Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method capable of starting cooling of a sublimable substance-containing liquid simultaneously with supplying the sublimable substance-containing liquid to a substrate and efficiently cooling the sublimable substance-containing liquid on the substrate.SOLUTION: The substrate processing method includes a preprocessing liquid supplying step of covering the upper surface of the substrate W with a liquid film of a preprocessing liquid having a higher temperature than a cooling substance while bringing the cooling substance into contact with the lower surface of the substrate W, a sublimable substance-containing liquid supplying step of covering the upper surface of the substrate W with a liquid film of a sublimable substance-containing liquid having a higher temperature than the cooling substance while bringing the cooling substance into contact with the lower surface of the substrate W, a solidified film forming step of changing the preprocessing liquid on the upper surface of the substrate W into the solidified film SF containing the sublimable substance, and a sublimation step of removing the solidified film SF from the upper surface of the substrate W by sublimating the solidified film SF.SELECTED DRAWING: FIGS. 11A-D

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing substrates, including, for example, semiconductor wafers, substrates for FPDs (Flat Panel Displays) such as liquid crystal displays and organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells. [Background technology]

[0002] Patent Document 1 discloses a method of supplying a treatment liquid containing a sublimable substance to a substrate, and then sublimating and removing a solidified form of the sublimable substance from the substrate. Patent Document 1 discloses a method of maintaining the temperature of a treatment liquid film formed on a pattern forming surface within a temperature range equal to or higher than the melting point of the sublimable substance and lower than the boiling point of the sublimable substance, and then supplying a refrigerant to the rear surface of the substrate to cool the treatment liquid film through the substrate to a temperature equal to or lower than the freezing point of the sublimable substance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-114774 Summary of the Invention [Problem to be solved by the invention]

[0004] At least one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus that can start cooling of a sublimable substance-containing liquid simultaneously with supplying the sublimable substance-containing liquid to a substrate, and can efficiently cool the sublimable substance-containing liquid on the substrate. [Means for solving the problem]

[0005] One embodiment of the present invention provides a substrate processing method for processing a substrate having an upper surface formed with a pattern including a plurality of convex portions and a plurality of concave portions, the method including: a pre-treatment liquid supplying step of covering the upper surface of the substrate with a liquid film of a pre-treatment liquid having a temperature higher than that of a cooling substance while bringing the cooling substance into contact with the lower surface of the substrate; a sublimable substance-containing liquid supplying step of covering the upper surface of the substrate with a liquid film of the sublimable substance-containing liquid having a temperature higher than that of the cooling substance while bringing the cooling substance into contact with the lower surface of the substrate by replacing the pre-treatment liquid on the upper surface of the substrate with a sublimable substance-containing liquid; a solidified film forming step of changing the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into a solidified film containing a sublimable substance; and a sublimation step of removing the solidified film from the upper surface of the substrate by sublimating it.

[0006] In the above embodiment, at least one of the following features may be added to the substrate processing method.

[0007] The pretreatment liquid supply process includes a process of reducing the rotation speed of the substrate while ejecting the pretreatment liquid toward the upper surface of the substrate, and a process of starting to bring the cooling substance into contact with the lower surface of the substrate after the rotation speed of the substrate starts to decrease.

[0008] The pretreatment liquid supply process includes a process of ejecting the pretreatment liquid toward the upper surface of the substrate, and a process of bringing the cooling substance into contact with the lower surface of the substrate while the ejection of the pretreatment liquid toward the upper surface of the substrate is stopped and the upper surface of the substrate is covered with a liquid film of the pretreatment liquid.

[0009] The pretreatment liquid supplying step includes a puddling step of increasing the thickness of the liquid film of the pretreatment liquid on the upper surface of the substrate by reducing the rotation speed of the substrate, and a step of bringing the cooling substance into contact with the lower surface of the substrate in a state where the thickness has increased, and the sublimable substance-containing liquid supplying step includes a sublimable substance-containing liquid ejecting step of ejecting the sublimable substance-containing liquid toward the upper surface of the substrate in a state where the thickness has increased, thereby replacing the pretreatment liquid on the upper surface of the substrate with the sublimable substance-containing liquid.

[0010] The puddle process includes a step of reducing the rotation speed of the substrate to a puddle speed while the upper surface of the substrate is covered with the liquid film of the pretreatment liquid, and the sublimable substance-containing liquid ejection process includes a step of ejecting the sublimable substance-containing liquid toward the upper surface of the substrate while maintaining the rotation speed of the substrate at the puddle speed.

[0011] The solidified film forming process includes a process of changing the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into the solidified film by strengthening the airflow flowing along the upper surface of the substrate while the cooling substance is not in contact with the lower surface of the substrate.

[0012] Another embodiment of the present invention provides a substrate processing apparatus including: a substrate holder for holding a substrate having an upper surface formed with a pattern including a plurality of protrusions and a plurality of recesses; a cooler for cooling the substrate by contacting a cooling substance with an underside of the substrate held by the substrate holder; at least one liquid nozzle for individually discharging a plurality of processing liquids toward the upper surface of the substrate held by the substrate holder, the processing liquids including a pre-treatment liquid having a temperature higher than that of the cooling substance and a sublimable substance-containing liquid having a temperature higher than that of the cooling substance; at least one liquid valve for causing the at least one liquid nozzle to individually discharge the plurality of processing liquids; at least one gas nozzle for discharging a gas toward the upper surface of the substrate held by the substrate holder; at least one gas valve for causing the at least one gas nozzle to discharge the gas; and a spin motor for rotating the substrate held by the substrate holder. The at least one liquid valve may cause the at least one liquid nozzle to individually discharge the plurality of processing liquids while the cooling substance is in contact with the underside of the substrate held by the substrate holder.

[0013] In the above embodiment, at least one of the following features may be added to the substrate processing apparatus.

[0014] The cooler and at least one liquid valve may perform a pre-treatment liquid supplying step of covering the upper surface of the substrate with a liquid film of the pre-treatment liquid having a temperature higher than that of the cooling substance while bringing the cooling substance into contact with the lower surface of the substrate, and a sublimable substance-containing liquid supplying step of covering the upper surface of the substrate with a liquid film of the sublimable substance-containing liquid having a temperature higher than that of the cooling substance while bringing the cooling substance into contact with the lower surface of the substrate by replacing the pre-treatment liquid on the upper surface of the substrate with the sublimable substance-containing liquid. One or both of the at least one gas valve and the spin motor may perform a solidified film forming step of changing the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into the solidified film containing the sublimable substance, and a sublimation step of removing the solidified film from the upper surface of the substrate by sublimating it.

[0015] The at least one liquid valve and spin motor reduce the rotation speed of the substrate while causing the at least one liquid nozzle to eject the pretreatment liquid toward the upper surface of the substrate, and the cooler begins to bring the cooling material into contact with the lower surface of the substrate after the rotation speed of the substrate begins to decrease.

[0016] The at least one liquid valve causes the at least one liquid nozzle to eject the pretreatment liquid toward the upper surface of the substrate, and the cooler brings the cooling substance into contact with the lower surface of the substrate while the ejection of the pretreatment liquid toward the upper surface of the substrate is stopped and the upper surface of the substrate is covered with a liquid film of the pretreatment liquid.

[0017] The spin motor performs a puddle process of increasing the thickness of the liquid film of the pretreatment liquid on the upper surface of the substrate by reducing the rotation speed of the substrate, the cooler brings the cooling material into contact with the lower surface of the substrate in a state where the thickness has increased, and the at least one liquid valve causes the at least one liquid nozzle to eject the sublimable substance-containing liquid toward the upper surface of the substrate in a state where the thickness has increased, thereby performing a sublimable substance-containing liquid ejection process of replacing the pretreatment liquid on the upper surface of the substrate with the sublimable substance-containing liquid.

[0018] The puddle process includes a step of reducing the rotation speed of the substrate to a puddle speed while the upper surface of the substrate is covered with the liquid film of the pretreatment liquid, and the sublimable substance-containing liquid ejection process includes a step of ejecting the sublimable substance-containing liquid toward the upper surface of the substrate while maintaining the rotation speed of the substrate at the puddle speed.

