TW202410187A - Substrate processing method and substrate processing device - Google Patents

Abstract

[Problem] Provide a technology for suppressing the generation of particles on the substrate surface by covering the entire substrate surface with a mixture of sulfuric acid and hydrogen peroxide water when the substrate surface is hydrophobic. [Solution] A substrate treatment method comprising: the steps of rotating the substrate while holding it horizontally; supplying a hydrophilizing liquid containing hydrogen peroxide water or ozone water to the hydrophobic surface of the rotating substrate; the hydrophilizing liquid After supplying, the step of supplying a mixture of sulfuric acid and hydrogen peroxide water to the surface of the rotating substrate.

Description

Substrate processing method and substrate processing device

The present disclosure relates to a substrate processing method and a substrate processing apparatus.

The substrate processing method described in Patent Document 1 uses a mixed solution of sulfuric acid and hydrogen peroxide water to process the substrate. Sulfuric acid and hydrogen peroxide water are supplied to the surface of the substrate from the nozzle respectively, and are mixed on the surface of the substrate. The mixed solution is used to peel off the photoresist film. After peeling off the photoresist film, SC1 (a mixture of ammonia water and hydrogen peroxide water) is supplied to the surface of the substrate in order to remove the residues and particles of the sulfur component. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application No. 2004-288858

[Problem to be solved by the invention]

One aspect of the present disclosure provides a technology in which the substrate surface is hydrophobic and the entire substrate surface is covered with a mixture of sulfuric acid and hydrogen peroxide water to suppress the generation of particles on the substrate surface. [Means to solve problems]

One aspect of the substrate processing method of the present disclosure includes: the steps of holding and rotating the substrate horizontally; the step of supplying a hydrophilization solution containing hydrogen peroxide water or ozone water to the hydrophobic surface of the rotating substrate; After supplying the hydrophilization liquid, a mixed liquid of sulfuric acid and hydrogen peroxide water is supplied to the surface of the rotating substrate. [Effects of the invention]

According to one aspect of the present disclosure, when the substrate surface is hydrophobic, the entire substrate surface is coated with a mixture of sulfuric acid and hydrogen peroxide to suppress the generation of particles on the substrate surface.

Hereinafter, embodiments related to the present disclosure will be described with reference to the drawings. In addition, in each drawing, the same or corresponding structure is attached|subjected to the same code|symbol, and description may be abbreviate|omitted. In this specification, the X-axis direction, the Y-axis direction, and the Z-axis direction are mutually perpendicular directions. The X-axis direction and the Y-axis direction are horizontal directions, and the Z-axis direction is the vertical direction.

First, the substrate processing method of the previous example is described with reference to FIG. 7 and FIG. 8. As shown in FIG. 7, the substrate processing method has steps S201 to S205. Step S201 includes holding the substrate horizontally and rotating it. While rotating the substrate, DHF (dilute hydrofluoric acid) is supplied (step S202), DIW (deionized water) is supplied (step S203), and SPM (a mixture of sulfuric acid and hydrogen peroxide) is supplied (step S204) to the surface of the substrate. After that, the substrate is dried (step S205).

Before supplying SPM (step S204), supplying DHF (step S202) can improve the processing efficiency of the substrate surface by SPM. However, DHF hydrophobicizes the substrate surface. The longer the supply time of DHF, the more hydrophobization of the substrate surface proceeds.

The hydrophobized substrate surface repels SPM. SPM cannot spread moisture uniformly, and SPM may scatter thinly. In addition, the SPM may form a plurality of spiral arms as shown in FIG. 8 . Since SPM cannot cover the entire substrate surface, particles may be generated on the substrate surface. The generation of particles is significant in the outer peripheral portion of the substrate surface.

Details will be described later, but the technology disclosed in this disclosure supplies HPS (hydrogen peroxide water) after the supply of DHF and before the supply of SPM. After supplying HPS to hydrophilize the substrate surface, SPM is supplied. Thereby, SPM can be uniformly moistened and spread over the entire surface of the substrate, and the generation of particles on the surface of the substrate can be suppressed.

In addition, the technology disclosed in the present invention starts supplying HPS after supplying DIW starts and before supplying DIW ends. That is, the technology disclosed in the present invention supplies DIW and HPS simultaneously. By supplying DIW and HPS simultaneously, it is possible to suppress drying of the substrate surface before the hydrophilization of the substrate surface is fully performed, and to suppress the generation of particles.

