JP2015050352A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress local temperature change of a substrate at the time of starting process liquid supply.SOLUTION: A substrate processing method includes a SPM supply step S2 for supplying high temperature SPM to the upper surface of a substrate, a DIW supply step S8 for washing away the liquid remaining on the substrate, by supplying DIW of room temperature to the upper surface of a substrate after the SPM supply step S2, and steps S5, S6 for lowering the temperature of SPM, by discharging the SPM toward the upper surface of a substrate, after the SPM supply step S2 and before the DIW supply step S8, and reducing the ratio of sulphuric acid in the SPM.

Description

  The present invention relates to a substrate processing method and a substrate processing apparatus 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 photomasks. Substrate, ceramic substrate, solar cell substrate and the like.

  In a manufacturing process of a semiconductor device, a liquid crystal display device, or the like, processing liquids having different temperatures may be sequentially supplied to the substrate while the substrate is rotated by a spin chuck. For example, in Patent Document 1, high-temperature SPM (Sulfuric Acid-Hydrogen Peroxide Mixture) is supplied to the upper surface of a rotating substrate, and then room temperature DIW (Deionzied Water) is supplied to the upper surface of the substrate covered with SPM. Thus, it is disclosed that the SPM adhering to the upper surface of the substrate is washed away.

JP 2009-238862 A

  When a high temperature processing solution such as high temperature SPM is supplied to the substrate, the substrate itself becomes high temperature. When the supply of a low temperature processing liquid such as room temperature DIW is started while the substrate is covered with the high temperature processing liquid, the position of the low temperature processing liquid and the vicinity thereof (hereinafter referred to as “the vicinity of the liquid injection position”). Accordingly, the temperature of the substrate decreases rapidly and rapidly in the region), so that a stress that causes the substrate to contract is generated in the region near the liquid landing position and between the region near the liquid landing position and another region that is in a high temperature state. If the substrate is warped or undulated due to the temperature difference, the temperature difference of each part of the substrate will be reduced if the low-temperature processing solution is sufficiently spread over the substrate. Until then, the substrate continues to be deformed.

  In the sandwich type spin chuck, a plurality of chuck pins are pressed against the peripheral edge of the substrate. If the substrate is deformed in a state where the plurality of chuck pins are pressed against the peripheral edge of the substrate, the pressing pressure of each chuck pin against the substrate may change, and the stability of holding the substrate by the spin chuck may be reduced. Further, in the vacuum type spin chuck, the lower surface of the substrate is attracted to the upper surface of the spin base (adsorption base). If the substrate is deformed in a state where the lower surface of the substrate is attracted to the upper surface of the spin base, the contact state between the lower surface of the substrate and the upper surface of the spin base changes, and the stability of holding the substrate by the spin chuck may be reduced. is there.

  Patent Document 1 discloses that a high temperature (for example, 150 ° C.) SPM and a room temperature (for example, 25 ° C.) DIW are supplied to a substrate. Therefore, supply of DIW as a low-temperature processing liquid can be started in a state where a temperature difference of 100 ° C. or more exists between the substrate and DIW. According to the present inventors, the above-described deformation of the substrate occurs not only when the temperature difference between the substrate and the low-temperature treatment liquid is 100 ° C. or more, but also when it is less than 100 ° C. (for example, 60 ° C.). It has been confirmed that Therefore, the above-described deformation of the substrate is not limited to the case where the high temperature SPM and the room temperature DIW are sequentially supplied, but can also occur when another processing liquid having a temperature difference is sequentially supplied to the substrate.

  Accordingly, one of the objects of the present invention is to provide a substrate processing method and a substrate processing apparatus that can suppress local temperature changes of the substrate at the start of supply of the processing liquid.

  The invention described in claim 1 for achieving the object includes a chemical solution supplying step of supplying a chemical solution having a first temperature to the main surface of the substrate, and a second temperature lower than the first temperature after the chemical solution supplying step. Is supplied to the main surface of the substrate to generate an exothermic reaction by mixing the rinse liquid supply step for washing away the liquid remaining on the substrate and the chemical solution supplied to the substrate in the chemical solution supply step. A reaction liquid and a heat-generating liquid that generates heat by mixing with the reaction liquid at least at the start of discharge, and a reaction liquid-containing liquid having a liquid temperature equal to or lower than the first temperature and equal to or higher than the second temperature after the chemical supply step and Before the rinsing liquid supply process, the reaction liquid supply process for discharging the chemical liquid supplied to the substrate in the chemical liquid supply process toward the main surface of the substrate while remaining on the substrate; and the reaction liquid supply process; In parallel, discharge toward the board The reaction liquid concentration change is made to lower the temperature of the reaction liquid containing liquid discharged toward the substrate from the temperature of the reaction liquid containing liquid at the start of discharge by reducing the ratio of the exothermic liquid contained in the reaction liquid containing liquid. A substrate processing method. The main surface of the substrate may be a surface on which a device is formed, or may be a back surface opposite to the front surface.

  According to this method, the chemical solution at the first temperature (the temperature of the chemical solution before being supplied to the substrate) is supplied to the main surface of the substrate. Then, the reaction liquid-containing liquid is supplied to the main surface of the substrate while the chemical liquid remains on the substrate. The reaction liquid-containing liquid supplied to the substrate is mixed with the chemical liquid remaining on the substrate. Therefore, the ratio of the reaction liquid-containing liquid in the liquid remaining on the substrate increases, and the concentration of the chemical liquid decreases. The rinse liquid at the second temperature (the temperature of the rinse liquid before being supplied to the substrate) lower than the first temperature is supplied to the main surface of the substrate after the reaction liquid-containing liquid is supplied to the substrate. Thereby, the liquid (liquid containing the chemical solution and the reaction solution-containing liquid) remaining on the substrate is washed away.

The reaction liquid-containing liquid at the start of discharge is a mixed liquid generated by mixing the reaction liquid and the exothermic liquid. The reaction liquid is a liquid that generates an exothermic reaction when mixed with the chemical liquid. The exothermic liquid is a liquid that generates heat when mixed with the reaction liquid. The reaction liquid is heated by the exothermic liquid by being mixed with the exothermic liquid.
When the supply of the reaction liquid-containing liquid is started, the temperature of the substrate approaches the temperature of the reaction liquid-containing liquid. The temperature of the reaction liquid-containing liquid before being supplied to the substrate is equal to or lower than the temperature of the chemical liquid (first temperature) and equal to or higher than the temperature of the rinse liquid (second temperature). The reaction liquid-containing liquid generates an exothermic reaction when mixed with the chemical liquid. Therefore, when the reaction liquid-containing liquid is supplied to the main surface of the substrate while the chemical liquid remains on the substrate, an exothermic reaction occurs at the position where the reaction liquid-containing liquid is deposited and in the vicinity thereof, and the liquid deposition position The amount of temperature drop of the substrate in the vicinity region is reduced. Therefore, the temperature of the substrate gradually approaches the temperature of the reaction liquid-containing liquid.

  Furthermore, since the ratio of the exothermic liquid contained in the reaction liquid-containing liquid is smaller than that at the start of discharge of the reaction liquid-containing liquid, the ratio of the reaction liquid lower than that of the exothermic liquid is increased. The temperature drops. Accordingly, a reaction liquid-containing liquid having a temperature lower than that of the reaction liquid-containing liquid at the start of discharge is supplied to the main surface of the substrate, and the temperature of the reaction liquid-containing liquid approaches the temperature of the rinse liquid (second temperature). Therefore, the temperature drop of the substrate in the region near the liquid landing position is further moderated. Therefore, compared with the case where the rinsing liquid is supplied subsequent to the supply of the chemical liquid, a rapid and rapid temperature drop of the substrate can be suppressed, and the deformation amount of the substrate can be reduced.

  According to the second aspect of the present invention, the reaction liquid concentration changing step may be performed on the substrate from a mixing ratio in which the ratio of the exothermic liquid is larger than the ratio of the reaction liquid to a mixing ratio in which the ratio of the exothermic liquid is smaller than the ratio of the reaction liquid. By reducing the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate, the temperature of the reaction liquid-containing liquid discharged toward the substrate is made lower than the temperature of the reaction liquid-containing liquid at the start of discharge. It is a substrate processing method of Claim 1 including a process.

  According to this method, the reaction liquid-containing liquid having a large proportion of the high-temperature exothermic liquid is discharged toward the main surface of the substrate. Thereafter, from the mixing ratio in which the ratio of the exothermic liquid is larger than the ratio of the reaction liquid to the mixing ratio in which the ratio of the exothermic liquid is smaller than the ratio of the reaction liquid, the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate The rate is reduced. Therefore, the temperature of the reaction liquid-containing liquid discharged toward the substrate is gradually greatly reduced. Therefore, even when the temperature difference between the chemical liquid and the rinsing liquid is large, that is, when the difference between the first temperature and the second temperature is large, the temperature of the substrate can be gradually and uniformly brought close to the temperature of the rinsing liquid. it can. Thereby, the deformation | transformation of the board | substrate resulting from a temperature difference can be suppressed or prevented.

According to a third aspect of the present invention, the reaction liquid concentration changing step is discharged toward the substrate by reducing the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate to zero. The substrate processing method according to claim 1, further comprising a step of lowering the temperature of the reaction liquid-containing liquid from the temperature of the reaction liquid-containing liquid at the start of discharge.
According to this method, the ratio of the exothermic liquid contained in the reaction liquid-containing liquid is reduced to zero. Therefore, the exothermic liquid contained in the reaction liquid-containing liquid disappears, and only the reaction liquid is discharged toward the substrate. For this reason, the temperature of the reaction liquid-containing liquid discharged toward the substrate gradually decreases greatly and the temperature change amount of the reaction liquid-containing liquid increases. Therefore, even when the temperature difference between the chemical liquid and the rinse liquid is large, the temperature of the substrate can be brought close to the temperature of the rinse liquid gradually and uniformly.

  According to a fourth aspect of the present invention, the chemical liquid supplied to the substrate in the chemical liquid supply step is a mixed liquid of the reactive chemical liquid and an exothermic chemical liquid that is hotter than the reactive chemical liquid and generates heat when mixed with the reactive chemical liquid. The substrate processing according to claim 1, wherein the reaction liquid-containing liquid at the start of discharge is a mixed liquid of a reactive chemical liquid as a reaction liquid and an exothermic chemical liquid as a exothermic liquid. Is the method.