[0019] The at least one gas valve and / or the spin motor strengthens the airflow flowing along the upper surface of the substrate while the cooling substance is not in contact with the lower surface of the substrate, thereby changing the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into a solidified film containing the sublimable substance. [Brief explanation of the drawings]

[0020] [Figure 1A] 1 is a schematic plan view showing a layout of a substrate processing apparatus according to an embodiment; [Figure 1B] FIG. 2 is a schematic side view of the substrate processing apparatus. [Figure 2] 1 is a schematic diagram showing the interior of a processing unit provided in a substrate processing apparatus as viewed horizontally. [Figure 3] FIG. 3 is a schematic cross-sectional view showing a vertical cross section of the blocking member. [Figure 4] FIG. 4 is a schematic view of the central opening of the blocking member as viewed from below. [Figure 5] 3 is a horizontal schematic view of a processing unit different from the processing unit shown in FIG. 2. FIG. [Figure 6] 6 is a schematic diagram showing a spin chuck and a heating / cooling plate provided in the processing unit shown in FIG. 5, as viewed from above. [Figure 7] FIG. 2 is a block diagram showing an electrical configuration of the substrate processing apparatus. [Figure 8] 1 is a schematic cross-sectional view showing an example of the structure of a substrate to be processed by a substrate processing apparatus. [Figure 9] 5A to 5C are process diagrams for explaining an example of substrate processing performed by the substrate processing apparatus. [Figure 10] 10 is a timing chart for explaining a specific example of steps from a pre-treatment liquid supply step to a sublimation step. [Figure 11A-D] FIG. 1 is a schematic diagram of a substrate viewed horizontally. [Figure 11E-G] FIG. 2 is a schematic cross-sectional view of a substrate. [Figure 11H-I] FIG. 2 is a schematic cross-sectional view of a substrate. DETAILED DESCRIPTION OF THE INVENTION

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

[0022] In the following description, unless otherwise specified, the air pressure inside the substrate processing apparatus 1 is maintained at the air pressure inside the clean room in which the substrate processing apparatus 1 is installed (for example, 1 atmosphere or a value close to that).

[0023] 1A is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment, and FIG.

[0024] The substrate processing apparatus 1 is a single-wafer processing apparatus that processes disk-shaped substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 includes a load port LP that holds carriers CA that accommodate substrates W, a plurality of processing units 2 that process the substrates W transferred from the carriers CA on the load port LP with processing fluids such as processing liquids and processing gases, a transfer system TS that transfers the substrates W between the carriers CA on the load port LP and the plurality of processing units 2, and a control device 3 that controls the substrate processing apparatus 1.

[0025] The multiple processing units 2 form multiple towers TW. FIG. 1A shows an example in which four towers TW are formed. As shown in FIG. 1B, the multiple processing units 2 included in one tower TW are stacked one on top of the other. As shown in FIG. 1A, the multiple towers TW form two rows extending in the depth direction of the substrate processing apparatus 1 in a plan view. In a plan view, the two rows face each other across the transport path TP.

[0026] The transport system TS includes an indexer robot IR that loads and unloads substrates W into and from carriers CA on the load port LP, and a center robot CR that loads and unloads substrates W into and from multiple processing units 2. The center robot CR is disposed on the transport path TP. The indexer robot IR is disposed between the load port LP and the center robot CR in a plan view. The indexer robot IR hands over substrates W to the center robot CR and receives substrates W from the center robot CR. The same is true for the center robot CR.

[0027] The indexer robot IR includes one or more hands Hi that support a substrate W horizontally. The hands Hi can move parallel to both the horizontal and vertical directions. The hands Hi can rotate about a vertical line. The hands Hi can load and unload a substrate W to and from a carrier CA on any of the load ports LP, and can transfer a substrate W to and from the center robot CR.

[0028] The center robot CR includes one or more hands Hc that support the substrate W horizontally. The hands Hc can move parallel to both the horizontal and vertical directions. The hands Hc can rotate about a vertical line. The hands Hc can transfer the substrate W to and from the indexer robot IR, and can transport the substrate W into and out of any of the processing units 2.

[0029] Next, the processing unit 2 will be described.

[0030] Fig. 2 is a horizontal schematic view of the interior of the processing unit 2 provided in the substrate processing apparatus 1. Fig. 3 is a schematic cross-sectional view showing a vertical cross section of the blocking member 51. Fig. 4 is a schematic view of the central opening 61 of the blocking member 51 as seen from below. "Sublimation" in Figs. 2 and 3 represents the sublimable substance-containing liquid.

[0031] As shown in Figure 2, the processing unit 2 includes a box-shaped chamber 4 having an internal space, a spin chuck 10 that holds one substrate W horizontally within the chamber 4 and rotates it around a vertical rotation axis A1 passing through the center of the substrate W, and a cylindrical processing cup 21 that surrounds the spin chuck 10 around the rotation axis A1.

[0032] The chamber 4 includes a box-shaped partition wall 5 having an inlet / outlet port 5b through which the substrate W passes, and a shutter 7 that opens and closes the inlet / outlet port 5b. The FFU 6 (fan filter unit 6) is disposed above an air outlet 5a disposed at the top of the partition wall 5. The FFU 6 constantly supplies clean air (air filtered by a filter) into the chamber 4 through the air outlet 5a. The gas within the chamber 4 is exhausted from the chamber 4 through an exhaust duct 8 connected to the bottom of the processing cup 21. This constantly creates a downflow of clean air within the chamber 4. The flow rate of the exhaust air discharged into the exhaust duct 8 is changed according to the opening of an exhaust valve 9 disposed within the exhaust duct 8.

[0033] The spin chuck 10 includes a disk-shaped spin base 12 held horizontally, a plurality of chuck pins 11 that hold the substrate W horizontally above the spin base 12, a spin shaft 13 that extends downward from the center of the spin base 12, and a spin motor 14 that rotates the spin shaft 13 to rotate the spin base 12 and the plurality of chuck pins 11.

[0034] The spin chuck 10 is not limited to a clamping type chuck in which multiple chuck pins 11 contact the edge surface of the substrate W, but may also be a vacuum type chuck that holds the substrate W horizontally by adsorbing the back surface (lower surface) of the substrate W, which is the non-device forming surface, to the upper surface 12u of the spin base 12. When the spin chuck 10 is a clamping type chuck, the multiple chuck pins 11 correspond to the substrate holder. When the spin chuck 10 is a vacuum type chuck, the spin base 12 corresponds to the substrate holder.

[0035] The processing cup 21 includes a plurality of guards 24 that receive the processing liquid discharged outward from the substrate W, a plurality of cups 23 that receive the processing liquid guided downward by the plurality of guards 24, and a cylindrical outer wall member 22 that surrounds the plurality of guards 24 and the plurality of cups 23. Figure 2 shows an example in which four guards 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third guard 24 from the top.

[0036] The guard 24 includes a cylindrical portion 25 that surrounds the spin chuck 10 and an annular ceiling portion 26 that extends obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. The multiple ceiling portions 26 are stacked one on top of the other, and the multiple cylindrical portions 25 are arranged concentrically. The upper end of the annular ceiling portion 26 corresponds to an upper end 24u of the guard 24 that surrounds the substrate W and the spin base 12 in a plan view. The multiple cups 23 are respectively arranged below the multiple cylindrical portions 25. The cups 23 form annular grooves that receive the processing liquid guided downward by the guard 24.

[0037] The processing unit 2 includes an elevation actuator 27 that raises and lowers the multiple guards 24 individually. The elevation actuator 27 positions the guards 24 at any position within a range from the upper position to the lower position. FIG. 2 shows a state in which two guards 24 are positioned at the upper position and the remaining two guards 24 are positioned at the lower position. The upper position is a position in which the upper ends 24u of the guards 24 are positioned above the holding position where the substrate W held by the spin chuck 10 is positioned. The lower position is a position in which the upper ends 24u of the guards 24 are positioned below the holding position.

[0038] An actuator is a device that converts driving energy, such as electrical, fluid, magnetic, thermal, or chemical energy, into mechanical work, i.e., the movement of a tangible object. Actuators include electric motors (rotary motors), linear motors, air cylinders, and other devices. When the movement of the actuator differs from the movement of the object, a motion converter may be provided to convert the movement of the actuator into linear motion or rotation. For example, if the actuator is an electric motor that moves the object linearly, the rotation of the electric motor may be converted into linear motion by a motion converter such as a ball screw and ball nut.

[0039] The processing unit 2 includes a plurality of nozzles that discharge a processing fluid toward the substrate W held on the spin chuck 10. The plurality of nozzles includes a first chemical liquid nozzle 31a and a second chemical liquid nozzle 31b that discharge a chemical liquid toward the upper surface of the substrate W, and a first rinse liquid nozzle 35a and a second rinse liquid nozzle 35b that discharge a rinse liquid toward the upper surface of the substrate W. The plurality of nozzles also includes a center nozzle 55 and a bottom nozzle 71, which will be described later. The bottom nozzle 71 is included in the cooler. The cooler also includes a rinse liquid valve 73, a central opening 61, an inert gas valve 84, a heating / cooling plate 92, and an elevation actuator 98, which will be described later.

[0040] First chemical liquid nozzle 31a may be a scan nozzle that moves the collision position of the chemical liquid on substrate W within the upper surface of substrate W, or may be a fixed nozzle that cannot move the collision position of the chemical liquid on substrate W. The same applies to the other nozzles. Figure 2 shows an example in which first chemical liquid nozzle 31a, second chemical liquid nozzle 31b, first rinse liquid nozzle 35a, and second rinse liquid nozzle 35b are scan nozzles, and the other nozzles are fixed nozzles.

