JP6593591B2 - Substrate processing method - Google Patents

Description

  The present invention relates to a substrate processing method for processing a substrate. Examples of substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, FED (Field Emission Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, and photomask substrates. Substrates, ceramic substrates, solar cell substrates and the like are included.

  Patent Document 1 discloses a single-wafer type substrate processing apparatus that processes substrates one by one. The substrate processing apparatus includes a spin chuck that rotates around a vertical rotation axis passing through the center of the substrate while holding the substrate horizontally, and a plurality of processing liquids that are discharged toward the upper surface of the substrate held by the spin chuck. And a nozzle. In this substrate processing apparatus, SPM, which is a mixed solution of sulfuric acid and hydrogen peroxide solution, is supplied to the upper surface of the substrate, and then hydrogen peroxide solution is supplied to the upper surface of the substrate.

JP2015-50350 A

  If a high temperature SPM and a room temperature hydrogen peroxide solution are sequentially supplied to the surface of the substrate in order to remove the resist film from the surface of the substrate on which the pattern is formed, pattern collapse may occur. According to the study by the present inventors, such a pattern collapse is caused when bubbles of a size that can be visually observed are formed in the liquid film of the hydrogen peroxide solution when the SPM on the substrate is replaced with the hydrogen peroxide solution. It turns out that it happens in some cases.

  SPM is a mixed solution of sulfuric acid and hydrogen peroxide solution, and contains caro's acid. According to the study by the present inventors, it is considered that the gas causing bubbles is mainly generated by the decomposition of caroic acid. Furthermore, according to the research by the present inventors, it is found that when the SPM on the substrate is replaced with hydrogen peroxide water, if a sudden temperature change occurs in each part of the substrate, bubbles are likely to be generated in the liquid film. It was.

  Furthermore, if the rotation speed of the substrate when supplying hydrogen peroxide solution to the substrate is small, the flow rate of the liquid discharged from the substrate is small, so that the gas gradually accumulates in the liquid film and can be visually observed. It was found that bubbles were generated. Increasing the rotation speed of the substrate can reduce gas stagnation on the substrate. However, if the rotation speed of the substrate is high, the flow rate of the liquid discharged from the substrate is large, thereby preventing the substrate from being partially exposed. Therefore, the hydrogen peroxide solution must be supplied to the substrate at a large flow rate. Therefore, the consumption of hydrogen peroxide water increases.

  Accordingly, one of the objects of the present invention is to suppress the generation of bubbles in the liquid film of hydrogen peroxide solution when replacing the SPM on the substrate with the hydrogen peroxide solution.

  The invention according to claim 1 for achieving the above object is a substrate processing method for removing a resist covering a pattern formed on an upper surface of a substrate from the substrate, wherein the substrate is rotated with sulfuric acid and peroxide. An SPM supplying step of covering the upper surface of the substrate with a liquid film of SPM that is a mixed solution with hydrogen water, and after the SPM supplying step, the position of the hydrogen peroxide solution landing on the upper surface of the substrate is the center of the substrate 20-50 rpm (revolution per minute) while discharging hydrogen peroxide solution toward the upper surface of the substrate covered with the liquid film of SPM so as to be located in the middle of the substrate between the outer periphery of the substrate And a hydrogen peroxide solution supply step of rotating the substrate at a low rotation speed.

  According to this method, SPM is supplied to the upper surface of the substrate in order to remove the resist on the pattern. Thereafter, hydrogen peroxide solution is supplied to the upper surface of the substrate covered with the liquid film of SPM. The hydrogen peroxide solution lands on the upper surface of the substrate and then flows outward along the upper surface of the substrate by centrifugal force. Most of the SPM is discharged outward from the substrate by supplying hydrogen peroxide water to the substrate. A part of the SPM is mixed with the hydrogen peroxide solution on the substrate, and then discharged to the outside together with the hydrogen peroxide solution. In this way, the SPM on the substrate is replaced with the hydrogen peroxide solution.

  The hydrogen peroxide solution is discharged toward the middle of the substrate between the center of the substrate and the outer periphery of the substrate. As will be described later, when the hydrogen peroxide solution is discharged toward the middle of the substrate, the rapid temperature drop at the center of the substrate can be suppressed compared to the case where the hydrogen peroxide solution is discharged toward the center of the substrate. it can. Thereby, generation | occurrence | production of a bubble can be suppressed and collapse of the pattern formed in the upper surface of a board | substrate can be suppressed.

  Further, the hydrogen peroxide solution is discharged toward the upper surface of the substrate rotating at a low rotation speed of 20 to 50 rpm. When the hydrogen peroxide solution is discharged toward the middle of the substrate, the generation of bubbles due to a rapid temperature drop can be suppressed, but the generation of bubbles is not completely eliminated. When the rotation speed of the substrate is extremely low, the gas gradually accumulates in the liquid film, and bubbles of a size that can be visually observed are generated.

As will be described later, when the rotation speed of the substrate was 20 to 50 rpm, no visible bubbles were confirmed or hardly confirmed. Therefore, the collapse of the pattern formed on the upper surface of the substrate can be reduced. Furthermore, since the rotation speed of the substrate is relatively low, it is possible to prevent the upper surface of the substrate from being partially exposed without supplying the hydrogen peroxide solution at a large flow rate. Therefore, the collapse of the pattern can be reduced while suppressing the consumption amount of the hydrogen peroxide solution.
Furthermore, according to this method, after the hydrogen peroxide solution is discharged toward the middle of the substrate, the position of the hydrogen peroxide solution landing on the upper surface of the substrate moves from the middle of the substrate to the center of the substrate. When the hydrogen peroxide solution is discharged toward the middle of the rotating substrate, a part of the hydrogen peroxide solution that has landed on the upper surface of the substrate flows inward along the upper surface of the substrate. Thereby, SPM is removed from the center of the substrate. Further, when the position where the hydrogen peroxide solution is deposited moves from the middle of the substrate to the center of the substrate, the hydrogen peroxide solution directly hits a circular region from the middle of the substrate to the center of the substrate. Therefore, the hydrogen peroxide solution can surely reach between two adjacent patterns. Thereby, the SPM on the substrate can be efficiently replaced with the hydrogen peroxide solution.