  According to this method, the exothermic chemical liquid (for example, sulfuric acid) having a temperature higher than that of the reactive chemical liquid (for example, hydrogen peroxide solution) is mixed with the reactive chemical liquid at a predetermined mixing ratio, thereby generating the first temperature chemical liquid. The Similarly, the exothermic chemical liquid is mixed with the reactive chemical liquid at a predetermined mixing ratio to generate a reaction liquid-containing liquid. The reaction liquid-containing liquid containing the exothermic chemical liquid and the reactive chemical liquid is discharged toward the substrate while the chemical liquid remains on the substrate. Therefore, the reactive chemical liquid contained in the reaction liquid-containing liquid is mixed with the exothermic chemical liquid contained in the chemical liquid remaining on the substrate, and an exothermic reaction occurs at the position where the reaction liquid-containing liquid is deposited and in the vicinity thereof. Therefore, the amount of temperature drop of the substrate in the vicinity of the landing position is reduced. Furthermore, a liquid containing the same component chemical solution as the chemical solution, that is, a liquid having high affinity with the chemical solution is used as the reaction solution-containing solution, so that the chemical solution and the reaction solution-containing solution can be efficiently mixed.

  The invention according to claim 5 is a liquid mixture of the chemical liquid supplied to the substrate in the chemical liquid supply step and the exothermic chemical liquid that is higher in temperature than the reactive chemical liquid and generates heat when mixed with the reactive chemical liquid. The reaction liquid-containing liquid at the start of discharge is a reaction liquid that generates an exothermic reaction by being mixed with the chemical liquid supplied to the substrate in the chemical liquid supply step, and an exothermic chemical liquid-containing liquid as a exothermic liquid containing the exothermic chemical liquid The substrate processing method according to any one of claims 1 to 3, which is a mixed solution of

  According to this method, the exothermic chemical liquid (for example, sulfuric acid) having a temperature higher than that of the reactive chemical liquid (for example, hydrogen peroxide solution) is mixed with the reactive chemical liquid at a predetermined mixing ratio, thereby generating the first temperature chemical liquid. The Similarly, an exothermic chemical liquid-containing liquid as an exothermic liquid containing an exothermic chemical liquid is mixed with a reaction liquid (for example, pure water) at a predetermined mixing ratio, thereby generating a reaction liquid-containing liquid. The reaction liquid-containing liquid including the reaction liquid and the exothermic chemical liquid-containing liquid is discharged toward the substrate in a state where the chemical liquid remains on the substrate. Accordingly, the reaction liquid contained in the reaction liquid-containing liquid mixes with the chemical liquid remaining on the substrate, and an exothermic reaction occurs at the position where the reaction liquid-containing liquid is deposited and in the vicinity thereof. Therefore, the amount of temperature drop of the substrate in the vicinity of the landing position is reduced. Furthermore, since a liquid containing the same component chemical as the chemical is used as the reaction liquid-containing liquid, the chemical liquid and the reaction liquid-containing liquid can be efficiently mixed.

  According to a sixth aspect of the present invention, the reaction solution has the same composition as the rinse solution supplied to the substrate in the rinse solution supply step, and heat is generated by mixing with the chemical solution supplied to the substrate in the chemical solution supply step. The reaction solution concentration changing step is a reaction solution discharged toward the substrate by reducing the ratio of the exothermic liquid contained in the reaction solution-containing solution discharged toward the substrate to zero. The temperature of the liquid containing liquid is made lower than the temperature of the reaction liquid containing liquid at the start of discharge, and the composition of the reaction liquid containing liquid discharged toward the substrate is set in the rinse liquid supplied to the substrate in the rinse liquid supplying step. It is a substrate processing method as described in any one of Claims 1-3 including the process made to correspond with a composition.

  According to this method, the composition of the reaction liquid contained in the reaction liquid-containing liquid is the same as that of the rinse liquid, and the ratio of the exothermic liquid contained in the reaction liquid-containing liquid is reduced to zero. Therefore, the exothermic liquid contained in the reaction liquid-containing liquid disappears, and only the reaction liquid, that is, the same kind of liquid as the rinse liquid is discharged toward the substrate. Therefore, not only the temperature of the reaction liquid-containing liquid gradually decreases greatly, but also the affinity between the liquid remaining on the substrate and the rinse liquid before the rinsing liquid supply step increases. Therefore, by supplying the rinse liquid after supplying the reaction liquid-containing liquid, the liquid remaining on the substrate can be washed away smoothly.

  In the substrate processing method, the substrate and the chemical solution are heated at a heating temperature higher than the first temperature in a state where the chemical solution supplied to the substrate in the chemical solution supply step remains on the substrate before the reaction solution supply step. The heating process to perform may be further included. In this case, the heating step may include an infrared heating step of heating the substrate and the chemical solution at a heating temperature with an infrared heater facing the main surface of the substrate. According to this method, since the temperature of the substrate and the chemical solution rises to a heating temperature higher than the temperature of the chemical solution before being supplied to the substrate (first temperature), the efficiency of the chemical treatment is increased.

  The invention according to claim 7 is a substrate holding means for holding and rotating the substrate, a chemical liquid supply means for discharging the chemical liquid at the first temperature toward the main surface of the substrate held by the substrate holding means, A rinsing liquid supply means for discharging a rinsing liquid having a second temperature lower than the first temperature toward the main surface of the substrate held by the substrate holding means, and a reaction liquid for generating an exothermic reaction by mixing with the chemical liquid And a reaction liquid-containing liquid whose temperature is lower than the first temperature and higher than the second temperature is generated by mixing the exothermic liquid that is hotter than the reaction liquid and generates heat when mixed with the reaction liquid. A reaction liquid nozzle that discharges toward the main surface of the substrate held by the substrate holding means; and a concentration changing means that changes the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged from the reaction liquid nozzle; Including a reaction liquid supply means, The substrate holding means, and a control means for controlling chemical supply means, the rinse liquid supply means, and the reaction liquid supply means, a substrate processing apparatus.

  The controller is configured to supply a chemical solution at a first temperature to the main surface of the substrate, and after the chemical solution supply step, to supply a rinse liquid at a second temperature to the main surface of the substrate, thereby remaining on the substrate. A rinsing liquid supply step for washing away the liquid being run, and a reaction liquid-containing liquid having a liquid temperature not higher than the first temperature and not lower than the second temperature after the chemical liquid supplying step and before the rinsing liquid supplying step. In the supply process, the chemical solution supplied to the substrate is discharged toward the main surface of the substrate while remaining in the substrate, and is discharged toward the substrate in parallel with the reaction solution supply step. A reaction liquid concentration changing step for reducing the temperature of the reaction liquid containing liquid discharged toward the substrate from the temperature of the reaction liquid containing liquid at the start of discharge by reducing the ratio of the exothermic liquid contained in the reaction liquid containing liquid; Execute. According to this configuration, each step of the above-described substrate processing method is executed by the control unit controlling the substrate processing apparatus. Therefore, the same effect as described above can be obtained.

1 is a schematic plan view of a substrate processing apparatus according to a first embodiment of the present invention. It is the schematic diagram which looked at the inside of the chamber with which the substrate processing apparatus concerning 1st Embodiment of this invention was equipped horizontally. It is a typical top view of a spin base and the structure relevant to this. It is a longitudinal cross-sectional view of an infrared heater. It is a time chart which shows the outline of the 1st process example performed by the process unit. It is a specific time chart of a part of the first processing example.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic plan view of a substrate processing apparatus 1 according to the first embodiment of the present invention. FIG. 2 is a schematic view of the inside of the chamber 4 provided in the substrate processing apparatus 1 according to the first embodiment of the present invention viewed horizontally. FIG. 3 is a schematic plan view of the spin base 7 and the configuration related thereto. FIG. 4 is a longitudinal sectional view of the infrared heater 58.

  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 includes a plurality of processing units 2 that process a substrate W using a processing liquid and a processing gas, a substrate transport robot CR that loads and unloads the substrate W into and from the chamber 4 of each processing unit 2, and a substrate processing And a control device 3 that controls the operation of the device provided in the device 1 and the opening and closing of a valve.

  As shown in FIG. 2, each processing unit 2 is a single-wafer type unit. Each processing unit 2 holds a box-shaped chamber 4 having an internal space and a single substrate W in the chamber 4 in a horizontal posture, and a substrate around a vertical substrate rotation axis A1 passing through the center of the substrate W. A spin chuck 5 that rotates W, a processing liquid supply device that supplies a processing liquid such as a chemical liquid or a rinsing liquid to the substrate W held by the spin chuck 5, and a substrate W held by the spin chuck 5 And a cylindrical cup 6 surrounding the spin chuck 5 around the substrate rotation axis A1.

  As shown in FIG. 2, the spin chuck 5 includes a disc-shaped spin base 7 held in a horizontal posture, a plurality of chuck pins 8 protruding upward from the outer peripheral portion of the upper surface of the spin base 7, and a plurality of chucks. A chuck opening / closing mechanism (not shown) for opening and closing the pin 8. The spin chuck 5 further rotates the spin shaft 9 downward from the center of the spin base 7 along the substrate rotation axis A1 and rotates the spin shaft 9 to move the spin base 7 and the chuck pin 8 around the substrate rotation axis A1. And a spin motor 10 that rotates the motor.

  As shown in FIG. 2, the outer diameter of the spin base 7 is larger than the diameter of the substrate W. The center line of the spin base 7 is disposed on the substrate rotation axis A1. The plurality of chuck pins 8 are held by the spin base 7 at the outer periphery of the spin base 7. The plurality of chuck pins 8 are arranged at intervals in the circumferential direction (direction around the substrate rotation axis A1). The chuck pin 8 has a spin base 7 around a vertical pin rotation axis between a closed position where the chuck pin 8 is pressed against the peripheral end surface of the substrate W and an open position where the chuck pin 8 is separated from the peripheral end surface of the substrate W. Can be rotated with respect to. The chuck opening / closing mechanism rotates the chuck pin 8 around the pin rotation axis.

  The control device 3 controls the chuck opening / closing mechanism so that the plurality of chuck pins 8 are in a closed state in which the plurality of chuck pins 8 grip the substrate W and between the open state in which the plurality of chuck pins 8 are released from gripping the substrate W. The state of the plurality of chuck pins 8 is switched. When the substrate W is transported to the spin chuck 5, the control device 3 retracts each chuck pin 8 to the open position. In this state, the control device 3 places the substrate W on the plurality of chuck pins 8 by operating the substrate transport robot CR. Thereafter, the control device 3 moves each chuck pin 8 to the closed position. Accordingly, the substrate W is held by the plurality of chuck pins 8 in a state where the lower surface of the substrate W and the upper surface of the spin base 7 are separated in the vertical direction. In this state, when the control device 3 rotates the spin motor 10, the substrate W rotates around the substrate rotation axis A <b> 1 together with the spin base 7 and the chuck pins 8.