Furthermore, the technology disclosed in the present disclosure replaces the nozzle located at the center from the nozzle that discharges DIW to the nozzle that discharges HPS from the start of supply of DIW to the completion of simultaneous supply of DIW and HPS. During the replacement of the nozzle, at least one of DIW and HPS is usually supplied to the substrate surface. Therefore, drying of the substrate surface can be suppressed, and the generation of particles can be suppressed.

In addition, after the substrate surface is hydrophilized, the supply of the processing liquid can be suspended after the nozzle is replaced. If the suspension time is short, the substrate surface will not dry out. This is because it takes longer for the processing liquid to flow out of the hydrophilized substrate surface than the hydrophobic substrate surface.

A substrate processing apparatus 1 according to an embodiment will be described with reference to FIGS. 1 and 2 . The substrate processing apparatus 1 supplies a processing liquid to the upper surface Wa of the substrate W, and processes the surface Wa of the substrate W. The substrate processing apparatus 1 treats the substrate W with, for example, DHF, DIW, HPS, SPM, HPS, SC1 (a mixed liquid of ammonia water and hydrogen peroxide water), and a second fluid (a mixed fluid of DIW and gas) in this order. The surface Wa is supplied (see Figure 3).

The substrate processing device 1, for example, has a processing container 10, a substrate holding part 20, a substrate rotating part 25, a first supply part 31, a second supply part 32, a third supply part 33, a fourth supply part 34, a first nozzle 41, a second nozzle 42, a third nozzle 43, a fourth nozzle 44, a first moving part 51, a second moving part 52, a third moving part 53, a recovery part 60, and a control part 90.

The processing container 10 accommodates the substrate holding part 20 and the like. A gate 12 and a gate valve 13 for opening and closing the gate 12 are provided on the side wall of the processing container 10 . The substrate W is carried into the inside of the processing container 10 via the gate 12 by a transport device (not shown). Next, the substrate W is processed with a processing liquid inside the processing container 10 . Thereafter, the substrate W is transported out of the processing container 10 through the gate 12 by the transport device.

The substrate holding part 20 is provided inside the processing container 10 to hold the substrate W horizontally. The substrate holding part 20 has, for example, claws 21 for holding the outer peripheral portion of the substrate W. The claws 21 are provided in a plurality at equal intervals in the circumferential direction of the substrate W. In addition, although not shown in the figure, the substrate holding part 20 may also vacuum-absorb the bottom surface of the substrate W.

The substrate rotating part 25 rotates the substrate holding part 20 to rotate the substrate W together with the substrate holding part 20. The substrate holding part 20 holds the substrate W so that the rotation center line of the substrate W coincides with the center of the surface Wa of the substrate W.

The first supply part 31 supplies DHF or DIW to the surface Wa of the substrate W via the first nozzle 41 . The first supply part 31 has, for example, a common line 31a connected to the first nozzle 41, a plurality of individual lines 31b branched from the common line 31a, and a device 31c provided for each individual line 31b. The machine 31c has, for example, a switching valve, a flow meter, and a flow controller.

The second supply unit 32 supplies DIW or SC1 to the surface Wa of the substrate W via the second nozzle 42. The second supply unit 32 includes, for example, a common line 32a connected to the second nozzle 42, a plurality of individual lines 32b branching from the common line 32a, and a machine 32c provided in each individual line 32b. The machine 32c includes, for example, a switch valve, a flow meter, and a flow controller.

The third supply part 33 supplies HPS or SPM to the surface Wa of the substrate W via the third nozzle 43 . SPM is a mixture of HPS and sulfuric acid. The third supply part 33 has, for example, a common line 33a connected to the third nozzle 43, a plurality of individual lines 33b branched from the common line 33a, and a device 33c provided for each individual line 33b. The machine 33c has, for example, a switching valve, a flow meter, and a flow controller.

The fourth supply part 34 supplies a mixed fluid of DIW and gas to the surface Wa of the substrate W via the fourth nozzle 44 . The fourth nozzle 44 is a two-fluid nozzle. The fourth supply unit 34 includes, for example, a plurality of individual lines 34b connected to the fourth nozzle 44, and a machine 34c provided for each individual line 34b. The machine 34c has, for example, a switching valve, a flow meter, and a flow controller.