[0041] First chemical liquid nozzle 31a is connected to first chemical liquid pipe 32a that guides the chemical liquid. Second chemical liquid nozzle 31b is connected to second chemical liquid pipe 32b that guides the chemical liquid. When first chemical liquid valve 33a attached to first chemical liquid pipe 32a is opened, the chemical liquid is continuously discharged downward from the discharge port of first chemical liquid nozzle 31a. Similarly, when second chemical liquid valve 33b attached to second chemical liquid pipe 32b is opened, the chemical liquid is continuously discharged downward from the discharge port of second chemical liquid nozzle 31b.

[0042] FIG. 2 shows an example in which first chemical liquid nozzle 31a dispenses DHF and second chemical liquid nozzle 31b dispenses SC1. DHF (dilute hydrogen fluoride) represents dilute hydrofluoric acid. SC1 represents a liquid containing ammonium hydroxide, hydrogen peroxide, and water. The chemical liquid dispensed from first chemical liquid nozzle 31a may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, hydrogen peroxide water, organic acid (e.g., citric acid, oxalic acid, etc.), organic alkali (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and corrosion inhibitor, or may be another liquid. The same applies to the chemical liquid dispensed from second chemical liquid nozzle 31b. The chemical liquid dispensed from second chemical liquid nozzle 31b is a liquid that differs from the chemical liquid dispensed from first chemical liquid nozzle 31a in at least one of its composition and temperature.

[0043] Although not shown, first chemical liquid valve 33a includes a valve body with an annular valve seat through which the chemical liquid passes, a valve element movable relative to the valve seat, and an actuator that moves the valve element between a closed position in which the valve element contacts the valve seat and an open position in which the valve element is separated from the valve seat. The same applies to the other valves. The actuator may be a pneumatic actuator, an electric actuator, or another type of actuator. Control device 3 controls the actuator to open and close first chemical liquid valve 33a, etc.

[0044] The first rinse liquid nozzle 35a is connected to a first rinse liquid pipe 36a that guides the rinse liquid. The second rinse liquid nozzle 35b is connected to a second rinse liquid pipe 36b that guides the rinse liquid. When a first rinse liquid valve 37a attached to the first rinse liquid pipe 36a is opened, the rinse liquid is continuously discharged downward from the discharge port of the first rinse liquid nozzle 35a. Similarly, when a second rinse liquid valve 37b attached to the second rinse liquid pipe 36b is opened, the rinse liquid is continuously discharged downward from the discharge port of the second rinse liquid nozzle 35b.

[0045] FIG. 2 shows an example in which the first rinse liquid nozzle 35a and the second rinse liquid nozzle 35b discharge DIW. DIW (Deionized Water) stands for pure water (deionized water). The rinse liquid discharged from the first rinse liquid nozzle 35a may be any of carbonated water, electrolytic ionized water, hydrogen water, ozone water, and hydrochloric acid water with a diluted concentration (for example, about 10 to 100 ppm), or may be a liquid other than these. The same applies to the rinse liquid discharged from the second rinse liquid nozzle 35b. The rinse liquid discharged from the second rinse liquid nozzle 35b may have the same composition and temperature as the rinse liquid discharged from the first rinse liquid nozzle 35a, or may be different.

[0046] First chemical liquid nozzle 31a and first rinse liquid nozzle 35a are connected to first nozzle actuator 34a, which moves first chemical liquid nozzle 31a and first rinse liquid nozzle 35a in at least one of the vertical and horizontal directions. First nozzle actuator 34a moves first chemical liquid nozzle 31a and first rinse liquid nozzle 35a horizontally between a processing position where the processing liquid discharged from first chemical liquid nozzle 31a or first rinse liquid nozzle 35a is supplied to the upper surface of substrate W and a standby position where first chemical liquid nozzle 31a and first rinse liquid nozzle 35a are positioned around processing cup 21 in a plan view.

[0047] Similarly, second chemical liquid nozzle 31b and second rinse liquid nozzle 35b are connected to second nozzle actuator 34b, which moves second chemical liquid nozzle 31b and second rinse liquid nozzle 35b in at least one of the vertical and horizontal directions. Second nozzle actuator 34b moves second chemical liquid nozzle 31b and second rinse liquid nozzle 35b horizontally between a processing position where the processing liquid discharged from second chemical liquid nozzle 31b or second rinse liquid nozzle 35b is supplied to the upper surface of substrate W and a standby position where second chemical liquid nozzle 31b and second rinse liquid nozzle 35b are positioned around processing cup 21 in a plan view.

[0048] The multiple nozzles include a lower surface nozzle 71 that ejects a processing liquid toward the center of the lower surface of the substrate W held on the spin chuck 10. The lower surface nozzle 71 includes a disk portion disposed between the upper surface 12u of the spin base 12 and the lower surface of the substrate W, and a cylindrical portion extending downward from the disk portion. The ejection port of the lower surface nozzle 71 opens at the center of the upper surface of the disk portion. When the substrate W is held on the spin chuck 10, the ejection port of the lower surface nozzle 71 faces the center of the lower surface of the substrate W in the vertical direction.

[0049] The lower surface nozzle 71 is connected to a rinse liquid pipe 72 that guides the rinse liquid. FIG. 2 shows an example in which the rinse liquid is deionized water (DIW). When a rinse liquid valve 73 attached to the rinse liquid pipe 72 is opened, the rinse liquid is continuously discharged upward from the discharge port of the lower surface nozzle 71. The temperature of the rinse liquid when discharged from the lower surface nozzle 71 may be room temperature (e.g., 20 to 30°C), or may be higher or lower than room temperature. In the latter case, hot water (deionized water that is higher than room temperature) or cold water (deionized water that is lower than room temperature) can be discharged from the lower surface nozzle 71.

[0050] The outer peripheral surface of the lower nozzle 71 and the inner peripheral surface of the spin base 12 form a cylindrical gas flow path 82 that extends vertically. The gas flow path 82 includes a central opening 81 that opens in the center of the upper surface 12u of the spin base 12. The gas flow path 82 is connected to an inert gas pipe 83 that guides the inert gas. When an inert gas valve 84 attached to the inert gas pipe 83 is opened, the inert gas is continuously discharged upward from the central opening 81 of the spin base 12 at a flow rate that corresponds to the opening of a flow rate adjustment valve 85 that changes the flow rate of the inert gas.

[0051] The inert gas discharged from the central opening 81 of the spin base 12 is nitrogen gas. The inert gas may be a gas other than nitrogen gas, such as helium gas or argon gas. When the substrate W is held by the spin chuck 10, the nitrogen gas is discharged from the central opening 81 of the spin base 12, and the nitrogen gas flows radially in all directions between the lower surface of the substrate W and the upper surface 12u of the spin base 12. This fills the space between the substrate W and the spin base 12 with nitrogen gas.

[0052] The liquid discharged from the lower nozzle 71 may be heated or cooled by an in-line heater or an in-line cooler, or by a Peltier element that also serves as an in-line heater and an in-line cooler. Similarly, the gas discharged from the gas flow path 82 may be heated or cooled by an in-line heater or an in-line cooler, or by a Peltier element that also serves as an in-line heater and an in-line cooler. Figure 2 shows an example in which the liquid discharged from the lower nozzle 71 is heated or cooled by a Peltier element 74, and the gas discharged from the gas flow path 82 is heated or cooled by a Peltier element 86.

[0053] The temperature of the liquid discharged from the lower surface nozzle 71 may be room temperature, or may be higher or lower than room temperature. The temperature of the substrate W when the liquid discharged from the lower surface nozzle 71 comes into contact with the substrate W may be room temperature, or may be higher or lower than room temperature. Similarly, the temperature of the gas discharged from the gas flow path 82 may be room temperature, or may be higher or lower than room temperature. The temperature of the substrate W when the gas discharged from the gas flow path 82 comes into contact with the substrate W may be room temperature, or may be higher or lower than room temperature.

[0054] The liquid discharged from the lower nozzle 71 may be a cooling liquid whose temperature is lower than room temperature. The gas discharged from the gas flow path 82 may be a cooling gas whose temperature is lower than room temperature. The cooling liquid and the cooling gas are examples of cooling substances. The cooling liquid and the cooling gas are fluids that do not react with the substrate W. As long as this requirement is met, the cooling liquid may be a rinse liquid other than pure water, or a liquid other than a rinse liquid. Similarly, the cooling gas may be an inert gas other than nitrogen gas, or a gas other than an inert gas such as air.

[0055] As shown in FIG. 2, the processing unit 2 includes a blocking member 51 arranged above the spin chuck 10. FIG. 2 shows an example in which the blocking member 51 is a disk-shaped blocking plate. The blocking member 51 includes a disk portion 52 arranged horizontally above the spin chuck 10. The blocking member 51 is supported horizontally by a cylindrical support shaft 53 extending upward from the center of the disk portion 52. The center line of the disk portion 52 is located on the rotation axis A1 of the substrate W. The lower surface of the disk portion 52 corresponds to the lower surface 51L of the blocking member 51. The lower surface 51L of the blocking member 51 is parallel to the upper surface of the substrate W and has an outer diameter equal to or greater than the diameter of the substrate W.