As shown in FIG. 2, the processing unit 2 includes a first chemical nozzle 11 that discharges a chemical solution such as SPM (mixed solution containing H ₂ SO ₄ and H ₂ O ₂ ) toward the upper surface of the substrate W, The 1st chemical | medical solution nozzle 11 is attached to the front-end | tip part, and the 1st nozzle arm 12 which moves the 1st chemical | medical solution nozzle 11 by moving the 1st nozzle arm 12 is included.
As shown in FIG. 2, the first chemical liquid nozzle 11 that also serves as the reaction liquid nozzle is held by the first nozzle arm 12 in an inward posture. The inward posture is a posture in which the processing liquid is discharged in a discharge direction inclined with respect to the upper surface of the substrate W so that the processing liquid is deposited inward (substrate rotation axis A1 side) from the processing liquid discharge port. It is. The first chemical liquid nozzle 11 is not limited to the inward posture, and may be held by the first nozzle arm 12 in a vertical posture for discharging the processing liquid in a direction perpendicular to the upper surface of the substrate W, or from the processing liquid discharge port. The first nozzle arm 12 in an outward posture that discharges the processing liquid in a discharge direction inclined with respect to the upper surface of the substrate W so that the processing liquid is deposited on the outer side (opposite to the substrate rotation axis A1). May be held.

  As shown in FIG. 3, the first nozzle moving device 13 rotates the first nozzle arm 12 about the first nozzle rotation axis A <b> 2 extending in the vertical direction around the spin chuck 5, so that the substrate is viewed in a plan view. The 1st chemical | medical solution nozzle 11 is moved horizontally along the locus | trajectory which passes along the upper surface center part of W. The first nozzle moving device 13 includes a processing position where the chemical 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 retracted around the spin chuck 5 in plan view. The first chemical solution nozzle 11 is moved horizontally between (the position shown in FIG. 3). Further, the first nozzle moving device 13 includes a central position where the chemical liquid discharged from the first chemical liquid nozzle 11 lands on the center of the upper surface of the substrate W, and the chemical liquid discharged from the first chemical liquid nozzle 11 on the upper surface of the substrate W. The first chemical liquid nozzle 11 is moved horizontally between an intermediate position where the liquid is deposited on the intermediate part and a peripheral position where the chemical liquid discharged from the first chemical liquid nozzle 11 is deposited on the peripheral edge of the upper surface of the substrate W. The center position, the intermediate position, and the peripheral position are all processing positions.

  The central portion of the upper surface of the substrate W is a circular region including the center of the upper surface, and the peripheral portion of the upper surface of the substrate W is an annular region including the outer edge of the upper surface. The upper surface middle portion of the substrate W is an annular region between the outer edge of the upper surface center portion and the inner edge of the upper surface peripheral edge portion. An example of the width of the upper surface center portion, the upper surface intermediate portion, and the upper surface peripheral edge portion of the substrate W is as follows. The width of the central portion (the radial distance from the center of the substrate W to the outer edge of the central portion): 5/15 of the radius of the substrate W. The width of the intermediate portion (the radial distance from the inner edge of the intermediate portion to the outer edge of the intermediate portion): 9/15 of the radius of the substrate W. Perimeter width (radial distance from the inner edge of the perimeter to the outer edge of the perimeter): 1/15 of the radius of the substrate W. These ratios are examples and do not preclude the application of other ratios.

As shown in FIG. 2, the processing unit 2 includes a first chemical liquid pipe 14 that guides a chemical liquid such as SPM to the first chemical liquid nozzle 11, and an agitation pipe that agitates the sulfuric acid and the hydrogen peroxide solution in the first chemical liquid pipe 14. 15 and a mixing valve 16 that mixes sulfuric acid and hydrogen peroxide solution supplied to the first chemical liquid pipe 14 upstream of the stirring pipe 15.
As shown in FIG. 2, the processing unit 2 includes a sulfuric acid tank 17 that contains sulfuric acid (liquid), which is an example of an exothermic chemical solution, and the temperature of sulfuric acid in the sulfuric acid tank 17 is higher than room temperature by heating the sulfuric acid. (A constant temperature within a range of 60 to 90 ° C., for example, 80 ° C.), a sulfuric acid pipe 18 for guiding the sulfuric acid in the sulfuric acid tank 17 to the mixing valve 16, and the interior of the sulfuric acid pipe 18. A sulfuric acid valve 19 that opens and closes and a sulfuric acid flow rate adjustment valve 20 that increases and decreases the flow rate of sulfuric acid supplied from the sulfuric acid pipe 18 to the mixing valve 16 are included.

  As shown in FIG. 2, the treatment unit 2 includes a hydrogen peroxide solution tank 22 that stores hydrogen peroxide solution that is an example of a reactive chemical solution, and a room temperature (within a range of 20 to 30 ° C.) in the hydrogen peroxide solution tank 22. Thus, for example, a hydrogen peroxide solution pipe 23 for guiding hydrogen peroxide solution at 25 ° C. to the mixing valve 16, a hydrogen peroxide solution valve 24 for opening and closing the inside of the hydrogen peroxide solution tube 23, and a hydrogen peroxide solution tube And a hydrogen peroxide solution flow rate adjusting valve 25 for increasing and decreasing the flow rate of the hydrogen peroxide solution supplied from 23 to the mixing valve 16.

  As shown in FIG. 2, the processing unit 2 further includes a pure water pipe 26 that guides pure water from a pure water supply source into the first chemical liquid pipe 14, and a pure water valve that opens and closes the inside of the pure water pipe 26. 27 and a pure water flow rate adjusting valve 28 for increasing or decreasing the flow rate of the hydrogen peroxide solution supplied from the pure water pipe 26 to the first chemical liquid pipe 14. The downstream end of the pure water pipe 26 is connected to the first chemical liquid pipe 14 at a position upstream of the stirring pipe 15. Although not shown, the pure water flow rate adjustment valve 28 includes a valve body provided with a valve seat therein, a valve body that opens and closes the valve seat, and an actuator that moves the valve body between an open position and a closed position. including. The same applies to other flow rate adjusting valves.

  When the sulfuric acid valve 19 is opened, high-temperature sulfuric acid is supplied from the sulfuric acid pipe 18 to the mixing valve 16 at a flow rate corresponding to the opening degree of the sulfuric acid flow rate adjusting valve 20. When the hydrogen peroxide solution valve 24 is opened, the hydrogen peroxide solution at room temperature in the hydrogen peroxide solution tank 22 flows at a flow rate corresponding to the opening of the hydrogen peroxide solution flow adjustment valve 25. It is supplied from the pipe 23 to the mixing valve 16. As a result, sulfuric acid and hydrogen peroxide water are supplied to the mixing valve 16 at a predetermined ratio (for example, X1> Y1 where the ratio of sulfuric acid is “X1” and the ratio of hydrogen peroxide water is “Y1”). The

  The sulfuric acid and the hydrogen peroxide solution supplied to the mixing valve 16 are supplied from the first chemical liquid pipe 14 to the first chemical liquid nozzle 11 via the stirring pipe 15. In the process, sulfuric acid and hydrogen peroxide solution are mixed by the mixing valve 16 and stirred by the stirring pipe 15. As a result, the sulfuric acid and the hydrogen peroxide solution are mixed uniformly, and the sulfuric acid and hydrogen peroxide solution mixture (SPM) becomes lower than the temperature of the sulfuric acid and hydrogen peroxide solution before mixing. Heating to a high first temperature (100 ° C. or higher, for example, 160 ° C.). Therefore, high temperature (first temperature) SPM generated by mixing sulfuric acid and hydrogen peroxide solution is discharged from the first chemical liquid nozzle 11. SPM is a mixed chemical solution containing peroxymonosulfuric acid having strong oxidizing power.

  Also, when the sulfuric acid valve 19 and the hydrogen peroxide water valve 24 are closed and the pure water valve 27 is opened, pure water at room temperature from the pure water supply source bypasses the mixing valve 16 and passes through the pure water. It flows from the pipe 26 to the first chemical liquid pipe 14. Accordingly, pure water at room temperature is supplied from the pure water pipe 26 to the first chemical liquid pipe 14 at a flow rate corresponding to the opening of the pure water flow rate adjustment valve 28. Therefore, when the sulfuric acid valve 19, the hydrogen peroxide water valve 24, and the pure water valve 27 are opened, the three flow rate adjusting valves (the sulfuric acid flow rate adjusting valve 20, the hydrogen peroxide water flow rate adjusting valve 25, and the pure water flow rate). A mixing ratio of SPM and pure water mixed at a mixing ratio corresponding to the opening of the adjusting valve 28) is discharged from the first chemical liquid nozzle 11.

As illustrated in FIG. 2, the processing unit 2 includes a second chemical liquid nozzle 29 that discharges a chemical liquid such as SC1 (mixed liquid containing NH ₄ OH and H ₂ O ₂ ) toward the upper surface of the substrate W, and a second chemical liquid nozzle 29. A second nozzle arm 30 having a chemical nozzle 29 attached to the tip thereof, and a second nozzle moving device 31 for moving the second chemical nozzle 29 by moving the second nozzle arm 30 are included. FIG. 2 shows an example in which the second chemical nozzle 29 is held by the second nozzle arm 30 in an inward posture. The 2nd chemical | medical solution nozzle 29 may be hold | maintained at the 2nd nozzle arm 30 not only in an inward attitude | position but with a vertical attitude | position or an outward attitude | position.

  As shown in FIG. 3, the second nozzle moving device 31 rotates the second nozzle arm 30 about the second nozzle rotation axis A <b> 3 extending in the vertical direction around the spin chuck 5, so that the substrate is viewed in a plan view. The 2nd chemical | medical solution nozzle 29 is moved horizontally along the locus | trajectory which passes along the upper surface center part of W. The second nozzle moving device 31 includes a processing position where the chemical liquid discharged from the second chemical liquid nozzle 29 is deposited on the upper surface of the substrate W, and a retreat position where the second chemical liquid nozzle 29 is retracted around the spin chuck 5 in plan view. The 2nd chemical | medical solution nozzle 29 is moved horizontally between. Further, the second nozzle moving device 31 moves the second chemical liquid nozzle 29 horizontally between the center position, the intermediate position, and the peripheral position.

  As shown in FIG. 2, the processing unit 2 uses the second chemical liquid that guides the SC1 having a temperature lower than the SPM temperature (first temperature) and higher than the room temperature (for example, 30 to 50 ° C.) to the second chemical liquid nozzle 29. The piping 33 and the 2nd chemical | medical solution valve | bulb 34 which opens and closes the inside of the 2nd chemical | medical solution piping 33 are included. When the second chemical liquid valve 34 is opened, SC1 from the second chemical liquid supply source is supplied from the second chemical liquid pipe 33 to the second chemical liquid nozzle 29. Thereby, SC1 (liquid) at 40 ° C., for example, is discharged from the second chemical liquid nozzle 29.

