if necessary, in which an organic solvent is supplied from an organic solvent nozzle 94 toward the main surface of the rotating substrate W.

[0163] The first transport robot IR removes the substrate W to be processed from the carrier C. This substrate W is then transported to the coating unit 2C by the second transport robot CR. Thereupon, a polymer coating process is carried out in the chamber 7 (first chamber) of the coating unit 2C. After the polymer coating process is completed, the second transport robot CR removes the substrate W from the coating unit 2C and transports it to the bake unit 2B. Thereupon, a bake process is carried out in the chamber 7 (second chamber) of the bake unit 2B. After the bake process is completed, the second transport robot CR removes the substrate W from the bake unit 2B and transports it to the liquid processing unit 2L. Thereupon, an oxidizing agent supply process (organic matter removal process), a parallel heating process, a rinsing process, an organic solvent supply process as needed, and a drying process are carried out in the chamber 7 (third chamber) of the liquid processing unit 2L. After processing, the substrate W is removed from the liquid processing unit 2L by the second transport robot CR and then passed to the first transport robot IR, where it is placed back into the carrier C. In this manner, substrate processing to remove resist from substrate W is performed through a process in which the substrate W moves between multiple processing units.

[0164] In the configuration shown in Figure 3, the polymer coating process, baking process, oxidizing agent supply process, parallel heating process, rinsing process, organic solvent supply process, and drying process are performed within a single processing unit 2 (i.e., within a single chamber 7). In contrast, in the configuration shown in Figure 9, a series of processes are performed by a transfer process in which the substrate W moves between multiple processing units 2. The configuration in Figure 3 has the advantage of not requiring the substrate W to be transported between processes. On the other hand, the configuration in Figure 9 has the advantage of the short time that a single processing unit is occupied for processing a single substrate W.

[0165] While embodiments of this invention have been described above, this invention can also be implemented in other forms.

[0166] For example, the polymer coating and baking processes may be performed in another substrate processing apparatus 101 (see Figure 3; an example of a first substrate processing apparatus), and a carrier C containing a substrate W having a polymer film P on its main surface may be introduced into the substrate processing apparatus 1 (an example of a second substrate processing apparatus). In this case, the processing unit 2 of the substrate processing apparatus 1 only needs to perform each of the processes from the oxidizing agent supply process onward, and it is sufficient for it to be equipped with the necessary configurations for performing each of those processes.

[0167] In each of the embodiments described above, the processing liquid (liquid or vapor) is discharged from multiple movable nozzles. However, unlike the embodiments described above, the processing liquid may be discharged from a fixed nozzle whose position in the horizontal direction is fixed, or all processing liquids may be discharged from a single nozzle.

[0168] Heating of the substrate W is not limited to heating by the heater unit 14 with the configuration described above. Specifically, the heater unit may include an infrared lamp facing the upper surface of the substrate W, or a heater facing the upper surface of the substrate W. Alternatively, the heater unit may include a heating fluid nozzle that supplies a heating fluid such as nitrogen gas or hot water to the lower surface of the substrate W. The heater unit may be configured to heat the plate body 60 by circulating the heating fluid within the plate body 60. When using a heating fluid, the temperature of the substrate W is adjusted by adjusting the opening of a valve that controls the flow rate of the heating fluid.

[0169] In the embodiments described above, the spin chuck 8 is a gripping-type spin chuck that grips the periphery of the substrate W with a plurality of gripping pins 20. However, the spin chuck 8 is not limited to a gripping-type spin chuck. For example, the spin chuck 8 may be a vacuum suction-type spin chuck that adsorbs the substrate W onto the spin base 21.

[0170] In each of the embodiments described above, the controller 3 controls the entire substrate processing apparatus 1. However, the controllers that control each component of the substrate processing apparatus 1 may be distributed in multiple locations. Furthermore, the controller 3 does not need to directly control each component; the signals output from the controller 3 may be received by slave controllers that control each component of the substrate processing apparatus 1.

[0171] Furthermore, in the above-described embodiment, the substrate processing apparatus 1 comprises a transport robot (first transport robot IR and second transport robot CR), a plurality of processing units 2, and a controller 3. However, the substrate processing apparatus 1 may consist of a single processing unit 2 and a controller 3, and may not include a transport robot. Alternatively, the substrate processing apparatus 1 may consist of only a single processing unit 2. In other words, the processing unit 2 may be an example of a substrate processing apparatus.