In the invention according to claim 2 , in the hydrogen peroxide solution supply step, the rotation speed of the substrate when the landing position of the hydrogen peroxide solution with respect to the upper surface of the substrate is located in the middle of the substrate, 2. The substrate processing method according to claim 1 , wherein the hydrogen peroxide solution landing position with respect to the upper surface of the substrate is smaller than a rotation speed of the substrate when located at a center of the substrate.
When the rotation speed of the substrate decreases, the thickness (film thickness) of the liquid film covering the upper surface of the substrate increases. According to this method, when the landing position of the hydrogen peroxide solution is located in the middle of the substrate, the rotation speed of the substrate is relatively small, so the thickness of the liquid film covering the upper surface of the substrate is relatively large. . Even if minute bubbles that cannot be visually observed are generated in the liquid film, if the film thickness is increased, the density of the bubbles in the liquid film decreases. Thereby, the influence which a bubble has on a pattern can be made small.

  On the other hand, when the landing position of the hydrogen peroxide solution is located at the center of the substrate, the rotation speed of the substrate is relatively large and the film thickness is relatively small, but almost all SPM is separated from the substrate. Since it is removed, the amount of bubbles generated is small. Further, since the rotation speed of the substrate is relatively high, even if minute bubbles are generated in the liquid film, the bubbles are discharged from the substrate together with the hydrogen peroxide solution relatively quickly. Therefore, it is possible to efficiently replace the SPM at the center of the substrate with the hydrogen peroxide solution while avoiding the influence of bubbles on the pattern.

According to a third aspect of the present invention, in the hydrogen peroxide solution supplying step, the hydrogen peroxide solution is inclined with respect to the upper surface of the substrate so as to move away from the center of the substrate as it approaches the upper surface of the substrate. 3. The substrate processing method according to claim 1, wherein the substrate is discharged in an inclined discharge direction.
According to this method, since the discharge direction of the hydrogen peroxide solution is inclined outward with respect to the upper surface of the substrate, the hydrogen peroxide solution that is scattered in the discharge direction toward the upper surface of the substrate is placed on the outer periphery of the substrate. It has kinetic energy in the direction of heading. Accordingly, the hydrogen peroxide solution that has landed on the upper surface of the substrate flows outward more quickly than when the hydrogen peroxide solution is discharged in a direction perpendicular to the upper surface of the substrate. Therefore, the SPM in the annular region outside the landing position can be efficiently replaced with the hydrogen peroxide solution.

  Furthermore, by discharging the hydrogen peroxide solution in a direction inclined outward with respect to the upper surface of the substrate, a flow of the hydrogen peroxide solution toward the outer periphery of the substrate can be formed on the substrate, thereby reducing the rotation speed of the substrate. Even if it makes it, SPM on a board | substrate can be substituted efficiently. When the rotation speed of the substrate is lowered, the flow rate of the liquid discharged from the substrate is decreased, so that the thickness of the liquid film covering the upper surface of the substrate is increased. Therefore, the film thickness can be increased and the SPM on the substrate can be efficiently replaced.

If the substrate is a disc shape having a diameter of 300 mm, as in the invention according to claim 4, an intermediate of the substrate, the radius may be a position of 58～108Mm. In this case, as will be described later, it was confirmed that a rapid temperature decrease at the center of the substrate was reduced. Therefore, it is possible to reduce the generation of bubbles due to a rapid temperature drop.
The invention according to claim 5 is a substrate processing method for removing a resist covering a pattern formed on an upper surface of a substrate from the substrate, wherein the mixed solution of sulfuric acid and hydrogen peroxide solution is rotated while the substrate is rotated. The SPM is discharged toward the upper surface of the substrate to form a liquid film forming step of covering the upper surface of the substrate with the liquid film of SPM, and the SPM toward the upper surface of the substrate covered with the liquid film of SPM. A decelerating step of reducing the rotation speed of the substrate from the first rotation speed to the second rotation speed while discharging, and after the SPM supply step, the hydrogen peroxide solution to the upper surface of the substrate While discharging the hydrogen peroxide solution toward the upper surface of the substrate covered with the liquid film of SPM, the liquid deposition position is located in the middle of the substrate between the center of the substrate and the outer periphery of the substrate. At the second rotational speed Discharge step of rotating the serial board, including a hydrogen peroxide supply step including a substrate processing method.
The invention according to claim 6 is the substrate processing method according to claim 5, wherein the second rotation speed is 20 to 50 rpm.
In the invention according to claim 7, in the hydrogen peroxide solution supply step, after the discharge step, the rotation speed of the substrate is set to the second rotation while discharging the hydrogen peroxide solution toward the upper surface of the substrate. The substrate processing method according to claim 5, further comprising an acceleration step of increasing the speed to a third rotation speed.

It is the schematic diagram which looked at the inside of the processing unit with which the substrate processing apparatus concerning one embodiment of the present invention was equipped horizontally. It is a schematic diagram which shows the vertical cross section of a 1st chemical | medical solution nozzle. It is a schematic diagram which shows an example of the cross section of the board | substrate before and after processing by a processing unit. It is a flowchart which shows an example of the process of the board | substrate performed by the process unit. 5 is a time chart showing the rotation speed of the substrate when the SPM on the substrate is replaced with hydrogen peroxide water in the example of the substrate processing shown in FIG. 4. It is a graph which shows transition of the temperature of the center and outer periphery of a board | substrate when supply of the hydrogen peroxide solution with respect to the upper surface of a board | substrate is started in the center of a board | substrate. It is a graph which shows transition of the temperature of the center and outer periphery of a board | substrate when supply of the hydrogen peroxide solution with respect to the upper surface of a board | substrate is started in the middle of a board | substrate. It is a table | surface which shows the experimental result which confirmed whether the bubble was generated in the hydrogen peroxide solution on a board | substrate when replacing SPM on a board | substrate with hydrogen peroxide solution. It is a schematic diagram which shows the vertical cross section of the 1st chemical | medical solution nozzle which concerns on other embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of the inside of a processing unit 2 provided in a substrate processing apparatus 1 according to an embodiment of the present invention viewed horizontally. FIG. 2 is a schematic diagram showing a vertical cross section of the first chemical nozzle 11.
As shown in FIG. 1, the substrate processing apparatus 1 is a single-wafer type apparatus that processes a disk-shaped substrate W such as a semiconductor wafer one by one. The substrate processing apparatus 1 controls the processing unit 2 that processes the substrate W with a processing fluid such as processing liquid or processing gas, a transfer robot (not shown) that transfers the substrate W to the processing unit 2, and the substrate processing apparatus 1. And a control device 3 that performs the control. The control device 3 is a computer including a calculation unit and a storage unit.

  The processing unit 2 includes a chamber 4 having an internal space, a spin chuck 5 that rotates around a vertical rotation axis A1 that passes through a central portion of the substrate W while holding the substrate W horizontally in the chamber 4, and the substrate W A plurality of nozzles that discharge the processing liquid and a cup 41 that receives the processing liquid scattered outward from the substrate W. The plurality of nozzles include a first chemical liquid nozzle 11, a second chemical liquid nozzle 23, a first rinse liquid nozzle 31, and a second rinse liquid nozzle 36.