The first moving part 51 moves the first nozzle 41 in the horizontal direction and the vertical direction. The first moving part 51 has a first arm 51a and a first rotation mechanism 51b, for example, as shown in FIG. 2 . The first rotation mechanism 51b rotates the first arm 51a and moves the first nozzle 41 in the horizontal direction. Furthermore, the first rotating mechanism 51b raises and lowers the first arm 51a to move the first nozzle 41 in the vertical direction. In addition, the first moving part 51 may have a guide rail and a linear motion mechanism instead of the first arm 51a and the first rotation mechanism 51b. The linear motion mechanism moves the first nozzle 41 in the horizontal direction and the vertical direction along the guide rail.

The second moving part 52 moves the second nozzle 42 in the horizontal direction and the vertical direction independently of the first nozzle 41. The second moving part 52 has a second arm 52a and a second rotating mechanism 52b, for example, as shown in FIG. 2. The second rotating mechanism 52b rotates the second arm 52a to move the second nozzle 42 in the horizontal direction. Furthermore, the second rotating mechanism 52b raises and lowers the second arm 52a to move the second nozzle 42 in the vertical direction. In addition, the second moving part 52 may have a guide rail and a direct-acting mechanism instead of the second arm 52a and the second rotating mechanism 52b. The direct-acting mechanism moves the second nozzle 42 in the horizontal direction and the vertical direction along the guide rail. The second moving portion 52 moves the fourth nozzle 44 in the horizontal direction and the vertical direction together with the second nozzle 42 .

The third moving part 53 moves the third nozzle 43 in the horizontal direction and the vertical direction independently of the first nozzle 41 and the second nozzle 42. The third moving part 53 has a third arm 53a and a third rotating mechanism 53b, for example, as shown in FIG. 2. The third rotating mechanism 53b rotates the third arm 53a to move the third nozzle 43 in the horizontal direction. Furthermore, the third rotating mechanism 53b raises and lowers the third arm 53a to move the third nozzle 43 in the vertical direction. In addition, the third moving part 53 may have a guide rail and a direct-acting mechanism instead of the third arm 53a and the third rotating mechanism 53b. The direct-acting mechanism moves the third nozzle 43 in the horizontal direction and the vertical direction along the guide rail.

The recovery unit 60 recovers the processing liquid supplied to the substrate W. The recovery unit 60 has, for example, a cup 61. The cup 61 surrounds the outer periphery of the substrate W held by the substrate holding unit 20, and receives the processing liquid scattered from the outer periphery of the substrate W. The cup 61 does not rotate together with the substrate holding unit 20 in the present embodiment, but it may rotate together with the substrate holding unit 20. A drain pipe 62 and an exhaust pipe 63 are provided at the bottom of the cup 61. The drain pipe 62 discharges the liquid remaining in the cup 61. The exhaust pipe 63 discharges the gas remaining in the cup 61.

The control unit 90 is, for example, a computer, and includes a calculation unit 91 such as a CPU (Central Processing Unit) and a storage unit 92 such as a memory. In the storage unit 92, a program for controlling various processes executed in the substrate processing apparatus 1 is stored. The control unit 90 controls the operation of the substrate processing apparatus 1 by causing the calculation unit 91 to execute the program stored in the storage unit 92.

Referring to FIG. 3 to FIG. 6 , a substrate processing method according to an embodiment will be described. The substrate processing method, for example, as shown in FIG. 3 , includes steps S101 to S110. Steps S101 to S110 are performed under the control of the control unit 90. The processing after step S101 starts after a transport device (not shown) moves the substrate W into the processing container 10. In addition, the substrate processing method may not include all of steps S101 to S110, but may include at least steps S101, S105, and S106 in sequence.

First, the substrate holding part 20 holds the substrate W horizontally, and then the substrate rotating part 25 rotates the substrate W together with the substrate holding part 20 (step S101). The substrate holding part 20 holds the substrate W in such a way that the rotation center line of the substrate W passes through the center of the surface Wa of the substrate. In FIGS. 4 to 6 , the rotation center line of the substrate W is represented by a dot chain.

While the substrate W is rotating, steps S101 to S110 are performed on the surface Wa of the substrate W. The surface Wa of the substrate W is the upper surface of the substrate W. Hereinafter, the surface Wa of the substrate W will also be described as the substrate surface Wa. In addition, the position directly above the center of the substrate surface Wa is also described as the center position.