[0172] Furthermore, various design modifications can be made within the scope of the matters described in the patent claims. [Explanation of symbols]

[0173] 1: Substrate processing equipment 2: Processing Unit 2B: Bake Unit 2C: Coating Unit 2L: Liquid processing unit 3: Controller 7: Chamber 8: Spin Chuck 9: Polymer solution supply unit 10: Liquid oxidizing agent supply unit 14: Heater Unit 40: Polymer solution piping 41: Common Piping 42: Chemical piping 43: Rinse fluid piping 45: Liquid oxidizing agent piping 61: Heater 66: Heater drive mechanism 70: Spin Chuck 71: Polymer solution nozzle 80: Hot plate 90: Spin Chuck 91: Oxidizing agent nozzle 92: Parallel heating unit 93: Rinse liquid nozzle 101: Substrate processing equipment 110: Oxidizer vapor supply unit 145: Oxidizer vapor piping N1: First mobile nozzle N2: Second mobile nozzle N3: Third mobile nozzle N4: Fourth mobile nozzle P: Polymer film W: Circuit board

Claims

1. A step of preparing a substrate having a polymer film containing a polymer with sulfonic acid groups as its main surface, An oxidizing agent supply step of supplying an oxidizing agent to the main surface of the substrate, A substrate processing method comprising: an organic matter removal step, which removes organic substances to be removed present on the main surface of the substrate by reaction products of the sulfonic acid groups in the polymer film and the oxidizing agent.

2. The substrate processing method according to claim 1, wherein the substance to be removed includes at least one of resist and residue after dry etching.

3. The substrate processing method according to claim 1, wherein the oxidizing agent supply step involves supplying a liquid or vapor oxidizing agent to the main surface of the substrate.

4. The substrate processing method according to claim 1, wherein the oxidizing agent comprises at least one of hydrogen peroxide and ozone.

5. The oxidizing agent supply step is, A continuous supply process in which hydrogen peroxide solution or ozonated water is discharged from a nozzle in a continuous flow and supplied to the main surface of the substrate, A mist supply step in which hydrogen peroxide solution, ozonated water, or a mixture of sulfuric acid and hydrogen peroxide solution is discharged in a mist form from a nozzle and supplied to the main surface of the substrate, A steam supply step in which hydrogen peroxide or ozone is mixed with water vapor and supplied to the main surface of the substrate, The substrate processing method according to claim 1, comprising at least one of the following.

6. Before the start of the oxidizing agent supply step, the polymer film is in a solidified state. The substrate processing method according to claim 1, wherein the oxidizing agent supply step includes a liquid oxidizing agent supply step of supplying a liquid oxidizing agent to the main surface of the substrate.

7. Before the start of the oxidizing agent supply step, the polymer film is in an unsolidified state. The substrate processing method according to claim 1, wherein the oxidizing agent supply step includes an oxidizing agent vapor supply step of supplying oxidizing agent vapor to the main surface of the substrate.

8. The substrate processing method according to claim 1, further comprising a parallel heating step of heating the substrate in parallel with the oxidizing agent supply step.

9. The substrate processing method according to claim 8, wherein the parallel heating step is started before the supply of the oxidizing agent is started.

10. The process of preparing the aforementioned substrate is as follows: A polymer coating step of applying a polymer containing sulfonic acid groups to the main surface of the substrate, A substrate processing method according to any one of claims 1 to 9, comprising a baking step of baking a polymer applied to the main surface of the substrate.

11. The polymer coating process is performed in the first chamber. The baking process is carried out in a second chamber separate from the first chamber. The substrate processing method according to claim 10, wherein the oxidizing agent supply step is performed in a third chamber separate from the first and second chambers.

12. The process of preparing the substrate is performed by the first substrate processing apparatus. The substrate processing method according to any one of claims 1 to 9, wherein the oxidizing agent supply step is performed in a second substrate processing apparatus separate from the first substrate processing apparatus.

13. The substrate processing method according to any one of claims 1 to 9, wherein the polymer containing the sulfonic acid group includes at least one of vinyl sulfonic acid-vinyl alcohol copolymer, vinyl sulfonic acid-styrene copolymer, polyvinyl sulfonic acid, polystyrene sulfonic acid, polystyrene partial sulfonate, ammonium sulfonate salt, and metal sulfonate salt.

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