  As shown in FIG. 2, the processing unit 2 includes a rinsing liquid nozzle 36 that discharges the rinsing liquid toward the upper surface of the substrate W, a third nozzle arm 37 with the rinsing liquid nozzle 36 attached to the tip, and a third nozzle arm 37. And a third nozzle moving device 38 that moves the rinsing liquid nozzle 36 by moving the nozzle arm 37. FIG. 2 shows an example in which the rinse liquid nozzle 36 is held by the third nozzle arm 37 in an inward posture. The rinsing liquid nozzle 36 is not limited to the inward posture, and may be held by the third nozzle arm 37 in a vertical posture or an outward posture.

  Although not shown, the third nozzle moving device 38 rotates the third nozzle arm 37 around the third nozzle rotation axis extending in the vertical direction around the spin chuck 5, so that the upper surface of the substrate W is viewed in plan view. The rinsing liquid nozzle 36 is moved horizontally along a trajectory passing through the central portion. The third nozzle moving device 38 includes a processing position where the rinsing liquid discharged from the rinsing liquid nozzle 36 is deposited on the upper surface of the substrate W, and a retreat position where the rinsing liquid nozzle 36 is retreated around the spin chuck 5 in plan view. In between, the rinse liquid nozzle 36 is moved horizontally. Further, the third nozzle moving device 38 moves the rinsing liquid nozzle 36 horizontally between the center position, the intermediate position, and the peripheral position.

As shown in FIG. 2, the processing unit 2 includes a first rinse liquid pipe 39 that guides the rinse liquid from the rinse liquid supply source to the rinse liquid nozzle 36, and a first rinse that opens and closes the inside of the first rinse liquid pipe 39. The liquid valve 40 and the 1st rinse liquid flow volume adjustment valve 41 which increases / decreases the flow volume of the rinse liquid supplied to the rinse liquid nozzle 36 from the 1st rinse liquid piping 39 are included.
When the first rinse liquid valve 40 is opened, a rinse liquid at room temperature (for example, 25 ° C.) is discharged from the rinse liquid nozzle 36 at a flow rate corresponding to the opening degree of the first rinse liquid flow rate adjustment valve 41. The rinse liquid discharged from the rinse liquid nozzle 36 is pure water (Deionzied water). The rinse liquid supplied to the rinse liquid nozzle 36 is not limited to pure water, but carbonated water, electrolytic ion water, hydrogen water, ozone water, IPA (isopropyl alcohol), or hydrochloric acid having a diluted concentration (for example, about 10 to 100 ppm). It may be water.

  As shown in FIG. 2, the processing unit 2 includes a lower surface nozzle 45 that discharges the heating liquid toward the center of the lower surface of the substrate W, a heating liquid pipe 46 that guides the heating liquid to the lower surface nozzle 45, and the heating liquid pipe 46. A heating liquid valve 47 for opening and closing the inside of the heating liquid, a heating liquid flow rate adjusting valve 48 for increasing and decreasing the flow rate of the heating liquid supplied from the heating liquid pipe 46 to the lower surface nozzle 45, and a heating liquid pipe 46 for supplying the lower surface nozzle 45. A heating liquid heater 49 that heats the heating liquid heating liquid at a temperature lower than the temperature of the SPM (first temperature) and higher than room temperature (for example, 50 to 90 ° C.).

  When the heating liquid valve 47 is opened, the heating liquid from the heating liquid supply source is supplied from the heating liquid pipe 46 to the lower surface nozzle 45 at a flow rate corresponding to the opening degree of the heating liquid flow rate adjustment valve 48. Thereby, a high-temperature (for example, 60 ° C.) heating liquid, which is an example of the heating fluid (heating liquid), is discharged from the lower surface nozzle 45. As shown in FIG. 2, the heating liquid supplied to the lower surface nozzle 45 is heated pure water. The kind of heating liquid supplied to the lower surface nozzle 45 is not limited to pure water, but carbonated water, electrolytic ion water, hydrogen water, ozone water, IPA (isopropyl alcohol), or diluted concentration (for example, about 10 to 100 ppm). It may be hydrochloric acid water or the like.

  As shown in FIGS. 2 and 3, the lower surface nozzle 45 includes a circular plate portion 50 arranged in a horizontal posture at a height between the upper surface central portion of the spin base 7 and the lower surface central portion of the substrate W, and And a cylindrical portion 51 extending downward from the plate portion 50. The heating liquid from the heating liquid pipe 46 is supplied to the inside of the cylindrical portion 51 and is discharged upward from a discharge port 45 a that opens at the upper surface of the disc portion 50. The disc part 50 and the cylindrical part 51 are not in contact with a rotating part such as the spin shaft 9, and the lower surface nozzle 45 is fixed at a fixed position. The cylindrical portion 51 is disposed in the cylindrical spin shaft 9. The inner peripheral surface of the spin shaft 9 surrounds the outer peripheral surface of the cylindrical portion 51 over the entire circumference with a gap in the radial direction. As shown in FIG. 2, the inner peripheral surface of the spin shaft 9 and the outer peripheral surface of the cylindrical part 51 form a cylindrical gas flow path 52 extending along the substrate rotation axis A1. The upper end of the gas flow path 52 as the gas discharge port 53 opens at the center of the upper surface of the spin base 7.

  As shown in FIG. 2, the processing unit 2 includes a gas pipe 54 that guides gas from a gas supply source to the gas flow path 52, a gas valve 55 that opens and closes the inside of the gas pipe 54, and a gas flow from the gas pipe 54. A gas flow rate adjusting valve 56 for increasing or decreasing the flow rate of the gas supplied to the passage 52, and a gas supplied from the gas pipe 54 to the gas flow channel 52 at a temperature lower than the SPM temperature (first temperature) and higher than the room temperature (first temperature). For example, the gas heater 57 heated at 50-90 degreeC) is included.

  When the gas valve 55 is opened, the gas from the gas supply source is supplied from the gas pipe 54 to the gas flow path 52 at a flow rate corresponding to the opening of the gas flow rate adjustment valve 56. The gas supplied to the gas flow path 52 flows upward in the gas flow path 52 and is discharged upward from the gas discharge port 53. The gas discharged from the gas discharge port 53 spreads radially between the lower surface of the substrate W and the upper surface of the spin base 7. Thereby, the space between the lower surface of the substrate W and the upper surface of the spin base 7 is filled with a high-temperature (for example, 80 ° C.) gas that is an example of the heating fluid (heating gas). The gas discharged from the gas discharge port 53 is nitrogen gas which is an example of an inert gas. The gas is not limited to nitrogen gas, and may be an inert gas other than nitrogen gas, or other gas such as water vapor.

  As shown in FIG. 2, the cup 6 is disposed outside the substrate W held by the spin chuck 5. The cup 6 surrounds the spin base 7. When the processing liquid is supplied to the substrate W while the spin chuck 5 is rotating the substrate W, the processing liquid is scattered from the substrate W to the periphery of the substrate W. When the processing liquid is supplied to the substrate W, the upper end portion of the cup 6 opened upward is disposed above the spin base 7. Therefore, the treatment liquid such as the chemical liquid and the rinse liquid discharged around the substrate W is received by the cup 6. Then, the processing liquid received by the cup 6 is sent to a collecting device or a draining device (not shown).

As shown in FIG. 2, the heating apparatus includes an infrared heater 58 disposed above the substrate W held by the spin chuck 5, a heater arm 59 having the infrared heater 58 attached to the tip, and a heater arm 59. And a heater moving device 60 that moves the infrared heater 58 by moving the heater.
As shown in FIG. 2, the infrared heater 58 includes an infrared lamp 61 that emits light including infrared rays, and a lamp housing 62 that houses the infrared lamp 61. The infrared lamp 61 is disposed in the lamp housing 62. As shown in FIG. 3, the lamp housing 62 is smaller than the substrate W in plan view. Therefore, the infrared heater 58 is smaller than the substrate W in plan view. The infrared lamp 61 and the lamp housing 62 are attached to the heater arm 59. Therefore, the infrared lamp 61 and the lamp housing 62 move together with the heater arm 59.

  As shown in FIG. 4, the infrared lamp 61 is connected to the control device 3. The power supplied to the infrared lamp 61 is adjusted by the control device 3. Infrared lamp 61 is, for example, a halogen lamp. The infrared lamp 61 may be another heating element such as a carbon heater instead of the halogen lamp. The infrared lamp 61 includes a filament and a quartz tube that accommodates the filament. At least a part of the lamp housing 62 is formed of a material having light transmissivity and heat resistance such as quartz. Therefore, when the infrared lamp 61 emits light, the light from the infrared lamp 61 passes through the lamp housing 62 and is emitted outward from the outer surface of the lamp housing 62.

  As shown in FIG. 4, the lamp housing 62 has a bottom wall parallel to the upper surface of the substrate W. The infrared lamp 61 is disposed above the bottom wall. The bottom surface of the bottom wall includes a substrate facing surface 58a that is parallel to and flat with the top surface of the substrate W. In a state where the infrared heater 58 is disposed above the substrate W, the substrate facing surface 58a of the infrared heater 58 faces the upper surface of the substrate W in the vertical direction with a space therebetween. When the infrared lamp 61 emits light in this state, light including infrared light is directed from the substrate facing surface 58a toward the upper surface of the substrate W and is irradiated onto the upper surface of the substrate W. The substrate facing surface 58a is, for example, a circle having a diameter smaller than the radius of the substrate W. The substrate facing surface 58a is not limited to a circle, and may have a rectangular shape whose length in the longitudinal direction is not less than the radius of the substrate W and less than the diameter of the substrate W, or may be a shape other than a circle and a rectangle. .

  As shown in FIG. 4, the infrared lamp 61 includes a ring-shaped end portion 63 arranged along a horizontal plane, and a pair of vertical portions 64 extending upward from one end and the other end of the ring-shaped portion 63. Including. The lamp housing 62 includes a transmission member that transmits infrared rays. The transmission member includes a cylindrical storage portion 65 extending in the vertical direction and a disk-shaped bottom plate portion 66 that closes the lower end of the storage portion 65. The lamp housing 62 further includes a lid member 67 that closes the upper end of the accommodating portion 65 and a support member 68 that supports the pair of vertical portions 64 of the infrared lamp 61. The infrared lamp 61 is supported by the lid member 67 via the support member 68. The annular portion 63 of the infrared lamp 61 is disposed in a space defined by the accommodating portion 65, the bottom plate portion 66, and the lid member 67. The bottom plate portion 66 is disposed below the infrared lamp 61 and faces the infrared lamp 61 in the vertical direction with a space therebetween.

  As shown in FIG. 2, the heater moving device 60 holds the infrared heater 58 at a predetermined height. As shown in FIG. 3, the heater moving device 60 moves the infrared heater 58 horizontally by rotating the heater arm 59 around the heater rotation axis A <b> 4 extending in the vertical direction around the spin chuck 5. Thereby, the irradiation position (a part of the region within the upper surface of the substrate W) irradiated with infrared rays moves within the upper surface of the substrate W. The heater moving device 60 moves the infrared heater 58 horizontally along a locus passing through the center of the substrate W in plan view. Therefore, the infrared heater 58 moves in a horizontal plane including the upper side of the spin chuck 5. The heater moving device 60 changes the distance between the substrate facing surface 58a and the substrate W by moving the infrared heater 58 in the vertical direction.