Next, as shown in FIG. 4(A), the first nozzle 41 supplies DHF to the substrate surface Wa (step S102). DHF is an example of a cleaning liquid. The cleaning liquid may contain hydrofluoric acid. The first nozzle 41 supplies DHF to the center of the substrate surface Wa at the center position. DHF flows radially outward of the substrate surface Wa due to the centrifugal force, and forms a liquid film on the entire substrate surface Wa. Due to the supply of DHF, the substrate surface Wa has hydrophobicity.

Next, as shown in FIG. 4(B) , the first nozzle 41 stops the supply of DHF and supplies DIW to the substrate surface Wa (step S103). DIW is an example of pure water. The first nozzle 41 remains stopped at the center position and supplies DHF and DIW in sequence. Eliminates the hassle of replacing a centrally located nozzle. DIW replaces DHF and flows outward in the radial direction of the substrate surface Wa by centrifugal force, forming a liquid film on the entire substrate surface Wa.

Next, the first nozzle 41 supplies DIW to the substrate surface Wa, and at the same time moves from the center position to the first eccentric position (the position shown in FIG. 4 (C)). The first eccentric position is a position offset outward in the radial direction of the substrate surface Wa based on the center position. The first eccentric position is set so that there is no hole in the center of the DIW liquid film (that is, the DIW liquid film covers the entire substrate surface Wa).

While the first nozzle 41 moves from the center position to the first eccentric position, the second nozzle 42 moves from the second main position to the second eccentric position (the position shown in FIG. 4(C) ). The second position is set outside the cup 61. The second eccentric position is set similarly to the first eccentric position. While the second nozzle 42 moves from the second home position to the second eccentric position, it does not discharge DIW.

Next, as shown in FIG. 4(C), the first nozzle 41 discharges DIW at the first eccentric position, and the second nozzle 42 discharges DIW at the second eccentric position. The first nozzle 41 and the second nozzle 42 simultaneously supply DIW to the substrate surface Wa. Thereafter, the first nozzle 41 stops discharging DIW and moves to the first home position. The first home position is set on the outer side of the cup 61.

Next, the third nozzle 43 moves from the third main position to the third eccentric position (the position shown in FIG. 4(D) ). The third position is set outside the cup 61. The third eccentric position is set similarly to the first eccentric position. While the third nozzle 43 moves from the third main position to the third eccentric position, the HPS is not discharged.

Next, as shown in FIG. 4(D), the third nozzle 43 supplies HPS to the substrate surface Wa, while the second nozzle 42 supplies DIW to the substrate surface Wa (step S104). HPS is an example of a hydrophilic liquid. The hydrophilic liquid may contain HPS or ozone water. SC1 may also be used as the hydrophilic liquid. SC1 contains HPS.

According to this embodiment, the supply of HPS is started after the supply of DIW is started and before the supply of DIW is completed. That is, according to this embodiment, DIW and HPS are supplied simultaneously. By supplying DIW and HPS at the same time, drying of the substrate surface Wa can be suppressed before the hydrophilization of the substrate surface Wa proceeds sufficiently, and the generation of particles can be suppressed.

Next, as shown in FIG. 5(A) , the third nozzle 43 supplies HPS to the substrate surface Wa while moving from the third eccentric position to the center position. During this time, the second nozzle 42 supplies DIW to the substrate surface Wa while moving away from the center position so as not to interfere with the movement of the third nozzle 43 .

According to this embodiment, from the start of supply of DIW to the end of simultaneous supply of DIW and HPS, the nozzle located at the center is replaced from the first nozzle 41 that discharges DIW to the third nozzle 43 that discharges HPS. During the replacement of the nozzle, usually at least one of DIW and HPS is supplied to the substrate surface Wa. Therefore, drying of the substrate surface Wa can be suppressed, and the generation of particles can be suppressed.

In addition, in the present embodiment, during the nozzle replacement, the second nozzle 42 supplies DIW to the substrate surface Wa, but the second nozzle 42 may not be used. In a state where the first nozzle 41 and the third nozzle 43 simultaneously supply DIW and HPS to the substrate surface Wa, the nozzle located at the center may be replaced from the first nozzle 41 that discharges DIW to the third nozzle 43 that discharges HPS.