[0056] Blocking member 51 is connected to vertical actuator 54v, which moves blocking member 51 vertically in parallel. Vertical actuator 54v positions blocking member 51 at any position within a range from an upper position (the position shown in FIG. 2) to a lower position (see FIG. 11D). The lower position is a proximity position where lower surface 51L of blocking member 51 is close to the upper surface of substrate W to a height where a scan nozzle such as first chemical liquid nozzle 31a cannot enter between substrate W and blocking member 51. The upper position is a standby position where blocking member 51 is retracted to a height where a scan nozzle can enter between blocking member 51 and substrate W.

[0057] The blocking member 51 is further connected to a rotation actuator 54r that rotates the blocking member 51 around a vertical rotation axis A1 that passes through the center of the blocking member 51. The rotation axis A1 of the blocking member 51 is the same axis as the rotation axis A1 of the substrate W. As shown in FIG. 3, the blocking member 51 is supported by a support arm 54s via the rotation actuator 54r. The rotation actuator 54r rotates the blocking member 51 relative to the support arm 54s. The vertical actuator 54v raises and lowers the support arm 54s, thereby raising and lowering the blocking member 51. The support arm 54s is disposed above the disk portion 52 of the blocking member 51.

[0058] The multiple nozzles include a central nozzle 55 that discharges a processing fluid such as a processing liquid or a processing gas downward through a central opening 61 that opens in the center of the lower surface 51L of the blocking member 51. The central nozzle 55 extends vertically along the rotation axis A1. The inner circumferential surface of the blocking member 51 surrounds the outer circumferential surface of the center nozzle 55 at a distance. The inner circumferential surface of the blocking member 51 forms a flow path that extends upward from the central opening 61. The central nozzle 55 moves up and down together with the blocking member 51. The discharge port of the central nozzle 55 that discharges the processing fluid is located above the central opening 61 of the blocking member 51.

[0059] The central nozzle 55 includes multiple inner tubes that discharge the treatment fluid downward and a cylindrical casing 55d that surrounds the multiple inner tubes. Figures 3 and 4 show an example in which three inner tubes, namely, a first tube 55a, a second tube 55b, and a third tube 55c, are provided. The inner circumferential surface of the blocking member 51 surrounds the outer circumferential surface of the casing 55d with a gap therebetween. The outer circumferential surface of the casing 55d corresponds to the outer circumferential surface of the central nozzle 55. The outlets of the first tube 55a, the second tube 55b, and the third tube 55c correspond to the outlets of the central nozzle 55.

[0060] As shown in Fig. 3, the first tube 55a is connected to a sublimable substance-containing liquid pipe 42 that guides the sublimable substance-containing liquid. The second tube 55b is connected to a pre-treatment liquid pipe 44 that guides the pre-treatment liquid. The third tube 55c is connected to an inert gas pipe 56 that guides the inert gas. Fig. 3 shows an example in which the pre-treatment liquid is IPA (isopropyl alcohol) and the inert gas is nitrogen gas.

[0061] When the sublimable substance-containing liquid valve 43 attached to the sublimable substance-containing liquid pipe 42 is opened, the sublimable substance-containing liquid is continuously discharged downward from the outlet of the first tube 55a. When the pre-treatment liquid valve 45 attached to the pre-treatment liquid pipe 44 is opened, the pre-treatment liquid is continuously discharged downward from the outlet of the second tube 55b. When the inert gas valve 57 attached to the inert gas pipe 56 is opened, the inert gas is continuously discharged downward from the outlet of the third tube 55c at a flow rate corresponding to the opening of the flow rate adjustment valve 58 that changes the flow rate of the inert gas. The inert gas discharged from the outlet of the third tube 55c may be nitrogen gas or an inert gas other than nitrogen gas.

[0062] The central nozzle 55 is an example of a liquid nozzle and a gas nozzle. Specifically, the first tube 55a is an example of a liquid nozzle and a sublimable substance-containing liquid nozzle. The second tube 55b is an example of a liquid nozzle and a pre-treatment liquid nozzle. The third tube 55c is an example of a gas nozzle. The central opening 61 is another example of a gas nozzle. The sublimable substance-containing liquid valve 43 and the pre-treatment liquid valve 45 are examples of liquid valves. The inert gas valve 57 is an example of a gas valve.

[0063] The sublimable substance-containing liquid is a solution containing a sublimable substance corresponding to a solute and a solvent that dissolves in the sublimable substance. The sublimable substance-containing liquid may be a melt of the sublimable substance (liquid sublimable substance). The sublimable substance-containing liquid may further contain a substance other than the sublimable substance and the solvent. The sublimable substance may be a substance that changes from a solid to a gas without passing through a liquid state at room temperature (synonymous with room temperature) or normal pressure (pressure inside the substrate processing apparatus 1, for example, 1 atmosphere or a value thereabout).

[0064] The freezing point of the sublimable substance-containing liquid (freezing point at 1 atmosphere; the same applies below) is lower than room temperature (for example, 20 to 30°C). The substrate processing apparatus 1 is placed in a clean room maintained at room temperature. Therefore, the sublimable substance-containing liquid can be maintained in a liquid state without heating the sublimable substance-containing liquid. The freezing point of the sublimable substance is higher than the freezing point of the sublimable substance-containing liquid. The freezing point of the sublimable substance is higher than room temperature. At room temperature, the sublimable substance is solid. The freezing point of the sublimable substance may be higher than the boiling point of the solvent. The vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance.

[0065] The sublimable substance may be, for example, any of alcohols such as 2-methyl-2-propanol (also known as tert-butyl alcohol, t-butyl alcohol, or tertiary butyl alcohol) and cyclohexanol, fluorohydrocarbon compounds, 1,3,5-trioxane (also known as metaformaldehyde), camphor (also known as camphor), naphthalene, and iodine, or may be a substance other than these. The sublimable substance may be cyclohexanone oxime, pinacoline oxime, or acetophenone oxime.

[0066] The solvent may be at least one selected from the group consisting of pure water, IPA, methanol, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), and ethylene glycol. IPA has a higher vapor pressure and a lower surface tension than water.

[0067] As will be described later, the pretreatment liquid is supplied to the upper surface of the substrate W covered with a liquid film of the rinse liquid, and the sublimable substance-containing liquid is supplied to the upper surface of the substrate W covered with a liquid film of the pretreatment liquid. The pretreatment liquid may be any liquid as long as it is soluble in both the rinse liquid and the sublimable substance-containing liquid. The pretreatment liquid is, for example, IPA (liquid). The pretreatment liquid may be a mixed liquid of IPA and HFE, or may be other liquids. When the sublimable substance-containing liquid is a solution, the pretreatment liquid may be a liquid whose components are the same as the solvent of the sublimable substance-containing liquid.

[0068] As shown in Fig. 3, the inner peripheral surface of the blocking member 51 and the outer peripheral surface of the central nozzle 55 form a cylindrical gas flow path 62 extending vertically. The gas flow path 62 is connected to an inert gas pipe 63 that guides an inert gas. When an inert gas valve 64 attached to the inert gas pipe 63 is opened, the inert gas is continuously discharged downward from the central opening 61 of the blocking member 51 at a flow rate that corresponds to the opening of a flow rate adjustment valve 65 that changes the flow rate of the inert gas. The inert gas discharged from the central opening 61 of the blocking member 51 is nitrogen gas. The inert gas may be a gas other than nitrogen gas, such as helium gas or argon gas.

[0069] Next, a processing unit 2 different from the processing unit 2 shown in FIG. 2 will be described.

[0070] Fig. 5 is a horizontal schematic view of a processing unit 2 different from the processing unit 2 shown in Fig. 2. Fig. 6 is a top schematic view of the spin chuck 10 and the heating / cooling plate 92 provided in the processing unit 2 shown in Fig. 5. Components equivalent to those shown in Fig. 2 are given the same reference numerals as in Fig. 2, and descriptions thereof will be omitted.

[0071] The processing unit 2 shown in Figures 5 and 6 differs from the processing unit 2 shown in Figure 2 mainly in that a heating / cooling plate 92 is provided instead of the lower surface nozzle 71. The heating / cooling plate 92 is an example of an electrical device that generates and absorbs heat in response to the supply of power. As shown in Figure 5, the heating / cooling plate 92 is disposed between the substrate W and the spin base 12.

[0072] The heating / cooling plate 92 includes a Peltier element 93 that generates and absorbs heat in response to the supply of power, and an outer case 94 that houses the Peltier element 93. The Peltier element 93 and the outer case 94 are disposed below the substrate W. The Peltier element 93 is connected to wiring (not shown) that supplies a direct current to the Peltier element 93. When the substrate W is supported by the outer case 94, the substrate W is uniformly heated or cooled according to the direction of the direct current supplied to the Peltier element 93. The control device 3 controls the temperature of the substrate W supported by the outer case 94 by switching on and off the supply of direct current to the Peltier element 93 and switching the direction of the direct current supplied to the Peltier element 93.