  The spin chuck 5 is a disc-shaped spin base 7 that is held in a horizontal posture, a plurality of chuck pins 6 that hold the substrate W in a horizontal posture above the spin base 7, and a plurality of chuck pins 6 that are opened and closed. A chuck opening / closing mechanism (not shown). The spin chuck 5 further includes a spin shaft 8 that extends downward from the center of the spin base 7 and a spin motor 9 that rotates the substrate W and the spin base 7 around the rotation axis A1 by rotating the spin shaft 8. . The spin chuck 5 is not limited to a clamping chuck in which a plurality of chuck pins 6 are brought into contact with the peripheral end surface of the substrate W, and the back surface (lower surface) of the substrate W, which is a non-device forming surface, is adsorbed to the upper surface of the spin base 7. Thus, a vacuum chuck that holds the substrate W horizontally may be used.

  The first chemical nozzle 11 is a scan nozzle that can move in the chamber 4. The first chemical nozzle 11 is attached to the tip of a first nozzle arm 19 that extends horizontally in the chamber 4. The first chemical liquid nozzle 11 is connected to a first nozzle moving unit 20 that moves the first chemical liquid nozzle 11 in at least one of the vertical direction and the horizontal direction by moving the first nozzle arm 19. The first nozzle moving unit 20 is a turning mechanism for turning the first chemical liquid nozzle 11 around a turning axis extending vertically around the cup 41. The first nozzle moving unit 20 includes a processing position where the liquid discharged from the first chemical liquid nozzle 11 is deposited on the upper surface of the substrate W, and a retreat position where the first chemical liquid nozzle 11 is positioned around the spin chuck 5 in plan view. The 1st chemical | medical solution nozzle 11 is moved between.

  The first chemical liquid nozzle 11 is connected to a sulfuric acid pipe 12 that guides the sulfuric acid supplied to the first chemical liquid nozzle 11 and a hydrogen peroxide water pipe 16 that guides the hydrogen peroxide solution supplied to the first chemical liquid nozzle 11. Has been. A sulfuric acid valve 13 for switching supply and stop of supply of sulfuric acid to the first chemical liquid nozzle 11 and a sulfuric acid flow rate adjusting valve 14 for changing the flow rate of sulfuric acid supplied to the first chemical liquid nozzle 11 are interposed in the sulfuric acid pipe 12. Yes. Similarly, a hydrogen peroxide solution valve 17 for switching the supply and stop of supply of the hydrogen peroxide solution to the first chemical solution nozzle 11 and a hydrogen peroxide solution for changing the flow rate of the hydrogen peroxide solution supplied to the first chemical solution nozzle 11. The flow rate adjusting valve 18 is interposed in the hydrogen peroxide water pipe 16.

  Both sulfuric acid and hydrogen peroxide are examples of acidic chemicals. Sulfuric acid whose temperature is adjusted to a temperature higher than room temperature (for example, a constant temperature in the range of 60 to 90 ° C.) by the heater 15 is supplied from the sulfuric acid pipe 12 to the first chemical liquid nozzle 11. The first chemical nozzle 11 is supplied with hydrogen peroxide solution at room temperature (a constant temperature within a range of 20 to 30 ° C.) from the hydrogen peroxide solution pipe 16. When the control device 3 changes the opening degree of the sulfuric acid flow rate adjustment valve 14 and the hydrogen peroxide flow rate adjustment valve 18, the flow rates of sulfuric acid and hydrogen peroxide solution supplied to the first chemical liquid nozzle 11 are changed.

  When only one of the sulfuric acid valve 13 and the hydrogen peroxide water valve 17 is opened, only one of the sulfuric acid and the hydrogen peroxide water is supplied to the first chemical liquid nozzle 11. When both the sulfuric acid valve 13 and the hydrogen peroxide solution valve 17 are opened, both sulfuric acid and hydrogen peroxide solution are supplied to the first chemical liquid nozzle 11. As a result, sulfuric acid and hydrogen peroxide water are mixed in the first chemical nozzle 11 to generate SPM containing caloic acid (also referred to as peroxomonosulfuric acid) having strong oxidizing power. Further, SPM is heat generated by mixing sulfuric acid and hydrogen peroxide water, and is heated to a temperature (100 ° C. or higher, for example, 170 ° C.) higher than the temperature of sulfuric acid before mixing. Therefore, when both the sulfuric acid valve 13 and the hydrogen peroxide valve 17 are opened, SPM, which is an example of an acidic chemical solution, is discharged from the first chemical solution nozzle 11.

  As shown in FIG. 2, the first chemical nozzle 11 includes a mixing unit 21 that mixes the sulfuric acid supplied from the sulfuric acid pipe 12 and the hydrogen peroxide solution supplied from the hydrogen peroxide solution pipe 16, and the inside of the mixing unit 21. A discharge unit 22 that discharges the mixed solution of sulfuric acid and hydrogen peroxide solution mixed in the above. The sulfuric acid pipe 12 and the hydrogen peroxide water pipe 16 are flexible tubes. The first chemical nozzle 11 has higher rigidity than the sulfuric acid pipe 12 and the hydrogen peroxide pipe 16.

  The mixing part 21 of the first chemical liquid nozzle 11 mixes sulfuric acid and hydrogen peroxide solution, the first attachment part 21a to which the sulfuric acid pipe 12 is attached, the second attachment part 21b to which the hydrogen peroxide water pipe 16 is attached. And a mixing chamber 21c. The first attachment portion 21 a and the second attachment portion 21 b are disposed above the discharge portion 22 of the first chemical liquid nozzle 11. The discharge unit 22 continuously discharges the mixed solution of sulfuric acid and hydrogen peroxide solution mixed in the mixing unit 21 downward from the discharge port 11a.

  As shown in FIG. 1, the second chemical liquid nozzle 23 is connected to a second chemical liquid pipe 24 that guides an alkaline chemical liquid supplied to the second chemical liquid nozzle 23. A second chemical liquid valve 25 that switches between supplying and stopping supply of the alkaline chemical liquid to the second chemical liquid nozzle 23 is interposed in the second chemical liquid pipe 24. When the second chemical liquid valve 25 is opened, the alkaline chemical liquid is continuously discharged downward from the second chemical liquid nozzle 23. The alkaline chemical liquid is, for example, SC1 (mixed liquid of ammonia water, hydrogen peroxide water, and water). If it is an alkaline chemical, the alkaline chemical may be a liquid other than SC1.