  As shown in FIG. 4, the light from the infrared heater 58 is irradiated to the irradiation position in the upper surface of the substrate W. The control device 3 rotates the infrared heater 58 around the heater rotation axis A4 by the heater moving device 60 while rotating the substrate W by the spin chuck 5 in a state where the infrared heater 58 emits infrared rays. Thereby, the upper surface of the substrate W is scanned by the irradiation position as the heating position. Therefore, when the infrared lamp 61 emits infrared light while a liquid such as a processing liquid is held on the substrate W, the temperature of the substrate W and the processing liquid rises.

FIG. 5 is a time chart showing an outline of the first processing example performed by the processing unit 2. FIG. 6 is a specific time chart of a part of the first processing example. Hereinafter, with reference to FIGS. 2 and 5, a resist removal process for removing the resist pattern that is no longer needed from the substrate W will be described. Reference is made appropriately to FIG.
When the substrate W is processed by the processing unit 2, a loading process (step S <b> 1 in FIG. 5) for loading the substrate W into the chamber 4 is performed. Specifically, the control device 3 causes the hand of the substrate transport robot CR holding the substrate W to enter the chamber 4 in a state where all the nozzles and the like are retracted from above the spin chuck 5. Then, the control device 3 causes the substrate transport robot CR to place the substrate W on the plurality of chuck pins 8. Thereafter, the control device 3 retracts the hand of the substrate transport robot CR from the chamber 4. Further, after the substrate W is placed on the plurality of chuck pins 8, the control device 3 moves each chuck pin 8 from the open position to the closed position. Thereafter, the control device 3 starts the rotation of the substrate W by the spin motor 10.

  Next, a first chemical solution supply step (step S2 in FIG. 5) for supplying high temperature (first temperature) SPM, which is an example of the first chemical solution, to the substrate W is performed. Specifically, the control device 3 controls the spin motor 10 to accelerate the substrate W to the first chemical liquid rotation speed V1 (see FIG. 6), and rotates the substrate W at the first chemical liquid rotation speed V1. That is, the control device 3 maintains the rotation speed of the substrate W at the first chemical liquid rotation speed V1. Further, the control device 3 controls the first nozzle moving device 13 to move the first chemical liquid nozzle 11 from the retracted position to the processing position. Accordingly, the first chemical liquid nozzle 11 is disposed above the substrate W. Thereafter, the control device 3 opens the sulfuric acid valve 19 and the hydrogen peroxide solution valve 24 to direct the SPM of the first temperature (for example, 160 ° C.) toward the upper surface of the substrate W rotating at the first chemical solution rotation speed V1. Then, the first chemical solution nozzle 11 is discharged. The control device 3 controls the first nozzle moving device 13 to move the SPM liquid deposition position with respect to the upper surface of the substrate W between the central portion and the peripheral portion in this state.

  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 by centrifugal force. Therefore, SPM is supplied to the entire upper surface of the substrate W, and a liquid film of SPM that covers the entire upper surface of the substrate W is formed on the substrate W. As a result, the resist film and SPM chemically react, and the resist film on the substrate W is removed from the substrate W by SPM. Further, since the controller 3 moves the SPM landing position with respect to the upper surface of the substrate W between the central portion and the peripheral portion while the substrate W is rotating, the SPM landing position is determined by the substrate W The entire upper surface of the substrate W is scanned. Therefore, the SPM discharged from the first chemical solution nozzle 11 is supplied to the entire upper surface of the substrate W, and the entire upper surface of the substrate W is processed uniformly.

  Next, a paddle process (step S3 in FIG. 5) for holding the liquid film of SPM on the substrate W in a state where the discharge of SPM is stopped is performed. Specifically, the control device 3 controls the spin motor 10 so that the rotation speed of the substrate W in the first chemical solution supply step (in the state where the entire upper surface of the substrate W is covered with the SPM liquid film ( The substrate W is decelerated to a second chemical liquid rotation speed V2 (see FIG. 6) smaller than the first chemical liquid rotation speed V1), and the substrate W is rotated at the second chemical liquid rotation speed V2. Therefore, the centrifugal force applied to the SPM on the substrate W is weakened, and the amount of SPM discharged from the substrate W is reduced. The control device 3 closes the sulfuric acid valve 19 and the hydrogen peroxide solution valve 24 in a state where the substrate W is rotating at the second chemical solution rotation speed V <b> 2 and stops the SPM discharge from the first chemical solution nozzle 11. As a result, the SPM liquid film covering the entire upper surface of the substrate W is held on the substrate W in a state where the SPM discharge is stopped. After stopping the discharge of SPM, the control device 3 controls the first nozzle moving device 13 to place the first chemical liquid nozzle 11 on the upper side of the substrate W.

  Further, there is a heating process (step S4 in FIG. 5) in which the substrate W and the SPM on the substrate W are heated by the infrared heater 58 at a heating temperature higher than the SPM temperature (first temperature) before being supplied to the substrate W. The first chemical solution supply process (step S2 in FIG. 5) and the paddle process (step S3 in FIG. 5) are performed in parallel. Specifically, the control device 3 moves the infrared heater 58 from the retracted position to the processing position by controlling the heater moving device 60. Thereby, the infrared heater 58 is disposed above the substrate W. Thereafter, the control device 3 causes the infrared heater 58 to start light emission. Thereby, the temperature of the infrared heater 58 rises to a heating temperature (for example, 200 ° C. or higher) equal to or higher than the boiling point at the concentration of SPM, and is maintained at the heating temperature.

  After the infrared heater 58 starts to emit light above the substrate W, the control device 3 moves the infrared heater 58 by the heater moving device 60, thereby setting the infrared irradiation position on the upper surface of the substrate W within the upper surface of the substrate W. Move. Then, after the substrate W is heated by the infrared heater 58 for a predetermined time, the control device 3 rotates the substrate W at the second chemical liquid rotation speed V2 and covers the entire upper surface of the substrate W. Is stopped on the substrate W, the light emission of the infrared heater 58 is stopped. Thereafter, the control device 3 retracts the infrared heater 58 from above the substrate W by controlling the heater moving device 60. Note that the light emission and movement of the infrared heater 58 may be performed simultaneously, or the movement may be started after light emission.

  Thus, since the control apparatus 3 moves the infrared irradiation position with respect to the upper surface of the substrate W within the upper surface of the substrate W while rotating the substrate W, the substrate W is heated uniformly. Therefore, the SPM liquid film covering the entire upper surface of the substrate W is also heated uniformly. The heating temperature of the substrate W by the infrared heater 58 is set to a temperature equal to or higher than the boiling point at the concentration of SPM. Therefore, the SPM on the substrate W is heated to the boiling point at that concentration. In particular, when the heating temperature of the substrate W by the infrared heater 58 is set higher than the boiling point at the concentration of SPM, the temperature of the interface between the substrate W and SPM is maintained higher than the boiling point, Removal of foreign matter (resist film) from the substrate W is promoted.

  Next, a reaction liquid supply step (step S5 in FIG. 5) for supplying SPM, which is an example of a reaction liquid-containing liquid, to the substrate W and a ratio of sulfuric acid mixed with the hydrogen peroxide solution are reduced, thereby reducing the substrate W. The reaction liquid concentration changing step (step S6 in FIG. 5) for increasing the proportion of the hydrogen peroxide solution in the SPM discharged toward is performed in parallel. Further, in parallel with the reaction liquid supply process and the reaction liquid concentration changing process, the temperature is lower than the temperature of the SPM (first temperature) and supplied to the substrate W in the first rinse liquid supply process (step S8 in FIG. 5) described later. A first temperature drop suppressing step (step S7 in FIG. 5) for supplying pure water, which is an example of a heating fluid having a first intermediate temperature higher than the temperature of the rinse liquid (second temperature), to the lower surface of the substrate W. Done in parallel.

  With respect to the reaction liquid supply process, the control device 3 controls the first nozzle moving device 13 so that the processing liquid discharged from the first chemical liquid nozzle 11 reaches the intermediate position where it reaches the upper surface intermediate portion of the substrate W. One chemical nozzle 11 is positioned. Thereafter, the control device 3 opens the sulfuric acid valve 19 and the hydrogen peroxide water valve 24 to cause the first temperature SPM (reaction liquid-containing liquid) to be placed on the upper surface of the substrate W rotating at the second chemical liquid rotation speed V2. Then, the first chemical solution nozzle 11 is discharged. Thereby, the supply of new SPM (reaction liquid-containing liquid) unreacted with the substrate W is started at the upper surface intermediate portion of the substrate W.

  After the supply of the SPM (reaction liquid-containing liquid) is started, the control device 3 controls the first nozzle moving device 13 so that the substrate W is rotated at the second chemical liquid rotation speed V2 in the second state. One chemical solution nozzle 11 is moved from the upper surface intermediate portion to the center position. As a result, the SPM liquid deposition position with respect to the upper surface of the substrate W moves to the center. Thereafter, the control device 3 closes the sulfuric acid valve 19 and the hydrogen peroxide water valve 24 to stop the discharge of SPM from the first chemical liquid nozzle 11. Subsequently, the control device 3 controls the first nozzle moving device 13 to retract the first chemical solution nozzle 11 from above the substrate W. Thereby, a reaction liquid supply process is complete | finished.

  Regarding the reaction liquid concentration changing step, the control device 3 adjusts the opening degree of the sulfuric acid flow rate adjusting valve 20 and the hydrogen peroxide flow rate adjusting valve 25 while the reaction solution supplying step is being performed, so that the first chemical solution is adjusted. The mixing ratio of sulfuric acid and hydrogen peroxide solution is changed while maintaining the discharge flow rate of the reaction liquid-containing liquid discharged from the nozzle 11 constant. As shown in the upper part of FIG. 6, for example, the control device 3 gradually decreases the flow rate of sulfuric acid supplied to the first chemical solution nozzle 11 and at the same time the flow rate of hydrogen peroxide water supplied to the first chemical solution nozzle 11. Increase gradually. Finally, the control device 3 continuously changes the mixing ratio of sulfuric acid and hydrogen peroxide solution from 2 (sulfuric acid) to 1 (hydrogen peroxide solution) to 1 (sulfuric acid) to 1 (hydrogen peroxide solution), for example. Change in stages. Therefore, the mixing ratio immediately before the SPM discharge is stopped is set to 1 (sulfuric acid) to 1 (hydrogen peroxide solution).