[0073] The outer case 94 of the heating / cooling plate 92 includes a disk-shaped base portion 95 disposed below the substrate W, and a plurality of hemispherical protrusions 96 protruding upward from the upper surface of the base portion 95. The upper surface of the base portion 95 is parallel to the lower surface of the substrate W and has an outer diameter smaller than the diameter of the substrate W. The plurality of protrusions 96 contact the lower surface of the substrate W at positions spaced upward from the upper surface of the base portion 95. The plurality of protrusions 96 are disposed at a plurality of positions within the upper surface of the base portion 95 so that the substrate W is supported horizontally. The substrate W is supported horizontally with the lower surface of the substrate W spaced upward from the upper surface of the base portion 95.

[0074] As shown in FIG. 6, multiple chuck pins 11 are arranged around a heating / cooling plate 92. The center line of the heating / cooling plate 92 is aligned with the rotation axis A1 of the substrate W. Even when the spin chuck 10 rotates, the heating / cooling plate 92 does not rotate. The outer diameter of the heating / cooling plate 92 is smaller than the diameter of the substrate W. The difference between the outer diameter of the heating / cooling plate 92 and the diameter of the substrate W is smaller than the height of the chuck pins 11 (see FIG. 5; the vertical length from the upper surface 12u of the spin base 12 to the upper end of the chuck pins 11).

[0075] As shown in FIG. 5, the heating / cooling plate 92 is supported horizontally by a support shaft 97 extending downward from the center of the heating / cooling plate 92. The heating / cooling plate 92 is movable up and down relative to the spin base 12. The heating / cooling plate 92 is connected to an elevation actuator 98 via the support shaft 97. The elevation actuator 98 translates the heating / cooling plate 92 up and down between an upper position (position indicated by a solid line in FIG. 5) and a lower position (position indicated by a two-dot chain line in FIG. 5). The upper position is a contact position where the heating / cooling plate 92 comes into contact with the lower surface of the substrate W. The lower position is a proximity position where the heating / cooling plate 92 is spaced apart from the substrate W and is positioned between the lower surface of the substrate W and the upper surface 12u of the spin base 12.

[0076] The lifting actuator 98 positions the heating and cooling plate 92 at any position within a range from the upper position to the lower position. When the substrate W is supported by the multiple chuck pins 11 and the heating and cooling plate 92 is raised to the upper position while the substrate W is released from its grip, the multiple protrusions 96 of the heating and cooling plate 92 come into contact with the underside of the substrate W, and the substrate W is supported by the heating and cooling plate 92. The substrate W is then lifted by the heating and cooling plate 92 and separated upward from the multiple chuck pins 11. When the heating and cooling plate 92 is lowered to the lower position in this state, the substrate W on the heating and cooling plate 92 is placed on the multiple chuck pins 11, and the heating and cooling plate 92 is separated downward from the substrate W. In this manner, the substrate W is transferred between the multiple chuck pins 11 and the heating and cooling plate 92.

[0077] Next, the electrical configuration of the substrate processing apparatus 1 will be described.

[0078] 7 is a block diagram showing the electrical configuration of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control device 3 that controls the electrical and electronic devices provided in the substrate processing apparatus 1. The control device 3 includes at least one computer that can communicate with each other. The computer includes a computer main body 3a and a peripheral device 3d connected to the computer main body 3a.

[0079] The computer main body 3a includes a CPU 3b (central processing unit) that executes various commands, and a memory 3c that stores information to be transmitted and received between the CPU 3b. The peripheral device 3d includes a storage 3e that stores information to be transmitted and received between the memory 3c, such as a program P, a reader 3f that reads information from removable media RM, and a communication device 3g that communicates with other devices such as a host computer HC. The memory 3c and the storage 3e are both examples of storage devices that store information to be transmitted and received between the CPU 3b.

[0080] The control device 3 is connected to an input device 3h and a display device 3i. The input device 3h is operated when an operator such as a user or a maintenance technician inputs information into the substrate processing apparatus 1. The information is displayed on the screen of the display device 3i. The input device 3h may be any one of a keyboard, a pointing device, and a touch panel, or may be a device other than these. The substrate processing apparatus 1 may be provided with a touch panel display that serves as both the input device 3h and the display device 3i.

[0081] The CPU 3b executes a program P stored in the storage 3e. The program P in the storage 3e may be one that has been pre-installed in the control device 3, or may be one that has been sent from a removable medium RM to the storage 3e via a reader 3f, or may be one that has been sent from an external device such as a host computer HC via a communication device 3g to the storage 3e.

[0082] The memory 3c is a volatile memory that retains its memory only when power is supplied. The storage 3e and the removable medium RM are non-volatile memories that retain their memory even when power is not supplied. The storage 3e is, for example, a magnetic storage device such as a hard disk drive. The removable medium RM is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a non-transitory tangible recording medium.

[0083] The storage 3e stores a plurality of recipes RC. The recipes RC are information that specifies the processing content, processing conditions, and processing procedures for the substrates W. The plurality of recipes RC differ from one another in at least one of the processing content, processing conditions, and processing procedures for the substrates W. The control device 3 controls the substrate processing apparatus 1 so that the substrates W are processed in accordance with the recipes RC specified by the host computer HC. The control device 3 is programmed to execute each of the processes described below. The programs P that execute each of the processes described below may be stored in either the storage 3e or the removable medium RM.

[0084] Next, an example of the structure of the substrate W will be described.

[0085] FIG. 8 is a schematic cross-sectional view showing an example of the structure of a substrate W processed by the substrate processing apparatus 1. The substrate W includes a front surface and a back surface that are parallel to each other, and an annular end surface that connects the outer edges of the front surface and the back surface along the entire periphery of the front surface and the back surface. FIG. 8 shows the state in which the front surface of the substrate W faces upward. The front surface of the substrate W corresponds to the upper surface of the substrate W. The front surface of the substrate W is a device formation surface on which devices are formed. The back surface of the substrate W is a non-device formation surface on which devices are not formed. Both the front surface and the back surface of the substrate W may be device formation surfaces.

[0086] The front and back surfaces of the substrate W are flat surfaces parallel to each other. When the pattern PA is formed on the surface of the substrate W, the surface of the substrate W is, strictly speaking, an uneven surface. The thickness direction of the substrate W is a direction perpendicular to the flat surface of the substrate W before the pattern PA is formed, and the surface direction of the substrate W is a direction parallel to the flat surface. In Figure 8, the up-down direction on the paper surface corresponds to the thickness direction of the substrate W, and the left-right direction on the paper surface corresponds to the surface direction of the substrate W. The pattern PA may be formed before the substrate processing apparatus 1 processes the substrate W, or may be formed while the substrate processing apparatus 1 is processing the substrate W.

[0087] FIG. 8 shows an example of a cross section of a substrate W cut along a plane perpendicular to the flat surface of the substrate W before the pattern PA is formed. In this example, a plurality of protrusions P1 are formed on the surface of a base layer s4 of the substrate W, extending in the thickness direction of the substrate W. The base layer s4 may be part of a disk-shaped semiconductor substrate, or a thin film formed on the substrate. The pattern PA includes a plurality of protrusions P1 and a plurality of recesses Q1. The plurality of protrusions P1 are spaced apart from each other in the surface direction of the substrate W. Two protrusions P1 face each other in the surface direction of the substrate W with a gap between them, forming recesses Q1 recessed in the thickness direction of the substrate W from the tips of the two protrusions P1.

[0088] FIG. 8 shows an example in which the cross section of the protrusion P1 is rectangular and extends in the thickness direction of the substrate W. The protrusion P1 may be cylindrical, prism-shaped, or plate-shaped, or may have other shapes. The recess Q1 may be a hole or a groove. The protrusion P1 may extend in the surface direction of the substrate W rather than in the thickness direction of the substrate W. The width of the protrusion P1 may be constant from the base of the protrusion P1 to the tip of the protrusion P1, or may vary. The width of the recess Q1 may be constant from the bottom of the recess Q1 to the entrance of the recess Q1, or may vary.

[0089] The protrusion P1 may be composed of only one layer, or may be composed of multiple layers stacked in the height direction of the protrusion P1. FIG. 8 shows an example of the former. In the latter case, all layers included in one protrusion P1 may be made of the same or different materials, or some of the layers may be made of the same material different from the rest of the layers. The material of the protrusion P1 may be one or more of a semiconductor, an insulator, and a metal, or may be other materials. The material of the end surface s1 of the protrusion P1 may be a silicon-containing material such as silicon dioxide, or may be other materials.