  The second chemical liquid nozzle 23 is a scan nozzle. The second chemical liquid nozzle 23 is attached to the tip of a second nozzle arm 26 that extends horizontally within the chamber 4. The second chemical liquid nozzle 23 is connected to a second nozzle moving unit 27 that moves the second chemical liquid nozzle 23 in at least one of the vertical direction and the horizontal direction by moving the second nozzle arm 26. The second nozzle moving unit 27 is a turning mechanism for turning the second chemical liquid nozzle 23 around a turning axis extending vertically around the cup 41. The second nozzle moving mechanism moves the second chemical liquid nozzle 23 between the processing position and the retracted position.

  The first rinse liquid nozzle 31 is connected to a first rinse liquid pipe 32 that guides the rinse liquid supplied to the first rinse liquid nozzle 31. A first rinsing liquid valve 33 that switches between supplying and stopping supply of the rinsing liquid to the first rinsing liquid nozzle 31 is interposed in the first rinsing liquid pipe 32. When the first rinse liquid valve 33 is opened, the rinse liquid is continuously discharged downward from the first rinse liquid nozzle 31. The rinse liquid discharged from the first rinse liquid nozzle 31 is, for example, carbonated water. Carbonated water is an example of a conductive static eliminating liquid having a specific resistance larger than that of SPM. The rinse liquid may be any of pure water (deionized water), electrolytic ion water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 to 100 ppm).

  The first rinse liquid nozzle 31 is a scan nozzle. The first rinsing liquid nozzle 31 is attached to the tip of a third nozzle arm 34 that extends horizontally in the chamber 4. The first rinsing liquid nozzle 31 is connected to a third nozzle moving unit 35 that moves the first rinsing liquid nozzle 31 in at least one of the vertical direction and the horizontal direction by moving the third nozzle arm 34. The third nozzle moving unit 35 is a turning mechanism that rotates the first rinse liquid nozzle 31 around a rotation axis that extends vertically around the cup 41. The third nozzle moving unit 35 moves the first rinse liquid nozzle 31 between the processing position and the retracted position.

  The second rinse liquid nozzle 36 is a fixed nozzle fixed at a predetermined position in the chamber 4. The second rinse liquid nozzle 36 may be a scan nozzle. The second rinse liquid nozzle 36 is connected to a second rinse liquid pipe 37 that guides the rinse liquid supplied to the second rinse liquid nozzle 36. A second rinse liquid valve 38 for switching between supply and stop of the rinse liquid to the second rinse liquid nozzle 36 is interposed in the second rinse liquid pipe 37. When the second rinse liquid valve 38 is opened, the rinse liquid is discharged downward from the second rinse liquid nozzle 36 toward the center of the upper surface of the substrate W. The rinse liquid discharged from the second rinse liquid nozzle 36 is, for example, pure water.

  The cup 41 surrounds the periphery of the spin chuck 5. The cup 41 includes a plurality of guards 42 that receive the processing liquid scattered outward from the substrate W and a plurality of trays 43 that receive the processing liquid guided downward by the plurality of guards 42. The plurality of guards 42 are arranged concentrically so as to surround the periphery of the spin chuck 5. The guard 42 includes a cylindrical inclined portion 42a that extends obliquely upward toward the rotation axis A1, and a cylindrical guide portion 42b that extends downward from the lower end portion (outer end portion) of the inclined portion 42a. The upper end of the inclined portion 42 a corresponding to the upper end of the guard 42 has an inner diameter larger than the outer diameter of the substrate W. The plurality of inclined portions 42a overlap in the vertical direction. The plurality of trays 43 correspond to the plurality of guards 42, respectively. The tray 43 forms an annular groove located below the lower end of the guide portion 42b.

  The plurality of guards 42 are connected to a guard lifting / lowering unit 44 that individually lifts and lowers the plurality of guards 42. The guard lifting / lowering unit 44 lifts and lowers the guard 42 vertically between the processing position and the retracted position. The processing position is an upper position where the upper end of the guard 42 is located above the substrate W. The retracted position is a lower position where the upper end of the guard 42 is positioned below the substrate W. FIG. 1 shows a state where the two outer guards 42 are arranged at the processing position and the remaining two guards 42 are arranged at the retracted position. When the processing liquid is supplied to the rotating substrate W, the guard lifting / lowering unit 44 positions one of the guards 42 at the processing position, and makes the inner peripheral surface of the guard 42 horizontal with respect to the peripheral end surface of the substrate W. Make them face each other.

FIG. 3 is a schematic diagram illustrating an example of a cross section of the substrate W before and after being processed by the processing unit 2. The left side of FIG. 3 shows a cross section of the substrate W before being processed by the processing unit 2, and the right side of FIG. 3 shows a cross section of the substrate W after being processed by the processing unit 2.
As shown in FIG. 3, the plurality of patterns are formed on the surface of a silicon wafer which is an example of the substrate W, and are arranged inside the resist layer. The pattern is, for example, a line having a width smaller than the height. The interval between two adjacent patterns is smaller than the pattern height. The surface layer of the resist forms a hardened layer hardened by ion implantation. Below, the resist peeling process which removes such a resist from the surface (upper surface) of the board | substrate W in which a device is formed is demonstrated.

FIG. 4 is a flowchart showing an example of the processing of the substrate W performed by the processing unit 2. In the following, reference is made to FIG. 1 and FIG.
When the substrate W is processed by the processing unit 2, a carry-in process (step S1 in FIG. 4) for carrying the substrate W into the chamber 4 is performed.
Specifically, the control device 3 causes the hand of the transfer robot holding the substrate W to enter the chamber 4 in a state where all the nozzles and the like are in the retracted position. Then, the control device 3 causes the transfer robot to place the substrate W on the plurality of chuck pins 6. Thereafter, the control device 3 retracts the hand of the transfer robot from the chamber 4. Further, after the substrate W is placed on the plurality of chuck pins 6, the control device 3 causes the plurality of chuck pins 6 to grip the substrate W. Thereafter, the control device 3 rotates the spin motor 9. Thereby, the rotation of the substrate W is started.

Next, a carbonated water supply step (step S2 in FIG. 4) for supplying carbonated water, which is an example of a rinse solution and a charge eliminating solution, to the substrate W is performed.
Specifically, the control device 3 controls the third nozzle moving unit 35 to move the first rinsing liquid nozzle 31 serving as a static elimination liquid nozzle from the retracted position to the processing position. Thereafter, the control device 3 opens the first rinsing liquid valve 33 and causes the first rinsing liquid nozzle 31 to discharge carbonated water at room temperature toward the center of the upper surface of the substrate W. When a predetermined time elapses after the first rinse liquid valve 33 is opened, the control device 3 closes the first rinse liquid valve 33 and stops the discharge of carbonated water from the first rinse liquid nozzle 31. Thereafter, the control device 3 retracts the first rinse liquid nozzle 31 from above the substrate W by controlling the third nozzle moving unit 35.