In the reaction liquid concentration changing step, the treatment is started gradually after starting the treatment at the mixing ratio (for example, 10 (sulfuric acid) to 1 (hydrogen peroxide solution)) in the first chemical liquid supply step (step S2 in FIG. 5). The mixing ratio may vary. Furthermore, in the final stage of the reaction solution concentration changing step, the ratio of sulfuric acid may be reduced to zero.
Regarding the first temperature decrease suppressing step, the control device 3 directs pure water having a first intermediate temperature (for example, a temperature higher than room temperature) toward the lower surface of the substrate W rotating at the second chemical liquid rotation speed V2. The lower nozzle 45 is discharged. The pure water discharged from the lower surface nozzle 45 lands on the center of the lower surface of the substrate W, and then flows outward along the lower surface of the substrate W to the periphery of the substrate W by centrifugal force. Thereby, pure water is supplied to the entire lower surface of the substrate W. Therefore, the temperature drop of the substrate W and SPM is suppressed. When a predetermined time elapses after the heating liquid valve 47 is opened, the control device 3 closes the heating liquid valve 47 and stops the discharge of pure water from the lower surface nozzle 45. Thereafter, the control device 3 temporarily discharges the nitrogen gas from the gas discharge port 53 by opening and closing the gas valve 55. Thereby, pure water is discharged from between the substrate W and the spin base 7.

  In the reaction liquid supply step, the ratio of the hydrogen peroxide solution contained in the reaction liquid-containing liquid (SPM) is gradually increased. When the ratio of the hydrogen peroxide solution at room temperature is increased, the temperature of the reaction solution-containing liquid is lower than the first temperature and is lowered to a temperature equal to or higher than room temperature. The reaction liquid-containing liquid that has reached the center of the upper surface of the substrate W spreads on the substrate W from the landing position to the periphery of the landing position. Furthermore, the reaction liquid-containing liquid on the substrate W flows outwardly on the substrate W toward the peripheral edge of the substrate W while flowing in the circumferential direction on the downstream side of the rotation direction on the substrate W. Thereby, the reaction liquid-containing liquid having a temperature lower than that of the substrates W and SPM is supplied to the entire upper surface of the substrate W covered with the SPM liquid film. Therefore, the reaction liquid-containing liquid flows on the substrate W while taking heat of the substrate W and the SPM that are higher in temperature than the reaction liquid-containing liquid.

  In the reaction liquid supply step, the reaction liquid-containing liquid having a temperature lower than the heating temperature by the infrared heater 58 is supplied to the substrate W, so that the temperatures of the substrate W and SPM (particularly, the temperature at the liquid landing position and the vicinity thereof) are lowered. . However, since the sulfuric acid contained in the SPM on the substrate W and the sulfuric acid contained in the reaction liquid-containing liquid generate heat due to the reaction with the hydrogen peroxide solution contained in the reaction liquid-containing liquid, the substrate W at the landing position is obtained. And a significant temperature drop of SPM is suppressed or prevented. Furthermore, since the first temperature decrease suppressing step is performed in parallel with the reaction solution supplying step, the amount of temperature decrease of the substrate W and the SPM at the landing position is reduced. Therefore, an increase in the temperature difference of the substrate W between the landing position and other positions can be suppressed. Thereby, the deformation | transformation of the board | substrate W resulting from a temperature difference can be suppressed, and the distortion amount of the board | substrate W can be reduced.

  Furthermore, since the reaction solution concentration changing step is performed in parallel with the reaction solution supply step, the amount of reaction heat generated is gradually reduced by gradually decreasing the sulfuric acid concentration in the reaction solution-containing solution. Therefore, the temperature of the reaction liquid-containing liquid itself supplied to the substrate W gradually decreases. For this reason, in the reaction liquid supply step, the temperatures of the substrate W and the SPM gradually decrease with the supply of the reaction liquid-containing liquid. Therefore, the temperature difference between the substrate W and SPM and the reaction liquid-containing liquid is greatest at the start of supply of the reaction liquid-containing liquid. The supply of the reaction liquid-containing liquid is started at the upper surface intermediate portion of the substrate W whose peripheral speed is higher than that of the upper surface center portion of the substrate W. Therefore, the supply flow rate of the reaction liquid-containing liquid per unit area is smaller than when the supply of the reaction liquid-containing liquid is started at the center of the upper surface of the substrate W. Therefore, it is possible to suppress or prevent the temperature of the substrate W and the SPM at the liquid landing position from rapidly and greatly decreasing due to the supply of a large amount of the reaction liquid-containing liquid. Furthermore, since the reaction liquid-containing liquid that has landed on the center of the upper surface of the substrate W is discharged to the periphery of the substrate W via the peripheral edge of the substrate W, the supply of the reaction liquid-containing liquid is performed at the peripheral edge of the upper surface of the substrate W. The residence time of the reaction liquid-containing liquid on the substrate W is longer than when it is started. Therefore, the reaction liquid-containing liquid can be used efficiently.

  Moreover, the 1st chemical | medical solution nozzle 11 discharges a reaction liquid containing liquid inward. Therefore, the reaction liquid-containing liquid discharged from the first chemical liquid nozzle 11 mainly flows inward from the liquid landing position on the substrate W. For this reason, the first chemical liquid nozzle 11 is discharged in a shorter time than when the reaction liquid-containing liquid is discharged in a direction perpendicular to the upper surface of the substrate W or when the first chemical liquid nozzle 11 discharges the reaction liquid-containing liquid outward. The reaction liquid-containing liquid can be spread to an area inside the liquid position. Furthermore, since the flow rate of the reaction liquid-containing liquid flowing inward from the landing position increases, the residence time of the reaction liquid-containing liquid on the substrate W increases. Therefore, the reaction liquid-containing liquid can be used efficiently.

  Next, the 1st rinse liquid supply process (step S8 of FIG. 5) which supplies the pure water of the room temperature which is an example of the rinse liquid of 2nd temperature to the board | substrate W is performed. Specifically, the control device 3 controls the third nozzle moving device 38 to move the rinse liquid nozzle 36 from the retracted position to the processing position. Thereafter, the control device 3 opens the first rinsing liquid valve 40 and discharges pure water at room temperature to the rinsing liquid nozzle 36 toward the center of the upper surface of the substrate W. Further, the control device 3 controls the spin motor 10 to accelerate the substrate W to a rinse rotational speed V3 (see FIG. 6) larger than the first chemical liquid rotational speed V1 and the second chemical liquid rotational speed V2, thereby performing the rinse rotation. The substrate W is rotated at the speed V3. When a predetermined time elapses after the first rinsing liquid valve 40 is opened, the control device 3 closes the first rinsing liquid valve 40 and stops the discharge of pure water from the rinsing liquid nozzle 36. Thereafter, the control device 3 controls the third nozzle moving device 38 to retract the rinse liquid nozzle 36 from above the substrate W.

  The pure water discharged from the rinsing liquid nozzle 36 is deposited on the center of the upper surface of the substrate W covered with the chemical liquid or the reaction liquid-containing liquid. Therefore, the chemical solution on the substrate W is pushed away from the central portion to the periphery thereof. The pure water that has landed on the center of the upper surface of the substrate W flows outward along the upper surface of the substrate W by centrifugal force. Similarly, the chemical solution on the substrate W flows outward along the upper surface of the substrate W by centrifugal force. Further, since the substrate W is rotating at the rinse rotational speed V3 that is larger than the first chemical liquid rotational speed V1 and the second chemical liquid rotational speed V2, a larger centrifugal force is generated than in the first chemical liquid supplying process and the reaction liquid supplying process. The liquid on the substrate W is added. Therefore, a liquid film of pure water spreads instantaneously from the center of the substrate W to the periphery of the substrate W, and the chemical solution on the substrate W is replaced with pure water in a short time. Thereby, the chemical solution on the substrate W is washed away with pure water.

  Next, SC1 which is an example of the second chemical liquid, which is lower than the temperature of the SPM (first temperature) and higher than the temperature of the rinse liquid (second temperature) before being supplied to the substrate W, is supplied to the substrate W. The second chemical liquid supply step (step S9 in FIG. 5) and the second intermediate in which the temperature before being supplied to the substrate W is lower than the temperature of the SPM (first temperature) and higher than the temperature of the rinse liquid (second temperature). A second temperature decrease suppressing step (step S10 in FIG. 5) for supplying pure water, which is an example of a heating fluid having a temperature, to the lower surface of the substrate W is performed in parallel.

  Regarding the second chemical solution supply step, the control device 3 controls the second nozzle moving device 31 to move the second chemical solution nozzle 29 from the retracted position to the processing position. After the second chemical liquid nozzle 29 is disposed above the substrate W, the control device 3 opens the second chemical liquid valve 34 and discharges the SC1 to the second chemical liquid nozzle 29 toward the upper surface of the rotating substrate W. . In this state, the control device 3 controls the second nozzle moving device 31 to move the SC1 liquid landing position relative to the upper surface of the substrate W between the central portion and the peripheral portion. And when predetermined time passes after the 2nd chemical | medical solution valve 34 opens, the control apparatus 3 will close the 2nd chemical | medical solution valve 34, and will stop discharge of SC1. Thereafter, the control device 3 retracts the second chemical liquid nozzle 29 from above the substrate W by controlling the second nozzle moving device 31.

  SC1 discharged from the second chemical liquid nozzle 29 lands on the upper surface of the substrate W and then flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the pure water on the substrate W is swept 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. Further, since the controller 3 moves the SC1 liquid landing position with respect to the upper surface of the substrate W between the central portion and the peripheral portion while the substrate W is rotating, the SC1 liquid landing position is the substrate W The entire upper surface of the substrate W is scanned. Therefore, SC1 discharged from the second chemical liquid nozzle 29 is supplied to the entire upper surface of the substrate W, and the entire upper surface of the substrate W is processed uniformly.

  Regarding the second temperature decrease suppression step, the control device 3 causes the lower surface nozzle 45 to discharge pure water having the second intermediate temperature toward the lower surface of the rotating substrate W. Thereby, pure water is supplied to the entire lower surface of the substrate W. Therefore, it is possible to prevent the temperature of the substrate W, whose temperature has been lowered to the second temperature by supplying the rinse liquid at the second temperature, from being locally changed by supplying SC1 having a temperature higher than the second temperature. When a predetermined time elapses after the heating liquid valve 47 is opened, the control device 3 closes the heating liquid valve 47 and stops the discharge of pure water from the lower surface nozzle 45. Thereafter, the control device 3 temporarily discharges the nitrogen gas from the gas discharge port 53 by opening and closing the gas valve 55. Thereby, pure water is discharged from between the substrate W and the spin base 7.