[0090] The surface of the pattern PA includes the surfaces of the convex portions P1 and the inner surfaces of the concave portions Q1. The surface of the convex portions P1 includes end faces s1 corresponding to the tips of the convex portions P1 and side faces s2 extending from the end faces s1 to the bases of the convex portions P1. The end faces s1 of the convex portions P1 correspond to the tip and top surfaces of the convex portions P1. The end faces s1 of the multiple convex portions P1 are arranged on a single plane. The end faces s1 of the multiple convex portions P1 correspond to part or all of the upper surface of the substrate W. The inner surfaces of the concave portions Q1 include bottom faces s3 corresponding to the bottom of the concave portions Q1 and side faces extending from the bottom faces s3 to the entrances of the concave portions Q1. The side faces of the concave portions Q1 may also serve as the side faces s2 of the convex portions P1, or may be different from the side faces s2. Figure 8 shows an example of the former. The side faces of the concave portions Q1 form the entrances of the concave portions Q1.

[0091] Next, an example of processing the substrate W will be described.

[0092] 9 is a process diagram for explaining an example of processing of a substrate W performed by the substrate processing apparatus 1. In the following, reference will be made to FIGS.

[0093] When the substrate W is processed by the substrate processing apparatus 1, a loading step (step S1 in FIG. 9) of loading the substrate W into the chamber 4 is performed.

[0094] Specifically, with the blocking member 51 in the upper position, all guards 24 in the lower position, and all scan nozzles in the standby position, the center robot CR (see FIG. 1A) supports the substrate W with the hand Hc and causes the hand Hc to enter the chamber 4. The center robot CR then places the substrate W on the hand Hc onto the multiple chuck pins 11 with the front surface of the substrate W facing upward. The multiple chuck pins 11 are then pressed against the edge surface of the substrate W, thereby gripping the substrate W. After placing the substrate W on the spin chuck 10, the center robot CR then retracts the hand Hc from the interior of the chamber 4.

[0095] Next, the inert gas valve 84 is opened, and the central opening 81 of the spin base 12 begins to discharge nitrogen gas. Similarly, the inert gas valve 64 is opened, and the central opening 61 of the blocking member 51 begins to discharge nitrogen gas. Meanwhile, the lifting actuator 27 raises at least one guard 24 from the lower position to the upper position. Thereafter, the spin motor 14 is driven, and the rotation of the substrate W begins (step S2 in FIG. 9). Similarly, the rotation actuator 54r is driven, and the rotation of the blocking member 51 begins. The rotation speed and rotation direction of the blocking member 51 are controlled to match the rotation speed and rotation direction of the substrate W until the rotation of the substrate W is stopped.

[0096] Next, a first chemical liquid supplying step (step S3 in FIG. 9) is performed in which DHF, which is an example of a chemical liquid, is supplied onto the upper surface of the substrate W to form a liquid film of DHF that covers the entire upper surface of the substrate W.

[0097] Specifically, with blocking member 51 in the upper position and at least one guard 24 in the upper position, first nozzle actuator 34a moves first chemical liquid nozzle 31a and first rinse liquid nozzle 35a from the standby position to the processing position. Then, first chemical liquid valve 33a is opened, and first chemical liquid nozzle 31a begins to discharge DHF. After a predetermined time has elapsed since first chemical liquid valve 33a was opened, first chemical liquid valve 33a is closed, and the discharge of DHF is stopped.

[0098] The DHF discharged from first chemical liquid nozzle 31a collides with the upper surface of substrate W, which is rotating at the first chemical liquid supply speed, and then flows outward along the upper surface of substrate W. Therefore, DHF is supplied to the entire upper surface of substrate W, and a DHF liquid film is formed covering the entire upper surface of substrate W. While first chemical liquid nozzle 31a is discharging DHF, first nozzle actuator 34a may move the collision position of DHF with the upper surface of substrate W so that the collision position passes through the center and the outer periphery, or may keep the collision position stationary at the center. Whether or not the collision position is moved applies similarly to the processing liquid supplied to the upper surface of substrate W after DHF.

[0099] Next, a first rinse liquid supplying step (step S4 in FIG. 9) is performed in which pure water, which is an example of a rinse liquid, is supplied to the upper surface of the substrate W to wash away DHF from the substrate W.

[0100] Specifically, with the blocking member 51 in the upper position, at least one guard 24 in the upper position, and the first chemical liquid nozzle 31a and the first rinse liquid nozzle 35a in the processing position, the first rinse liquid valve 37a is opened and the first rinse liquid nozzle 35a starts to discharge deionized water. Before the discharge of deionized water starts, the lifting actuator 27 may vertically move at least one guard 24 to switch the guard 24 that receives the liquid discharged from the substrate W. Whether or not to switch the guard 24 that receives the liquid discharged from the substrate W also applies to the processing liquid supplied to the upper surface of the substrate W after the deionized water.

[0101] The deionized water discharged from the first rinse liquid nozzle 35a collides with the upper surface of the substrate W, which is rotating at the first rinse liquid supply speed, and then flows outward along the upper surface of the substrate W. The DHF on the substrate W is replaced with the deionized water discharged from the first rinse liquid nozzle 35a. This forms a liquid film of deionized water that covers the entire upper surface of the substrate W. When a predetermined time has elapsed since the first rinse liquid valve 37a was opened, the first rinse liquid valve 37a is closed, and the discharge of deionized water is stopped. Thereafter, the first nozzle actuator 34a moves the first chemical liquid nozzle 31a and the first rinse liquid nozzle 35a to their standby positions.

[0102] Next, a second chemical liquid supplying step (step S5 in FIG. 9) is performed in which SC1, an example of a chemical liquid, is supplied onto the upper surface of the substrate W to form a liquid film of SC1 that covers the entire upper surface of the substrate W.

[0103] Specifically, with blocking member 51 in the upper position and at least one guard 24 in the upper position, second nozzle actuator 34b moves second chemical liquid nozzle 31b and second rinsing liquid nozzle 35b from the standby position to the processing position. Then, second chemical liquid valve 33b is opened, and second chemical liquid nozzle 31b starts discharging SC1.

[0104] SC1 discharged from second chemical liquid nozzle 31b collides with the upper surface of substrate W, which is rotating at the second chemical liquid supply speed, and then flows outward along the upper surface of substrate W. The pure water on substrate W is replaced with SC1 discharged from second chemical liquid nozzle 31b. This forms a liquid film of SC1 that covers the entire upper surface of substrate W. When a predetermined time has elapsed since second chemical liquid valve 33b was opened, second chemical liquid valve 33b is closed, and the discharge of SC1 is stopped.

[0105] Next, a second rinse liquid supplying step (step S6 in FIG. 9) is performed in which pure water, which is an example of a rinse liquid, is supplied to the upper surface of the substrate W to wash away SC1 on the substrate W.

[0106] Specifically, when the blocking member 51 is in the upper position, at least one guard 24 is in the upper position, and the second chemical liquid nozzle 31b and the second rinse liquid nozzle 35b are in the processing position, the second rinse liquid valve 37b is opened and the second rinse liquid nozzle 35b begins to spray pure water.

[0107] The deionized water discharged from second rinse liquid nozzle 35b collides with the upper surface of substrate W, which is rotating at the second rinse liquid supply speed, and then flows outward along the upper surface of substrate W. SC1 on substrate W is replaced with the deionized water discharged from second rinse liquid nozzle 35b. This forms a liquid film of deionized water that covers the entire upper surface of substrate W. When a predetermined time has elapsed since second rinse liquid valve 37b was opened, second rinse liquid valve 37b is closed, and the discharge of deionized water is stopped. Then, second nozzle actuator 34b moves second chemical liquid nozzle 31b and second rinse liquid nozzle 35b to the standby position.

[0108] Next, a pre-treatment liquid supplying step (step S7 in FIG. 9) is performed in which IPA, which is an example of a pre-treatment liquid, is supplied to the upper surface of the substrate W to replace the pure water on the substrate W with IPA.

[0109] Specifically, with the blocking member 51 in the upper position, at least one guard 24 in the upper position, and all scan nozzles in the standby position, the pretreatment liquid valve 45 is opened, and the center nozzle 55 starts to discharge IPA. After a predetermined time has elapsed since the pretreatment liquid valve 45 was opened, the pretreatment liquid valve 45 is closed, and the discharge of IPA is stopped. As shown in FIG. 9, the substrate W is cooled in the pretreatment liquid supplying step. The substrate W is also cooled in the sublimable substance-containing liquid supplying step (step S8 in FIG. 9), which will be described later. The cooling of the substrate W will be described later.

[0110] The IPA discharged from the central nozzle 55 collides with the upper surface of the substrate W, which is rotating at the pretreatment liquid supply speed, and then flows outward along the upper surface of the substrate W. The deionized water on the substrate W is replaced with the IPA discharged from the central nozzle 55. This forms a liquid film of IPA that covers the entire upper surface of the substrate W. After the central nozzle 55 stops discharging the IPA, the substrate W may be rotated at a paddle speed (for example, a speed greater than 0 and equal to or less than 30 rpm) while maintaining a state in which the entire upper surface of the substrate W is covered with the liquid film of IPA.