  The carbonated water discharged from the first rinse liquid nozzle 31 lands on the upper surface of the substrate W and then flows outward along the upper surface of the substrate W by centrifugal force. Accordingly, carbonated water is supplied to the entire upper surface of the substrate W, and a liquid film of carbonated water covering the entire upper surface of the substrate W is formed on the substrate W. Therefore, when the substrate W is charged, the charge moves from the substrate W to carbonated water, and the charge is removed from the substrate W. In particular, since the specific resistance of carbonated water is larger than the specific resistance of SPM, the charge slowly moves from the substrate W to the carbonated water. Therefore, it is possible to prevent damage to the device formed on the substrate W due to heat generation or discharge due to a rapid charge movement.

  When the first rinsing liquid nozzle 31 is discharging carbonated water, the control device 3 may make the carbonated liquid landing position with respect to the upper surface of the substrate W stationary at the central part, or the central part and the outer peripheral part. You may move between. In addition, after the carbonated water film is formed on the substrate W, the control device 3 rotates the substrate W at a predetermined rotation speed (for example, 1 to 30 rpm) or stops the rotation of the substrate W. By stopping the discharge of carbonated water from the 1 rinse liquid nozzle 31, the carbonated water liquid film covering the entire upper surface of the substrate W may be held on the substrate W in a state where the discharge of carbonated water is stopped. .

Next, an SPM supply step (step S3 in FIG. 4) for supplying SPM, which is an example of a resist stripping solution and an acidic chemical solution, to the substrate W is performed.
Specifically, the control device 3 controls the first nozzle moving unit 20 to move the first chemical liquid nozzle 11 from the retracted position to the processing position. Thereafter, the control device 3 opens the sulfuric acid valve 13 and the hydrogen peroxide water valve 17 to discharge the high-temperature SPM toward the upper surface of the substrate W. When the first chemical nozzle 11 is discharging SPM, the control device 3 may stop the SPM liquid deposition position with respect to the upper surface of the substrate W at the central portion, or move between the central portion and the outer peripheral portion. You may let them.

  The SPM discharged from the first chemical liquid nozzle 11 lands on the upper surface of the substrate W and then flows outward along the upper surface of the substrate W. The carbonated water on the substrate W is swept away by the SPM and discharged around the substrate W. Thereby, the liquid film of carbonated water on the substrate W is replaced with the liquid film of SPM covering the entire upper surface of the substrate W. Further, when the controller 3 moves the SPM landing position relative to the upper surface of the substrate W between the central portion and the outer peripheral portion, the SPM landing position passes through the entire upper surface of the substrate W, and The entire upper surface is scanned. In this way, SPM is supplied to the entire upper surface of the substrate W. As a result, the resist is removed from the substrate W.

Next, a hydrogen peroxide solution supply step (step S4 in FIG. 4) for supplying room temperature hydrogen peroxide solution, which is an example of an acidic chemical solution, to the substrate W is performed.
Specifically, the control device 3 operates in a state where the first chemical solution nozzle 11 is discharging SPM above the substrate W, that is, in a state where the sulfuric acid valve 13 and the hydrogen peroxide solution valve 17 are opened. 13 is closed. As a result, the supply of sulfuric acid to the first chemical liquid nozzle 11 is stopped, and only the hydrogen peroxide solution at room temperature is discharged from the first chemical liquid nozzle 11 toward the upper surface of the rotating substrate W. The hydrogen peroxide solution discharged from the first chemical solution nozzle 11 lands on the upper surface of the substrate W and then flows outward along the upper surface of the substrate W. Thereby, the SPM on the substrate W is replaced with the hydrogen peroxide solution, and a liquid film of the hydrogen peroxide solution covering the entire upper surface of the substrate W is formed. When a predetermined time elapses after the sulfuric acid valve 13 is closed, the control device 3 closes the hydrogen peroxide solution valve 17 and stops the discharge of the hydrogen peroxide solution from the first chemical solution nozzle 11. Thereafter, the control device 3 retracts the first chemical solution nozzle 11 from above the substrate W by controlling the first nozzle moving unit 20.

Next, the 2nd rinse liquid supply process (step S5 of FIG. 4) which supplies the pure water of room temperature which is an example of the rinse liquid to the board | substrate W is performed.
Specifically, the control device 3 opens the second rinsing liquid valve 38 and causes the second rinsing liquid nozzle 36 to discharge pure water at room temperature toward the center of the upper surface of the rotating substrate W. The pure water discharged from the second rinsing liquid nozzle 36 lands on the center of the upper surface of the substrate W and then flows outward along the upper surface of the substrate W. As a result, the hydrogen peroxide solution on the substrate W is washed away by the pure water, and a liquid film of pure water covering the entire upper surface of the substrate W is formed. When a predetermined time elapses after the second rinse liquid valve 38 is opened, the control device 3 closes the second rinse liquid valve 38 and stops the discharge of pure water from the second rinse liquid nozzle 36.

Next, the SC1 supply process (step S6 in FIG. 4) for supplying room temperature SC1, which is an example of the alkaline chemical solution, to the substrate W is performed.
Specifically, the control device 3 controls the second nozzle moving unit 27 to move the second chemical liquid nozzle 23 from the retracted position to the processing position. After the second chemical liquid nozzle 23 is disposed above the substrate W, the control device 3 opens the second chemical liquid valve 25 and discharges SC1 to the second chemical liquid nozzle 23 toward the upper surface of the rotating substrate W. Let When the second chemical liquid nozzle 23 is discharging SC1, the control device 3 may stop the SC1 liquid landing position with respect to the upper surface of the substrate W at the central portion, or move between the central portion and the outer peripheral portion. You may let them. When a predetermined time elapses after the second chemical liquid valve 25 is opened, the control device 3 closes the second chemical liquid valve 25 and stops the discharge of SC1. Thereafter, the control device 3 controls the second nozzle moving unit 27 to retract the second chemical solution nozzle 23 from above the substrate W.

  The SC 1 discharged from the second chemical liquid nozzle 23 lands on the upper surface of the substrate W and then flows outward along the upper surface of the substrate W. The pure water on the substrate W is washed away by the SC 1 and discharged around the substrate W. As a result, the pure water liquid film on the substrate W is replaced with the SC1 liquid film covering the entire upper surface of the substrate W. Furthermore, when the controller 3 moves the SC1 liquid landing position relative to the upper surface of the substrate W between the central portion and the outer peripheral portion, the SC1 liquid landing position passes through the entire upper surface of the substrate W, and The entire upper surface is scanned. Therefore, SC1 discharged from the second chemical liquid nozzle 23 is supplied to the entire upper surface of the substrate W, and the entire upper surface of the substrate W is processed uniformly.