  Next, the 2nd rinse liquid supply process (step S11 of FIG. 5) 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 controls the third nozzle moving device 38 to move the rinse liquid nozzle 36 from the retracted position to the processing position. After the rinse liquid nozzle 36 is disposed above the substrate W, the control device 3 opens the first rinse liquid valve 40 and causes the rinse liquid nozzle 36 to discharge pure water toward the upper surface of the rotating substrate W. . As a result, the SC1 on the substrate W is washed away by the pure water and discharged around the substrate W. Therefore, the liquid film of SC1 on the substrate W is replaced with a liquid film of pure water that covers the entire upper surface of the substrate W. And if predetermined time passes after the 1st rinse liquid valve 40 opens, the control apparatus 3 will close the 1st rinse liquid valve 40, and will stop discharge of pure water. Thereafter, the control device 3 controls the first nozzle moving device 13 to retract the rinse liquid nozzle 36 from above the substrate W.

  Next, a drying process (step S12 in FIG. 5) for drying the substrate W is performed. Specifically, the control device 3 controls the spin motor 10 so that the rotational speed from the first chemical liquid supply process (step S2 in FIG. 5) to the second rinse liquid supply process (step S11 in FIG. 5) is controlled. The substrate W is accelerated to a higher 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 10 to stop the rotation of the substrate W by the spin chuck 5.

  Next, an unloading step (Step S13 in FIG. 5) for unloading the substrate W from the chamber 4 is performed. Specifically, the control device 3 moves each chuck pin 8 from the closed position to the open position, and releases the grip of the substrate W by the spin chuck 5. Thereafter, the control device 3 causes the hand of the substrate transfer robot CR to enter the chamber 4 in a state where all the nozzles and the like are retracted from above the spin chuck 5. Then, the control device 3 holds the substrate W on the spin chuck 5 by the hand of the substrate transport robot CR. Thereafter, the control device 3 retracts the hand of the substrate transport robot CR from the chamber 4. Thereby, the processed substrate W is unloaded from the chamber 4.

  In the description of the first processing example described above, a hydrogen peroxide solution-containing solution (a mixed solution of sulfuric acid and hydrogen peroxide solution or a hydrogen peroxide solution) as a reaction solution-containing solution is applied to the substrate W in the reaction solution supply step. Although the case where it is supplied has been described, pure water containing pure water that generates an exothermic reaction by mixing with sulfuric acid, and having a liquid temperature not higher than the first temperature and not lower than the second temperature (mixed liquid of sulfuric acid and pure water) , A mixed solution of SPM and pure water, or pure water) may be supplied to the substrate W in the reaction liquid supply step. Specifically, a reaction liquid supply step (step S5a in FIG. 6) for supplying a pure water-containing liquid, which is an example of a reaction liquid-containing liquid, to the substrate W is a reaction liquid for supplying a hydrogen peroxide solution-containing liquid to the substrate W. Instead of the supply process (step S5 in FIG. 6), the reaction liquid concentration changing process and the first temperature decrease suppressing process may be performed in parallel.

  In this case, the control device 3 controls the first nozzle moving device 13 so that the first chemical solution nozzle 11 is positioned at an intermediate position where the processing liquid discharged from the first chemical solution nozzle 11 is deposited on the upper surface intermediate portion of the substrate W. Position. Thereafter, the control device 3 opens the sulfuric acid valve 19 and the pure water valve 27, and a mixed liquid (pure water-containing liquid) of sulfuric acid and pure water, which is lower than the first temperature and higher than the second temperature, The first chemical liquid nozzle 11 is discharged toward the upper surface of the substrate W rotating at the second chemical liquid rotation speed V2. Thereby, the supply of the mixed liquid of sulfuric acid and pure water (pure water-containing liquid) is started at the upper surface intermediate portion of the substrate W.

  After the supply of the mixed liquid of sulfuric acid and pure water (pure water-containing liquid) is started at the upper surface intermediate portion of the substrate W, the control device 3 opens the openings of the sulfuric acid flow rate adjustment valve 20 and the pure water flow rate adjustment valve 28. By adjusting, the mixing ratio of sulfuric acid and pure water is changed while the discharge flow rate of the pure water-containing liquid discharged from the first chemical liquid nozzle 11 is kept constant. As shown in the lower part of FIG. 6, the control device 3 gradually decreases the discharge flow rate of sulfuric acid discharged from the first chemical liquid nozzle 11, for example, by gradually decreasing the supply flow rate of sulfuric acid. In parallel with this, the control device 3 increases the flow rate of pure water supplied to the first chemical liquid nozzle 11. Finally, the control device 3 reduces the opening degree of the sulfuric acid flow rate adjustment valve 20 to zero. Therefore, the mixing ratio of sulfuric acid and pure water is finally changed to 0 (sulfuric acid) to 1 (pure water), and only room temperature pure water (pure water-containing liquid) is discharged from the first chemical liquid nozzle 11.

  Further, the control device 3 controls the first nozzle moving device 13 to change the mixing ratio of sulfuric acid and pure water, and the substrate W is rotating at the second chemical solution rotation speed V2. Thus, the first chemical liquid nozzle 11 is moved from the intermediate position to the center position. Thereby, the landing position of the pure water-containing liquid moves from the upper surface middle portion of the substrate W to the upper surface center portion. Thereafter, the control device 3 starts a first rinsing liquid supply step (step S8 in FIG. 5) for supplying pure water at room temperature, which is an example of a rinsing liquid at the second temperature, to the substrate W. Specifically, the control device 3 controls the spin motor 10 to rinse the substrate W while the first chemical solution nozzle 11 is discharging pure water at room temperature toward the center of the upper surface of the substrate W. Rotate at rotation speed V3. Thereafter, the control device 3 closes the pure water valve 27 and stops the discharge of pure water from the first chemical liquid nozzle 11. Subsequently, the control device 3 controls the first nozzle moving device 13 to retract the first chemical solution nozzle 11 from above the substrate W.

  As described above, in this embodiment, the chemical solution at the first temperature (the temperature of the chemical solution before being supplied to the substrate W) is supplied to the upper surface of the substrate W. Then, a reaction liquid-containing liquid (a liquid containing hydrogen peroxide or pure water as a reaction liquid) is supplied to the upper surface of the substrate W while the chemical liquid remains on the substrate W. The reaction liquid-containing liquid supplied to the substrate W is mixed with the chemical liquid remaining on the substrate W. Therefore, the ratio of the reaction liquid-containing liquid in the liquid remaining on the substrate W increases, and the concentration of the chemical liquid decreases. The rinse liquid at the second temperature (the temperature of the rinse liquid before being supplied to the substrate W) lower than the first temperature is supplied to the upper surface of the substrate W after the reaction liquid-containing liquid is supplied to the substrate W. Thereby, the liquid (liquid containing the chemical liquid and the reaction liquid-containing liquid) remaining on the substrate W is washed away.

  When the supply of the reaction liquid-containing liquid is started, the temperature of the substrate W approaches the temperature of the reaction liquid-containing liquid. The temperature of the reaction liquid-containing liquid before being supplied to the substrate W is equal to or lower than the temperature of the chemical liquid (first temperature) and equal to or higher than the temperature of the rinse liquid (second temperature). The reaction solution (hydrogen peroxide solution or pure water) contained in the reaction solution-containing solution generates an exothermic reaction when mixed with the chemical solution (SPM). Therefore, when the reaction liquid-containing liquid is supplied to the upper surface of the substrate W while the chemical liquid remains on the substrate W, an exothermic reaction occurs at the position where the reaction liquid-containing liquid is deposited and in the vicinity thereof. The amount of temperature drop of the substrate W in the region near the position is reduced. Therefore, the temperature of the substrate W gradually approaches the temperature of the reaction liquid-containing liquid. That is, a rapid temperature change of the substrate W is suppressed.

  Furthermore, since the ratio of the exothermic liquid (sulfuric acid or SPM) contained in the reaction liquid-containing liquid is smaller than that at the start of the discharge of the reaction liquid-containing liquid, the reaction liquid (hydrogen peroxide water or pure water) at a lower temperature than the exothermic liquid. As a result, the temperature of the reaction liquid-containing liquid decreases. Therefore, a reaction liquid-containing liquid having a temperature lower than that at the start of discharge is supplied to the upper surface of the substrate W, and the temperature of the reaction liquid-containing liquid approaches the temperature of the rinse liquid (second temperature). Therefore, the temperature drop of the substrate W in the region near the liquid landing position is further moderated. Therefore, the rapid and rapid temperature drop of the substrate W can be suppressed and the deformation amount of the substrate W can be reduced as compared with the case where pure water at room temperature is supplied following the supply of the high temperature SPM.

  In the present embodiment, the reaction liquid-containing liquid having a large proportion of the high-temperature exothermic liquid (SPM) is discharged toward the upper surface of the substrate W. Thereafter, the reaction liquid discharged toward the substrate W from the mixing ratio in which the ratio of the exothermic liquid (SPM) is larger than the ratio of the reaction liquid (pure water) to the mixing ratio in which the ratio of the exothermic liquid is smaller than the ratio of the reaction liquid. The ratio of the exothermic liquid contained in the containing liquid is reduced. Accordingly, the temperature of the reaction liquid-containing liquid discharged toward the substrate W is gradually lowered greatly. Therefore, even when the temperature difference between the chemical liquid and the rinsing liquid is large, that is, when the difference between the first temperature and the second temperature is large, the temperature of the substrate W is gradually and uniformly brought close to the temperature of the rinsing liquid. Can do. Thereby, the deformation | transformation of the board | substrate W resulting from a temperature difference can be suppressed or prevented.

  In this embodiment, the ratio of the exothermic liquid (sulfuric acid) contained in the reaction liquid-containing liquid is reduced to zero. Accordingly, the exothermic liquid contained in the reaction liquid-containing liquid disappears, and only the reaction liquid (pure water) is discharged toward the substrate W. For this reason, the temperature of the reaction liquid-containing liquid discharged toward the substrate W gradually decreases greatly, and the temperature change amount of the reaction liquid-containing liquid increases. Therefore, even when the temperature difference between the chemical liquid and the rinse liquid is large, the temperature of the substrate W can be gradually and uniformly brought close to the temperature of the rinse liquid.

  Moreover, in this embodiment, the reaction liquid containing liquid is comprised with the sulfuric acid and the pure water, and the ratio of the exothermic liquid (sulfuric acid) contained in the reaction liquid containing liquid is reduced to zero. Therefore, the exothermic liquid contained in the reaction liquid-containing liquid disappears, and only the reaction liquid, that is, the same type of liquid as the rinse liquid supplied to the substrate W in the second rinse liquid supply step (step S8 in FIG. 5) is supplied to the substrate W. It is discharged toward. Therefore, not only the temperature of the reaction liquid-containing liquid gradually decreases greatly, but also the affinity between the liquid remaining on the substrate W and the rinse liquid before the second rinse liquid supply step (step S8 in FIG. 5) is increased. Rise. Therefore, by supplying the rinse liquid after supplying the reaction liquid-containing liquid, the liquid remaining on the substrate W can be washed away smoothly.