[0111] Next, a sublimable substance-containing liquid supplying step (step S8 in FIG. 9) is performed in which the sublimable substance-containing liquid is supplied onto the upper surface of the substrate W to form a liquid film of the sublimable substance-containing liquid covering the entire upper surface of the substrate W.

[0112] Specifically, with the blocking member 51 in the upper position, at least one guard 24 in the upper position, and all scan nozzles in the standby position, the sublimable substance-containing liquid valve 43 is opened and the central nozzle 55 starts to discharge the sublimable substance-containing liquid. The sublimable substance-containing liquid discharged from the central nozzle 55 collides with the upper surface of the substrate W rotating at the sublimable substance supply speed, and then flows outward along the upper surface of the substrate W. The IPA on the substrate W is replaced with the sublimable substance-containing liquid discharged from the central nozzle 55. As a result, a liquid film of the sublimable substance-containing liquid is formed covering the entire upper surface of the substrate W. When a predetermined time has elapsed since the sublimable substance-containing liquid valve 43 was opened, the sublimable substance-containing liquid valve 43 is closed and the discharge of the sublimable substance-containing liquid is stopped.

[0113] Next, a solidified film forming step (step S9 in FIG. 9) is performed in which the liquid film of the sublimable substance-containing liquid on the substrate W is transformed into a solidified film SF (see FIG. 11D) containing the sublimable substance.

[0114] Specifically, with at least one guard 24 in the upper position, the vertical actuator 54v lowers the blocking member 51 to the lower position. Simultaneously with, before, or after the blocking member 51 reaches the lower position, the inert gas valve 57 is opened, and the center nozzle 55 begins to discharge nitrogen gas. Furthermore, simultaneously with, before, or after the blocking member 51 reaches the lower position, the spin motor 14 increases the rotation speed of the substrate W to a solidified film formation speed. The solidified film formation speed may be equal to or different from the sublimable material supply speed.

[0115] When the rotation of the substrate W at the solidified film formation speed is started, the evaporation of the sublimable substance-containing liquid is promoted. When the sublimable substance-containing liquid is a solution, the vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance corresponding to the solute, so the solvent evaporates at a rate higher than the evaporation rate of the sublimable substance. Therefore, the concentration of the sublimable substance gradually increases, while the film thickness of the sublimable substance-containing liquid gradually decreases. As a result, the sublimable substance is precipitated from the sublimable substance-containing liquid on the substrate W, and a solidified film SF is formed that covers the entire upper surface of the substrate W.

[0116] Next, a sublimation step (step S10 in FIG. 9) is performed in which the solidified film SF on the substrate W is sublimated and removed from the upper surface of the substrate W.

[0117] Specifically, with the blocking member 51 in the lower position and the central nozzle 55 discharging nitrogen gas, the spin motor 14 maintains the rotation speed of the substrate W at the sublimation speed. The sublimation speed may be equal to or different from the sublimable substance supply rate. Simultaneously with, before, or after the rotation speed of the substrate W reaches the sublimation speed, the flow rate of the nitrogen gas discharged from the central nozzle 55 may be increased or decreased. The same applies to the flow rate of the nitrogen gas discharged from the central opening 61 of the blocking member 51.

[0118] When the rotation of the substrate W at the sublimation speed starts, the solidified film SF on the substrate W starts to sublimate, and a gas containing a sublimable substance is generated from the solidified film SF on the substrate W. The gas (gas containing a sublimable substance) generated from the solidified film SF flows radially in the space between the substrate W and the blocking member 51, and is discharged from above the substrate W. After a certain amount of time has passed since the start of sublimation, all of the solidified film SF is removed from the substrate W. Thereafter, the spin motor 14 stops rotating. This stops the rotation of the substrate W (step S11 in FIG. 9).

[0119] Next, an unloading step (step S12 in FIG. 9) of unloading the substrate W from the chamber 4 is performed.

[0120] Specifically, the vertical actuator 54v raises the blocking member 51 to the upper position, and the lifting actuator 27 lowers all of the guards 24 to the lower position. Furthermore, the inert gas valve 57, the inert gas valve 64, and the inert gas valve 84 are closed. The center robot CR then causes the hand Hc to enter the chamber 4. After the chuck pins 11 release their grip on the substrate W, the center robot CR supports the substrate W on the spin chuck 10 with the hand Hc. The center robot CR then retracts the hand Hc from the interior of the chamber 4 while still supporting the substrate W with the hand Hc. This causes the processed substrate W to be removed from the chamber 4.

[0121] Next, a specific example of the steps from the pre-treatment liquid supply step to the sublimation step will be described.

[0122] Fig. 10 is a timing chart for explaining a specific example of the steps from the pre-treatment liquid supply step to the sublimation step. Figs. 11A, 11B, 11C, 11D, 11E, 11F, 11G, 11H, and 11I are schematic views showing the substrate W when the steps shown in Fig. 10 are being performed. Figs. 11A to 11D are schematic views of the substrate W viewed horizontally. Figs. 11E to 11I are schematic cross-sectional views of the substrate W. Each item on the vertical axis in Fig. 10, except for the position of the blocking member 51, indicates that the value increases as it moves away from 0 upward.

[0123] The pretreatment liquid supply step (step S7 in FIG. 9) includes a pretreatment liquid discharge step of discharging the pretreatment liquid toward the upper surface of the substrate W. The pretreatment liquid discharge step includes a discharge start step of starting the discharge of the pretreatment liquid toward the upper surface of the substrate W, and a discharge stop step of stopping the discharge of the pretreatment liquid toward the upper surface of the substrate W. FIG. 10 shows an example in which the discharge of the pretreatment liquid starts at time T0 and stops at time T3. The pretreatment liquid discharge step may be a step of discharging the pretreatment liquid toward the upper surface of the substrate W while rotating the substrate W, or a step of discharging the pretreatment liquid toward the upper surface of the substrate W while keeping the substrate W stationary. FIG. 10 shows the former example.

[0124] The pretreatment liquid supply step may include at least one of a replacement promotion step of promoting replacement with the pretreatment liquid and a puddle step of causing the pretreatment liquid to stagnate on the upper surface of the substrate W while maintaining a state in which the upper surface of the substrate W is covered with a liquid film of the pretreatment liquid, or may not include both the replacement promotion step and the puddle step. Fig. 10 shows an example in which the pretreatment liquid supply step includes both the replacement promotion step and the puddle step.

[0125] The puddling process is a process of rotating the substrate W at a stationary or low speed (for example, a speed exceeding 0 and not exceeding 30 rpm) while keeping the upper surface of the substrate W covered with a liquid film of the pretreatment liquid. The puddling process may be a process of performing the puddling process while or without discharging the pretreatment liquid toward the upper surface of the substrate W, or may include a process of performing the puddling process while discharging the pretreatment liquid toward the upper surface of the substrate W and a process of performing the puddling process without discharging the pretreatment liquid toward the upper surface of the substrate W.

[0126] The replacement promotion step is a step of increasing the rotation speed of the substrate W while discharging the pretreatment liquid toward the upper surface of the substrate W. The replacement promotion step may be a step of increasing the flow rate of the pretreatment liquid discharged toward the upper surface of the substrate W as the rotation speed of the substrate W increases, or a step of increasing the rotation speed of the substrate W while discharging the pretreatment liquid toward the upper surface of the substrate W at a constant flow rate regardless of the rotation speed of the substrate W. The replacement promotion step may be a step of increasing and then decreasing the rotation speed of the substrate W while discharging the pretreatment liquid toward the upper surface of the substrate W. In this case, the flow rate of the pretreatment liquid discharged toward the upper surface of the substrate W may decrease simultaneously or approximately simultaneously with the decrease in the rotation speed of the substrate W, or may decrease after the decrease in the rotation speed of the substrate W.

[0127] FIG. 10 shows an example in which the rotation speed of the substrate W increases from the promotion start speed V1 to the promotion maximum speed V2 and then decreases to the paddle speed V3 corresponding to the promotion stop speed, and the flow rate of the pretreatment liquid ejected onto the upper surface of the substrate W increases from the promotion start flow rate R1 to the promotion maximum flow rate R2 and then decreases stepwise to zero corresponding to the promotion stop flow rate.

[0128] The process in which the rotation speed of the substrate W increases from the promotion start speed V1 to the promotion maximum speed V2 is the rotation acceleration process, and the process in which the rotation speed decreases from the promotion maximum speed V2 to the paddle speed V3 is the rotation deceleration process. The process in which the flow rate of the pretreatment liquid discharged onto the upper surface of the substrate W increases from the promotion start flow rate R1 to the promotion maximum flow rate R2 is the flow rate increase process, and the process in which the flow rate decreases from the promotion maximum flow rate R2 to zero is the flow rate decrease process.