Next, as shown in FIG. 5(B), the third nozzle 43 stops at the center position and supplies HPS to the substrate surface Wa. Meanwhile, the second nozzle 42 supplies DIW to the substrate surface Wa and moves radially outward of the substrate surface Wa. In the process of expanding the HPS liquid film into concentric circles, DIW can be supplied to the outer side of the HPS liquid film, which can suppress the drying of the substrate surface Wa. In addition, if the substrate surface Wa is not dried, the process shown in FIG. 5(B) can be omitted.

Next, as shown in FIG. 5(C) , the third nozzle 43 supplies HPS to the substrate surface Wa (step S105). The third nozzle 43 supplies HPS to the center of the substrate surface Wa at a central position. The HPS flows outward in the radial direction of the substrate surface Wa due to centrifugal force, forming a liquid film on the entire substrate surface Wa. By supplying HPS, the entire substrate surface Wa can be made hydrophilic.

Next, as shown in FIG. 5(D) , the third nozzle 43 stops the supply of HPS and supplies SPM to the substrate surface Wa (step S106). The third nozzle 43 remains stopped at the center position and supplies HPS and SPM sequentially. Eliminates the hassle of replacing a centrally located nozzle.

SPM replaces HPS and flows radially outward from the substrate surface Wa by centrifugal force, forming a liquid film on the entire substrate surface Wa. SPM removes organic matter such as photoresist residues or abrasives. Abrasives are those remaining on the substrate surface Wa after CMP (Chemical Mechanical Polishing).

According to this embodiment, SPM is supplied after the hydrophilization liquid such as HPS is supplied. Since the entire hydrophobic substrate surface Wa is hydrophilized before SPM is supplied, the entire substrate surface Wa can be covered with SPM. As a result, the generation of particles on the substrate surface Wa can be suppressed.

Next, as shown in FIG. 6(A), the third nozzle 43 stops supplying SPM and supplies HPS to the substrate surface Wa (step S107). The third nozzle 43 is kept stopped at the center position and supplies HPS, SPM, and HPS in sequence. This eliminates the trouble of replacing the nozzle at the center position.

HPS replaces SPM and flows radially outward from the substrate surface Wa by centrifugal force, forming a liquid film on the entire substrate surface Wa. After the supply of SPM, the supply of HPS is carried out to remove the residual sulfur component (SO ₄ ^2- ). The supply of HPS is stopped after the set time.

Next, as shown in FIG6(B), the nozzle at the center position is replaced from the third nozzle 43 to the second nozzle 42, and the second nozzle 42 supplies SC1 to the substrate surface Wa (step S108). SC1 replaces HPS and flows radially outward of the substrate surface Wa by centrifugal force, forming a liquid film on the entire substrate surface Wa.

SC1 is an example of alkaline cleaning liquid. After the supply of SPM, the supply of alkaline cleaning liquid is carried out to remove the sulfur residue and particles. The alkaline cleaning liquid can suppress the adhesion of particles by making the zeta potential of both the substrate surface Wa and the particles negative. The supply of SC1 is stopped after the set time.

Next, as shown in FIG. 6(C), the nozzle at the center position is replaced by the fourth nozzle 44 from the second nozzle 42, and the fourth nozzle 44 supplies a mixed fluid of DIW and gas to the substrate surface Wa (step S109). The fine droplets of DIW collide with the substrate surface Wa, and the particles are removed by the impact. The fourth nozzle 44 may also move in the radial direction of the substrate surface Wa while the fourth nozzle 44 supplies the mixed fluid of DIW and gas to the substrate surface Wa.

Next, as shown in FIG. 6(D), after the supply of all the processing liquids is completed, the substrate rotating unit 25 rotates the substrate W together with the substrate holding unit 20 to spin dry the substrate W (step S110). The drying method of the substrate W is not limited to spin drying, and supercritical drying is also possible. Supercritical drying is performed in a pressure container different from the processing container 10.

Although the above describes the implementation forms of the substrate processing method and substrate processing device disclosed herein, the present disclosure is not limited to the above implementation forms, etc. Various changes, modifications, replacements, additions, deletions, and combinations can be made within the scope of the patent application, and of course, they also belong to the technical scope of the present disclosure.