Although the description of the embodiment of the present invention has been described above, the present invention is not limited to the contents of the above-described embodiment, and various modifications can be made within the scope of the claims.
For example, in the first processing example described above, the case where the paddle process in which the substrate W and the SPM are reacted in the state where the discharge of the SPM from the first chemical liquid nozzle 11 is stopped is described, but the paddle process is omitted. The reaction liquid supply process may be started following the end of the first chemical liquid supply process.

  In the first processing example described above, the case where the substrate W and SPM are heated by the infrared heater 58 has been described. However, the heating step (step S4 in FIG. 5) for heating the substrate W and SPM by the infrared heater 58 is omitted. May be. Similarly, at least one of the first temperature decrease suppressing step (step S7 in FIG. 5) and the second temperature decrease suppressing step (step S10 in FIG. 5) may be omitted.

Further, in the first processing example described above, the case where the supply of the reaction liquid-containing liquid to the upper surface of the substrate W is started at the middle portion of the upper surface of the substrate W has been described. You may start in positions (for example, upper surface peripheral part) other than an upper surface middle part.
In the first processing example described above, the case where the mixing ratio of sulfuric acid and hydrogen peroxide solution is finally changed to 1 (sulfuric acid) to 1 (hydrogen peroxide solution) has been described. May be finally reduced to zero, and only the hydrogen peroxide solution (hydrogen peroxide solution-containing liquid) at room temperature may be discharged from the first chemical nozzle 11.

  In the first processing example described above, the case where the first temperature decrease suppressing process is started simultaneously with the reaction liquid supplying process (step S5 in FIG. 5) has been described. Step S7) may be started before or after the start of the reaction liquid supply step. Similarly, the second temperature decrease suppression process (step S10 in FIG. 5) may be started before or after the second chemical liquid supply process (step S9 in FIG. 5) is started.

  Further, in the first processing example described above, after the first temperature decrease suppressing step (step S7 in FIG. 5) is completed, that is, after the discharge of the heating fluid is stopped, the second temperature decrease suppressing step (in FIG. 5). Although the case where step S10) is started has been described, the discharge of the heating fluid is continued from the start of the reaction liquid supply process (step S5 in FIG. 5) to the end of the second chemical liquid supply process (step S9 in FIG. 5). May be.

In the first processing example described above, the case where the processing unit 2 performs the resist removal process has been described. However, the processing performed in the processing unit 2 is not limited to the resist removal process, and other processes such as a cleaning process and an etching process are performed. It may be a process.
In the first processing example described above, a reaction liquid-containing liquid (a mixed liquid of sulfuric acid and hydrogen peroxide solution or a mixed liquid of sulfuric acid and pure water) mixed in advance is supplied to the first chemical liquid nozzle 11. However, the reaction liquid-containing liquid may be mixed on the substrate W. For example, when the reaction liquid-containing liquid is a mixed liquid of sulfuric acid and pure water, pure water may be discharged to the rinsing liquid nozzle 36 at the same time as sulfuric acid is discharged to the first chemical liquid nozzle 11.

In the above-described embodiment, the case where the spin chuck 5 is a sandwich type chuck including a plurality of chuck pins 8 has been described. However, the spin chuck 5 has a lower surface of the substrate W on the upper surface of the spin base (adsorption base). A vacuum chuck that adsorbs the (rear surface) may be used.
In the above-described embodiment, the case where the first chemical liquid nozzle 11, the second chemical liquid nozzle 29, and the rinse liquid nozzle 36 are attached to separate nozzle arms has been described, but two of these nozzles are used. The above may be attached to a common nozzle arm. Similarly, the infrared heater 58 may be attached to a common arm with the processing liquid nozzle that discharges the processing liquid such as the first chemical liquid nozzle 11.

In the above-described embodiment, the case where the hot water (pure water heated to the first intermediate temperature) as an example of the heating liquid is supplied to the lower surface of the substrate W has been described. However, the heating gas is used instead of the heating liquid. You may supply to the lower surface of W.
Specifically, the control device 3 opens the gas valve 55 in at least one of the first temperature decrease suppressing step (step S7 in FIG. 5) and the second temperature decrease suppressing step (step S10 in FIG. 5), A nitrogen gas having an intermediate temperature (for example, a temperature higher than room temperature) may be discharged to the gas discharge port 53 that opens at the center of the upper surface of the spin base 7. In this case, the nitrogen gas discharged from the gas discharge port 53 spreads radially from the center of the upper surface of the spin base 7 in the space between the lower surface of the substrate W and the upper surface of the spin base 7. Thereby, the space between the lower surface of the substrate W and the upper surface of the spin base 7 is filled with the nitrogen gas having the first intermediate temperature, and the temperature drop of the substrate W is suppressed by the nitrogen gas which is an example of the heating gas.

In the above-described embodiment, the case where the substrate processing apparatus 1 is an apparatus for processing the disk-shaped substrate W has been described. However, the substrate processing apparatus 1 is a polygonal substrate W such as a substrate for a liquid crystal display device. It may be a device for processing.
In addition, various design changes can be made within the scope of matters described in the claims.

1: substrate processing apparatus 3: control apparatus 5: spin chuck 11: first chemical liquid nozzle 18: sulfuric acid pipe 22: hydrogen peroxide water tank 23: hydrogen peroxide water pipe 26: pure water pipe 36: rinse liquid nozzle 39: first 1 rinse liquid piping 45: lower surface nozzle 45a: discharge port 46: heating liquid piping 52: gas flow channel 53: gas discharge port 54: gas piping 57: gas heater 58: infrared heater 61: infrared lamp 62: lamp housing

Claims (7)

A chemical supply process for supplying a first temperature chemical to the main surface of the substrate;
A rinsing liquid supply step for washing away the liquid remaining on the substrate by supplying a rinsing liquid having a second temperature lower than the first temperature to the main surface of the substrate after the chemical liquid supplying step;
The reaction liquid includes at least a reaction liquid that generates an exothermic reaction by mixing with the chemical liquid supplied to the substrate in the chemical liquid supply step and a heat generation liquid that generates heat by mixing with the reaction liquid, and the liquid temperature is the first temperature. In the following, the reaction liquid-containing liquid at the second temperature or higher is in a state in which the chemical liquid supplied to the substrate in the chemical liquid supply process remains on the substrate after the chemical liquid supply process and before the rinse liquid supply process. A reaction liquid supply step of discharging toward the main surface of the substrate;
In parallel with the reaction liquid supply step, the discharge of the temperature of the reaction liquid-containing liquid discharged toward the substrate is started by reducing the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate. And a reaction solution concentration changing step of lowering the temperature of the reaction solution-containing solution at the time.   In the reaction liquid concentration changing step, the reaction liquid-containing liquid is discharged toward the substrate from a mixing ratio in which the ratio of the exothermic liquid is larger than the ratio of the reaction liquid to a mixing ratio in which the ratio of the exothermic liquid is smaller than the ratio of the reaction liquid. 2. The method includes a step of reducing the temperature of the reaction liquid-containing liquid discharged toward the substrate from the temperature of the reaction liquid-containing liquid at the start of discharge by reducing the ratio of the exothermic liquid contained in the substrate. Substrate processing method.   The reaction liquid concentration changing step starts discharging the temperature of the reaction liquid-containing liquid discharged toward the substrate by reducing the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate to zero. The substrate processing method of Claim 1 or 2 including the process made to lower than the temperature of the reaction liquid containing liquid at the time. The chemical solution supplied to the substrate in the chemical solution supply step is a mixed solution of a reactive chemical solution and a exothermic chemical solution that is hotter than the reactive chemical solution and generates heat when mixed with the reactive chemical solution,
The substrate processing method according to claim 1, wherein the reaction liquid-containing liquid at the start of discharge is a mixed liquid of a reactive chemical liquid as a reaction liquid and an exothermic chemical liquid as a heat generating liquid. The chemical solution supplied to the substrate in the chemical solution supply step is a mixed solution of a reactive chemical solution and a exothermic chemical solution that is hotter than the reactive chemical solution and generates heat when mixed with the reactive chemical solution,
The reaction liquid-containing liquid at the start of discharge includes a reaction liquid that generates an exothermic reaction by mixing with the chemical liquid supplied to the substrate in the chemical liquid supply step, and an exothermic chemical liquid-containing liquid as a exothermic liquid containing the exothermic chemical liquid. The substrate processing method as described in any one of Claims 1-3 which is a liquid mixture. The reaction liquid has the same composition as the rinse liquid supplied to the substrate in the rinse liquid supply step, and is a liquid that generates an exothermic reaction when mixed with the chemical liquid supplied to the substrate in the chemical liquid supply step.
The reaction liquid concentration changing step starts discharging the temperature of the reaction liquid-containing liquid discharged toward the substrate by reducing the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate to zero. A step of lowering the temperature of the reaction liquid-containing liquid at the time, and matching the composition of the reaction liquid-containing liquid discharged toward the substrate with the composition of the rinse liquid supplied to the substrate in the rinse liquid supply process, The substrate processing method as described in any one of Claims 1-3. A substrate holding means for holding and rotating the substrate;
A chemical solution supply means for discharging the chemical solution at the first temperature toward the main surface of the substrate held by the substrate holding means;
Rinsing liquid supply means for discharging a rinsing liquid having a second temperature lower than the first temperature toward the main surface of the substrate held by the substrate holding means;
It is generated by mixing a reaction solution that generates an exothermic reaction when mixed with a chemical solution and a heat generating solution that is hotter than the reaction solution and generates heat when mixed with the reaction solution, and the liquid temperature is first. A reaction liquid nozzle that discharges a reaction liquid-containing liquid at a temperature lower than the second temperature and higher to a main surface of the substrate held by the substrate holding means; and a reaction liquid-containing liquid discharged from the reaction liquid nozzle. Reaction liquid supply means, including concentration changing means for changing the ratio of the exothermic liquid contained,
Control means for controlling the substrate holding means, the chemical liquid supply means, the rinse liquid supply means, and the reaction liquid supply means,
The control means includes
A chemical supply process for supplying a first temperature chemical to the main surface of the substrate;
After the chemical solution supplying step, supplying a second temperature rinsing solution to the main surface of the substrate to wash away the liquid remaining on the substrate;
A liquid containing a reaction liquid having a liquid temperature not higher than the first temperature and not lower than the second temperature is applied to the substrate after the chemical liquid supplying process and before the rinsing liquid supplying process. A reaction liquid supply step of discharging toward the main surface of the substrate in a remaining state;
In parallel with the reaction liquid supply step, the discharge of the temperature of the reaction liquid-containing liquid discharged toward the substrate is started by reducing the ratio of the exothermic liquid contained in the reaction liquid-containing liquid discharged toward the substrate. The substrate processing apparatus which performs the reaction liquid density | concentration change process reduced from the temperature of the reaction liquid containing liquid at the time.

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