Next, the 2nd rinse liquid supply process (step S7 of FIG. 4) which supplies the pure water of room temperature which is an example of a rinse liquid to the board | substrate W is performed.
Specifically, the control device 3 opens the second rinsing liquid valve 38 and causes the second rinsing liquid nozzle 36 to discharge pure water at room temperature toward the center of the upper surface of the rotating substrate W. The pure water discharged from the second rinsing liquid nozzle 36 lands on the center of the upper surface of the substrate W and then flows outward along the upper surface of the substrate W. As a result, the SC1 on the substrate W is washed away with pure water, and a liquid film of pure water covering the entire upper surface of the substrate W is formed. When a predetermined time elapses after the second rinse liquid valve 38 is opened, the control device 3 closes the second rinse liquid valve 38 and stops the discharge of pure water from the second rinse liquid nozzle 36.

Next, a drying process (step S8 in FIG. 4) for drying the substrate W is performed.
Specifically, the control device 3 controls the spin motor 9 to control the rotation speed from the carbonated water supply step (step S2 in FIG. 4) to the second rinse liquid supply step (step S7 in FIG. 4). The substrate W is accelerated to a large drying rotation speed (for example, several thousand rpm), and the substrate W is rotated at the drying rotation speed. Thereby, a large centrifugal force is applied to the liquid on the substrate W, and the liquid adhering to the substrate W is shaken off around the substrate W. In this way, the liquid is removed from the substrate W, and the substrate W is dried. When a predetermined time elapses after the high-speed rotation of the substrate W is started, the control device 3 controls the spin motor 9 to stop the rotation of the substrate W by the spin chuck 5.

Next, an unloading step (Step S9 in FIG. 4) for unloading the substrate W from the chamber 4 is performed.
Specifically, the control device 3 moves each chuck pin 6 from the closed position to the open position, and releases the grip of the substrate W by the plurality of chuck pins 6. Thereafter, the control device 3 causes the hand of the transfer robot to enter the chamber 4 in a state where all the nozzles and the like are located at the retracted position. Then, the control device 3 holds the substrate W on the spin chuck 5 on the hand of the transfer robot. Thereafter, the control device 3 retracts the hand of the transfer robot from the chamber 4. Thereby, the processed substrate W is unloaded from the chamber 4.

FIG. 5 is a time chart showing the rotation speed and the like of the substrate W when the SPM on the substrate W is replaced with hydrogen peroxide water in the example of the processing of the substrate W shown in FIG. 4 (step S4 in FIG. 4).
As shown in FIG. 5, the control device 3 causes the first chemical liquid nozzle 11 to discharge SPM toward the upper surface of the substrate W while rotating the substrate W at 200 rpm, for example. When a predetermined time (for example, 25 seconds) elapses after the rotation of the substrate W at 200 rpm starts, the control device 3 causes the first chemical solution nozzle 11 to discharge SPM and the rotation speed of the substrate W to, for example, 20 rpm. Decrease (time T1). At this time, the control device 3 may reduce the rotation speed of the substrate W to 50 rpm. In either case, since the rotation speed of the substrate W decreases, the flow rate of SPM discharged from the substrate W decreases. For this reason, the thickness of the SPM liquid film covering the entire upper surface of the substrate W increases.

  When a predetermined time (for example, 5 seconds) elapses after the rotation speed of the substrate W is reduced, the control device 3 stops supplying SPM to the substrate W and starts supplying hydrogen peroxide water to the substrate W. (Time T2). At this time, the control device 3 starts supplying hydrogen peroxide solution to the upper surface of the substrate W in the middle of the substrate W. The middle of the substrate W is a position between the center of the substrate W and the outer periphery of the substrate W. When the diameter of the substrate W is 300 mm, the middle of the substrate W is, for example, a position having a radius of 58 to 108 mm. As will be described later, by starting the supply of the hydrogen peroxide solution in the middle of the substrate W, it is possible to suppress a rapid temperature drop in each part of the substrate W.

When a predetermined time (for example, 5 seconds) elapses after the supply of the hydrogen peroxide solution is started, the control device 3 causes the hydrogen peroxide solution landing position on the upper surface of the substrate W while rotating the substrate W at 20 rpm. Is moved from the middle of the substrate W to the center of the substrate W (time T3). Therefore, the hydrogen peroxide solution directly hits a circular region from the middle of the substrate W to the center of the substrate W. Then, when a predetermined time (for example, 5 seconds) elapses after the landing position of the hydrogen peroxide solution moves to the center of the substrate W, the control device 3 stops the supply of the hydrogen peroxide solution to the substrate W. (Time T4). Thereafter, as described above, the control device 3 starts supplying pure water to the substrate W (step S5 in FIG. 4).

  FIG. 6 is a graph showing the transition of the temperature at the center and the outer periphery of the substrate W when the supply of the hydrogen peroxide solution to the upper surface of the substrate W is started at the center of the substrate W. FIG. 7 is a graph showing the transition of the temperature at the center and the outer periphery of the substrate W when the supply of hydrogen peroxide solution to the upper surface of the substrate W is started in the middle of the substrate W. In the measurement results shown in FIG. 6 and FIG. 7, the measurement conditions are the same except for the hydrogen peroxide solution landing position. The diameter of the substrate W used for the measurement is 300 mm. FIG. 7 shows a measurement result when supply of hydrogen peroxide water to the upper surface of the substrate W is started at a position where the radius is 75 mm.

  As shown in FIG. 6, when the hydrogen peroxide solution landing position with respect to the upper surface of the substrate W is at the center of the substrate W, the temperature at the center of the substrate W rapidly decreases compared to the outer periphery of the substrate W. ing. In particular, immediately after the start of supply of the hydrogen peroxide solution, the temperature at the center of the substrate W is drastically decreased. Further, the temperature difference between the center of the substrate W and the outer periphery of the substrate W is large, and the temperature amplitude (the amount of change in temperature in several seconds) of the outer periphery of the substrate W is large.

  As shown in FIG. 7, when the hydrogen peroxide solution landing position with respect to the upper surface of the substrate W is in the middle of the substrate W, compared to the case where the hydrogen peroxide solution landing position is at the center of the substrate W, The temperature at the center of the substrate W is gradually decreased. Further, the temperature of the outer periphery of the substrate W is lowered in the same manner as the center of the substrate W, and the temperature difference between the center of the substrate W and the outer periphery of the substrate W is small. Compared with the case where the hydrogen peroxide solution landing position is at the center of the substrate W, the temperature amplitude of the outer periphery of the substrate W is smaller.