1: Substrate processing device 20: Substrate holding unit 25: Substrate rotating unit 31: First supply unit 32: Second supply unit 33: Third supply unit 90: Control unit W: Substrate Wa: Substrate surface

[Fig. 1] Fig. 1 is a cross-sectional view of a substrate processing device according to an embodiment. [Fig. 2] Fig. 2 is a plan view showing an example of a first moving part, a second moving part, and a third moving part. [Fig. 3] Fig. 3 is a flow chart showing a substrate processing method according to an embodiment. [Fig. 4] Fig. 4(A) is a diagram showing an example of step S102; Fig. 4(B) is a diagram showing an example of the first stage of step S103; Fig. 4(C) is a diagram showing an example of the second stage of step S103; Fig. 4(D) is a diagram showing an example of the first stage of step S104. [Figure 5] Figure 5(A) is a diagram showing an example of the second stage of step S104; Figure 5(B) is a diagram showing an example of the third stage of step S104; Figure 5(C) is a diagram showing an example of step S105; Figure 5(D) is a diagram showing an example of step S106. [Figure 6] Figure 6(A) is a diagram showing an example of step S107; Figure 6(B) is a diagram showing an example of step S108; Figure 6(C) is a diagram showing an example of step S109; Figure 6(D) is a diagram showing an example of step S110. [Figure 7] Figure 7 is a flow chart showing a substrate processing method according to the previous example. [Figure 8] Figure 8 is an oblique view showing an example of step S204.

Claims (11)

A substrate processing method, which has the steps of: maintaining and rotating the substrate horizontally; The step of supplying a hydrophilization solution containing hydrogen peroxide water or ozone water to the hydrophobic surface of the rotating substrate; After supplying the hydrophilizing liquid, a mixed liquid of sulfuric acid and hydrogen peroxide is supplied to the surface of the rotating substrate. The substrate processing method according to Claim 1 further includes the step of supplying a cleaning solution containing hydrofluoric acid to the surface of the rotating substrate before supplying the hydrophilizing solution. The substrate processing method as recited in claim 2 comprises the step of supplying, after supplying the cleaning liquid, replacing the cleaning liquid with pure water and supplying the surface of the rotating substrate. The substrate processing method according to Claim 3, further comprising: starting the supply of the hydrophilizing liquid after the supply of the pure water starts and before the supply of the pure water ends; A step of simultaneously supplying the pure water and the hydrophilizing liquid to the surface of the rotating substrate. The substrate processing method according to claim 4, including: from the start of supply of the pure water to the end of simultaneous supply of the pure water and the hydrophilization liquid, the nozzle located directly above the center of the surface of the substrate is , a step of replacing the nozzle that discharges the pure water with the nozzle that discharges the hydrophilized liquid. The substrate processing method as described in claim 4 or 5 comprises the steps of: during the period when the pure water and the hydrophilizing liquid are simultaneously supplied to the surface of the rotating substrate, stopping the nozzle discharging the hydrophilizing liquid just above the center of the surface of the substrate, and moving the nozzle discharging the pure water to the outside in the radial direction of the substrate. The substrate processing method according to any one of claims 1 to 5, including the step of supplying the hydrophilizing liquid and the mixed liquid in this order from the same nozzle to the surface of the rotating substrate. The substrate processing method as recited in any one of claims 1 to 5 comprises the step of supplying hydrogen peroxide to the surface of the rotating substrate while stopping the supply of sulfuric acid after the supply of the mixed solution. The substrate processing method according to Claim 8 includes the step of supplying hydrogen peroxide water while stopping the supply of sulfuric acid, and then supplying an alkali cleaning solution to the surface of the rotating substrate. The substrate processing method according to Claim 9, further comprising: after supplying the alkali cleaning solution, supplying a mixed fluid of pure water and gas to the surface of the rotating substrate; A step of drying the substrate by rotating the substrate after supplying the mixed fluid of the pure water and the gas. A substrate processing device includes: a substrate holding portion that holds a substrate horizontally; a substrate rotating part that rotates the substrate holding part; a supply part for supplying a processing liquid to the surface of the substrate held by the substrate holding part; a control unit that controls the substrate rotating unit and the supply unit; The aforementioned control department performs: The step of supplying a hydrophilization solution containing hydrogen peroxide water or ozone water to the hydrophobic surface of the rotating substrate; After supplying the hydrophilizing liquid, a mixed liquid of sulfuric acid and hydrogen peroxide is supplied to the surface of the rotating substrate.

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