  In this way, by changing the landing position of the hydrogen peroxide solution when starting the supply of the hydrogen peroxide solution to the upper surface of the substrate W from the center of the substrate W to the middle of the substrate W, The rate of temperature change can be reduced. Thereby, generation | occurrence | production of the bubble in the center of the board | substrate W can be suppressed. Furthermore, by changing the liquid hydrogen peroxide landing position from the center of the substrate W to the middle of the substrate W, the temperature amplitude of the outer periphery of the substrate W can be reduced, so that bubbles are generated on the outer periphery of the substrate W. Can be suppressed.

FIG. 8 is a table showing experimental results for visually confirming whether or not bubbles are generated in the hydrogen peroxide solution on the substrate W when the SPM on the substrate W is replaced with the hydrogen peroxide solution. . In this experiment, the supply of hydrogen peroxide water to the upper surface of the substrate W was started in the middle of the substrate W. In the four experimental results shown in FIG. 8, the measurement conditions other than the rotation speed of the substrate W are the same.
When the rotation speed of the substrate W was 10 rpm, it was visually confirmed that many large bubbles were generated over the entire upper surface of the substrate W and the hydrogen peroxide solution on the substrate W was boiling.

When the rotation speed of the substrate W was 20 rpm, it was visually confirmed that bubbles were generated in the vicinity of the outer periphery of the substrate W. However, the number of bubbles per unit area was greatly reduced compared to the case of 10 rpm. The liquid level was almost not rippled.
When the rotation speed of the substrate W was 30 rpm, it was visually confirmed that bubbles were slightly generated near the outer periphery of the substrate W, but the number of bubbles per unit area decreased compared to the case of 20 rpm. It was.

When the rotation speed of the substrate W was 40 rpm, it was visually confirmed that no bubbles were generated at any position on the upper surface of the substrate W.
As described above, according to the experimental results shown in FIG. 8, when replacing the SPM on the substrate W with the hydrogen peroxide solution, the hydrogen peroxide on the substrate W is rotated by rotating the substrate W at a rotation speed of 20 rpm or more. The number of bubbles generated in the water can be dramatically reduced. Furthermore, the number of bubbles decreases as the rotation speed of the substrate W increases. In particular, when the rotation speed of the substrate W was 40 rpm, no visible bubbles were observed. Therefore, it is considered that bubbles having a size that can be visually observed are not generated even at a rotational speed exceeding 40 rpm.

  As described above, in this embodiment, SPM is supplied to the upper surface of the substrate W in order to remove the resist on the pattern. Thereafter, hydrogen peroxide solution is supplied to the upper surface of the substrate W covered with the liquid film of SPM. After the hydrogen peroxide solution has landed on the upper surface of the substrate W, it flows outward along the upper surface of the substrate W by centrifugal force. Most of the SPM is discharged outward from the substrate W by supplying hydrogen peroxide water to the substrate W. A part of the SPM is mixed with the hydrogen peroxide solution on the substrate W, and then discharged outward from the substrate W together with the hydrogen peroxide solution. In this way, the SPM on the substrate W is replaced with the hydrogen peroxide solution.

  The hydrogen peroxide solution is discharged toward the middle of the substrate W between the center of the substrate W and the outer periphery of the substrate W. As described above, when the hydrogen peroxide solution is discharged toward the middle of the substrate W, compared with the case where the hydrogen peroxide solution is discharged toward the center of the substrate W, a rapid temperature drop at the center of the substrate W is caused. Can be suppressed. Thereby, generation | occurrence | production of a bubble can be suppressed and collapse of the pattern formed in the upper surface of the board | substrate W can be suppressed.

  Further, the hydrogen peroxide solution is discharged toward the upper surface of the substrate W rotating at a low rotation speed of 20 to 50 rpm. When the hydrogen peroxide solution is discharged toward the middle of the substrate W, the generation of bubbles due to a rapid temperature drop can be suppressed, but the generation of bubbles is not completely eliminated. When the rotation speed of the substrate W is extremely low, the gas gradually accumulates in the liquid film, and bubbles of a size that can be visually observed are generated.

  As described above, when the rotation speed of the substrate W was 20 to 50 rpm, no visible bubbles were observed, or almost no bubbles were confirmed. Therefore, the collapse of the pattern formed on the upper surface of the substrate W can be reduced. Further, since the rotation speed of the substrate W is relatively low, it is possible to prevent the upper surface of the substrate W from being partially exposed without supplying the hydrogen peroxide solution at a large flow rate. Therefore, the collapse of the pattern can be reduced while suppressing the consumption amount of the hydrogen peroxide solution.

  In this embodiment, after the hydrogen peroxide solution is discharged toward the middle of the substrate W, the position of the hydrogen peroxide solution landing on the upper surface of the substrate W moves from the middle of the substrate W to the center of the substrate W. When the hydrogen peroxide solution is discharged toward the middle of the rotating substrate W, a part of the hydrogen peroxide solution that has landed on the upper surface of the substrate W flows inward along the upper surface of the substrate W. . As a result, the SPM is removed from the center of the substrate W. Further, when the position where the hydrogen peroxide solution is deposited moves from the middle of the substrate W to the center of the substrate W, the hydrogen peroxide solution directly hits a circular region from the middle of the substrate W to the center of the substrate W. Therefore, the hydrogen peroxide solution can surely reach between two adjacent patterns. Thereby, the SPM on the substrate W can be efficiently replaced with the hydrogen peroxide solution.

  When the rotation speed of the substrate W decreases, the thickness (film thickness) of the liquid film covering the upper surface of the substrate W increases. In the present embodiment, when the hydrogen peroxide solution landing position is located in the middle of the substrate W, the rotational speed of the substrate W is relatively small, so the thickness of the liquid film covering the upper surface of the substrate W is relatively small. Big. Even if minute bubbles that cannot be visually observed are generated in the liquid film, if the film thickness is increased, the density of the bubbles in the liquid film decreases. Thereby, the influence which a bubble has on a pattern can be made small.

  On the other hand, when the hydrogen peroxide solution landing position is located at the center of the substrate W, the rotational speed of the substrate W is relatively large and the film thickness is relatively small. Since it is removed from the substrate W, the amount of bubbles generated is small. Furthermore, since the rotation speed of the substrate W is relatively high, even if minute bubbles are generated in the liquid film, the bubbles are discharged from the substrate W together with the hydrogen peroxide solution relatively quickly. Therefore, it is possible to efficiently replace the SPM at the center of the substrate W with the hydrogen peroxide solution while avoiding the influence of bubbles on the pattern.

The present invention is not limited to the contents of the above-described embodiments, and various modifications can be made within the scope of the present invention.
For example, in the above-described embodiment, the case where the SPM and the hydrogen peroxide solution are discharged from the same nozzle (the first chemical solution nozzle 11) has been described, but the SPM and the hydrogen peroxide solution may be discharged from separate nozzles. Good.

  In the above-described embodiment, the case where the first chemical liquid nozzle 11 discharges the hydrogen peroxide solution downward in the direction perpendicular to the upper surface of the substrate W has been described. However, as illustrated in FIG. The oblique nozzle (in the example of FIG. 9, the first chemical liquid nozzle 11) that discharges in the direction inclined to the upper surface of the substrate W so as to move away from the center of the substrate W as it approaches the upper surface of the substrate W. Hydrogen peroxide solution may be discharged. The oblique nozzle may be a nozzle different from the first chemical nozzle 11.

  According to this configuration, since the discharge direction of the hydrogen peroxide solution is inclined outward with respect to the upper surface of the substrate W, the hydrogen peroxide solution scattered in the discharge direction toward the upper surface of the substrate W It has kinetic energy in the direction toward the outer periphery. Accordingly, the hydrogen peroxide solution that has landed on the upper surface of the substrate W flows outward more quickly than when the hydrogen peroxide solution is discharged in a direction perpendicular to the upper surface of the substrate W. Therefore, the SPM in the annular region outside the landing position can be efficiently replaced with the hydrogen peroxide solution.

  Furthermore, by discharging the hydrogen peroxide solution in a direction inclined outward with respect to the upper surface of the substrate W, a flow of the hydrogen peroxide solution toward the outer periphery of the substrate W can be formed on the substrate W. Even if the rotation speed is lowered, the SPM on the substrate W can be efficiently replaced. When the rotation speed of the substrate W is decreased, the flow rate of the liquid discharged from the substrate W is decreased, so that the thickness of the liquid film covering the upper surface of the substrate W is increased. Therefore, in the configuration of FIG. 9, the film thickness can be increased and the SPM on the substrate W can be efficiently replaced.

In the above-described embodiment, the case where the hydrogen peroxide solution landing position with respect to the upper surface of the substrate W is moved from the middle of the substrate W to the center of the substrate W has been described. The supply of the hydrogen peroxide solution to the substrate W may be terminated without moving to the center.
In the above-described embodiment, the rotation speed (intermediate rotation speed) of the substrate W when the hydrogen peroxide solution landing position is located in the middle of the substrate W is the same as the hydrogen peroxide solution landing position of the substrate W. Although the case where the rotation speed is lower than the rotation speed (central rotation speed) of the substrate W when positioned at the center has been described, the intermediate rotation speed may be equal to or higher than the central rotation speed.

Two or more of all the aforementioned configurations may be combined. Two or more of all the above steps may be combined.
In addition, various design changes can be made within the scope of matters described in the claims.

1: substrate processing device 3: control device 5: spin chuck 11: first chemical solution nozzle 11a: discharge port 12: sulfuric acid pipe 13: sulfuric acid valve 14: sulfuric acid flow rate adjusting valve 15: heater 16: hydrogen peroxide water pipe 17: excessive Hydrogen oxide water valve 18: Hydrogen peroxide water flow rate adjustment valve 19: First nozzle arm 20: First nozzle moving unit 21: Mixing part 21a: First mounting part 21b: Second mounting part 21c: Mixing chamber 22: Discharge part A1: rotation axis W: substrate

Claims (7)

A substrate processing method for removing a resist covering a pattern formed on an upper surface of a substrate from the substrate,
An SPM supplying step of covering the upper surface of the substrate with a liquid film of SPM, which is a mixed solution of sulfuric acid and hydrogen peroxide, while rotating the substrate;
After the SPM supply step, the SPM liquid film is covered so that the hydrogen peroxide solution landing position on the upper surface of the substrate is located in the middle of the substrate between the center of the substrate and the outer periphery of the substrate. while discharging the hydrogen peroxide toward the upper surface of the substrate cracks, seen containing a hydrogen peroxide supply step of rotating the substrate at a low rotational speed of 20～50Rpm, a,
In the hydrogen peroxide solution supplying step, the hydrogen peroxide solution landing position with respect to the upper surface of the substrate is stopped in the middle of the substrate, and then the substrate is rotated at the low rotation speed while the substrate is rotated with respect to the upper surface of the substrate. A substrate processing method of moving a hydrogen peroxide solution landing position from the middle of the substrate to the center of the substrate. In the hydrogen peroxide solution supplying step, the rotation speed of the substrate when the hydrogen peroxide solution landing position with respect to the upper surface of the substrate is located in the middle of the substrate is the hydrogen peroxide solution with respect to the upper surface of the substrate. The substrate processing method according to claim 1 , wherein the liquid deposition position is lower than a rotation speed of the substrate when the liquid deposition position is located at a center of the substrate. In the hydrogen peroxide solution supply step, the hydrogen peroxide solution is discharged in a discharge direction inclined obliquely with respect to the upper surface of the substrate so as to move away from the center of the substrate as it approaches the upper surface of the substrate. The substrate processing method according to claim 1 or 2 . The substrate has a disk shape with a diameter of 300 mm,
Intermediate of the substrate, a radius of the position of 58～108Mm, the substrate processing method according to any one of claims 1-3.   A substrate processing method for removing a resist covering a pattern formed on an upper surface of a substrate from the substrate,
  A liquid film forming step of covering the upper surface of the substrate with a liquid film of SPM by discharging SPM, which is a mixed solution of sulfuric acid and hydrogen peroxide solution, toward the upper surface of the substrate while rotating the substrate; A decelerating step of reducing the rotation speed of the substrate from the first rotation speed to the second rotation speed while discharging SPM toward the upper surface of the substrate covered with the liquid film of SPM;
  After the SPM supply step, the SPM liquid film is covered so that the hydrogen peroxide solution landing position on the upper surface of the substrate is located in the middle of the substrate between the center of the substrate and the outer periphery of the substrate. A hydrogen peroxide solution supply step including a discharge step of rotating the substrate at the second rotation speed while discharging the hydrogen peroxide solution toward the upper surface of the broken substrate.   The substrate processing method according to claim 5, wherein the second rotation speed is 20 to 50 rpm.   In the hydrogen peroxide solution supplying step, after the discharging step, the rotation speed of the substrate is increased from the second rotation speed to the third rotation speed while discharging the hydrogen peroxide solution toward the upper surface of the substrate. The substrate processing method according to claim 5, further comprising an acceleration step.

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