[0129] 10, the flow rate of the pretreatment liquid reaches the maximum promotion flow rate R2 before the rotation speed of the substrate W reaches the maximum promotion speed V2, and the flow rate of the pretreatment liquid is maintained at the maximum promotion flow rate R2 even after the rotation speed of the substrate W decreases from the maximum promotion speed V2. The flow rate of the pretreatment liquid starts to decrease before the rotation speed of the substrate W reaches the paddle speed V3. The flow rate of the pretreatment liquid decreases to zero after the rotation speed of the substrate W reaches the paddle speed V3. Therefore, in the example shown in FIG. 10, the discharge of the pretreatment liquid onto the upper surface of the substrate W is stopped, and the substrate W rotates at the paddle speed V3 (for example, a speed greater than 0 and equal to or less than 30 rpm) while the entire upper surface of the substrate W is kept covered with a liquid film of the pretreatment liquid.

[0130] When the substrate W reaches or immediately before the paddle speed V3, the flow rate of the pretreatment liquid supplied to the upper surface of the substrate W is greater than the flow rate of the pretreatment liquid discharged from the upper surface of the substrate W. Therefore, the thickness of the liquid film of the pretreatment liquid covering the upper surface of the substrate W continuously increases as the rotation speed of the substrate W approaches the paddle speed V3. When the substrate W is rotating at the paddle speed V3, no pretreatment liquid is discharged from the upper surface of the substrate W, or only a small amount of the pretreatment liquid is discharged from the upper surface of the substrate W. When the discharge of the pretreatment liquid onto the upper surface of the substrate W is stopped while the substrate W is rotating at the paddle speed V3, the thickness of the liquid film of the pretreatment liquid remains approximately the same as when the discharge was stopped. The thickness of the liquid film of the pretreatment liquid when the discharge of the pretreatment liquid onto the upper surface of the substrate W is stopped is greater than the thickness of the liquid film of the pretreatment liquid when the substrate W is rotating at the maximum acceleration speed V2.

[0131] After the pretreatment liquid supplying step is performed, a sublimable substance-containing liquid supplying step (step S8 in FIG. 9) is performed. The sublimable substance-containing liquid supplying step includes a sublimable substance-containing liquid discharging step of discharging the sublimable substance-containing liquid toward the upper surface of the substrate W. The sublimable substance-containing liquid discharging step includes a discharging start step of starting to discharge the sublimable substance-containing liquid toward the upper surface of the substrate W, and a discharging stop step of stopping the discharging of the sublimable substance-containing liquid toward the upper surface of the substrate W. FIG. 10 shows an example in which the discharging of the sublimable substance-containing liquid is started at time T4 and stopped at time T5. The sublimable substance-containing liquid discharging step may be a step of discharging the pretreatment liquid toward the upper surface of the substrate W while rotating the substrate W, or may be a step of discharging the pretreatment liquid toward the upper surface of the substrate W while keeping the substrate W stationary. FIG. 10 shows the former example.

[0132] 10, the rotation speed of the substrate W is maintained at the paddle speed V3 throughout the entire period during which the sublimable substance-containing liquid is discharged. That is, in this example, the paddle speed V3 corresponds to the sublimable substance supply speed. During the period during which the sublimable substance-containing liquid is discharged, the rotation speed of the substrate W may be maintained at a constant value other than the paddle speed V3, or may be changed.

[0133] The sublimable substance-containing liquid supplying step may or may not include a film thickness reducing step of reducing the film thickness (liquid film thickness) of the sublimable substance-containing liquid on the substrate W while maintaining a state in which the entire upper surface of the substrate W is covered with a liquid film of the sublimable substance-containing liquid. FIG. 10 shows an example of the former. In this example, after the discharge of the sublimable substance-containing liquid is stopped, the rotation speed of the substrate W increases from the paddle speed V3 to a first film thickness reducing speed V4 and then decreases to a second film thickness reducing speed V5. The rotation speed of the substrate W is maintained at the second film thickness reducing speed V5 for a period longer than the period during which the substrate W rotates at the first film thickness reducing speed V4. The second film thickness reducing speed V5 may be equal to or different from the paddle speed V3.

[0134] While the rotation speed of the substrate W changes from the paddle speed V3 to the second film thickness reduction speed V5, the sublimable substance-containing liquid is discharged from the upper surface of the substrate W. While the rotation speed of the substrate W changes from the first film thickness reduction speed V4 to the second film thickness reduction speed V5, the discharge flow rate of the sublimable substance-containing liquid (the amount of sublimable substance-containing liquid discharged from the substrate W per unit time) decreases. While the substrate W is rotating at the second film thickness reduction speed V5, the discharge flow rate of the sublimable substance-containing liquid decreases to zero or approximately zero, and the thickness of the liquid film of the sublimable substance-containing liquid on the substrate W stabilizes at a value corresponding to the rotation speed of the substrate W.

[0135] After the sublimable substance-containing liquid supplying step is performed, a solidified film forming step (step S9 in FIG. 9) is performed. The solidified film forming step includes an airflow forming step of forming an airflow that flows along the upper surface of the substrate W.

[0136] The airflow generating step may be either a substrate rotation step or a gas discharge step, or may be both a substrate rotation step and a gas discharge step. Figure 10 shows an example of the latter. The substrate rotation step is a step of forming an airflow that flows along the upper surface of the substrate W by rotating the substrate W. The gas discharge step is a step of forming an airflow that flows radially from the center of the upper surface of the substrate W to the outer periphery of the upper surface of the substrate W by discharging gas toward the center of the upper surface of the substrate W.

[0137] 10 shows an example in which the gas discharge step of the solidified film formation step is a step in which nitrogen gas is discharged from the center nozzle 55 toward the center of the upper surface of the substrate W while the blocking member 51 is positioned at the lower position. In this example, the blocking member 51 is lowered to the lower position at time T7 while rotating the substrate W at the second film thickness reduction speed V5. Thereafter, the rotation speed of the substrate W is increased from the second film thickness reduction speed V5 to the solidified film formation speed V6. Furthermore, simultaneously with, before, or after the blocking member 51 reaches the lower position, the center nozzle 55 starts discharging nitrogen gas, or the flow rate of the nitrogen gas discharged from the center nozzle 55 is increased.

[0138] The central nozzle 55 discharges nitrogen gas at a flow rate for forming a solidified film. The nitrogen gas discharged from the central nozzle 55 collides with the center of the upper surface of the substrate W, and then flows radially in all directions between the upper surface of the substrate W and the lower surface 51L of the blocking member 51 (see FIG. 11D). As a result, a flow of nitrogen gas is formed that flows radially from the center of the upper surface of the substrate W to the outer periphery of the upper surface of the substrate W along the upper surface of the substrate W, and the space between the substrate W and the blocking member 51 is filled with nitrogen gas. Furthermore, an airflow is also formed that flows along the upper surface of the substrate W as the substrate W rotates. This promotes evaporation of the sublimable substance-containing liquid, and the liquid film of the sublimable substance-containing liquid on the substrate W turns into a solidified film SF (see FIG. 11D) containing the sublimable substance.

[0139] 11D shows a state in which the shielding member 51 is disposed in the lower position. When the shielding member 51 is disposed in the lower position, a distance D1 (see FIG. 11D) from the upper surface of the substrate W held on the spin chuck 10 (see FIG. 2) to the lower surface 51L of the shielding member 51 may be a value greater than 0 that is smaller than a diameter D2 (see FIG. 11D) of the central opening 61 of the shielding member 51. The distance D1 may be a value (in millimeters) greater than 0 and equal to or less than 3, preferably 1. As the distance D1 decreases, the speed of the nitrogen gas flowing radially between the substrate W and the shielding member 51 increases. Therefore, the time required to form the solidified film SF can be shortened.

[0140] 10 shows an example in which the discharge of cold water starts at time T2 and stops at time T6. In this example, the discharge of cold water starts after the rotation speed of the substrate W is reduced from the maximum acceleration speed V2 and before the discharge of the pretreatment liquid onto the upper surface of the substrate W is stopped. Furthermore, in this example, the discharge of cold water stops after the discharge of the sublimable substance-containing liquid onto the upper surface of the substrate W is stopped and before the blocking member 51 reaches the lower position.

[0141] The discharge of cold water may be started simultaneously with the rotation speed of the substrate W decreasing from the maximum acceleration speed V2, or may be started before that. The discharge of cold water may be started simultaneously with the start of the discharge of the pretreatment liquid onto the upper surface of the substrate W, or may be started before or after that. If the upper surface of the substrate W is covered with a liquid film of the pretreatment liquid, the discharge of cold water may be started after the discharge of the pretreatment liquid onto the upper surface of the substrate W has stopped.

[0142] The discharge of cold water may be stopped at the same time as the discharge of the sublimable substance-containing liquid onto the upper surface of the substrate W is stopped, or may be stopped before that. The discharge of cold water may be stopped at the same time as the blocking member 51 reaches the lower position, or may be stopped thereafter. In the latter case, the discharge of cold water may be stopped while the solidified film SF is being formed, or after all of the sublimable substance-containing liquid on the substrate W has turned into the solidified film SF.

[0143] Cold water is an example of a cooling substance that is at a lower temperature than the substrate W. The temperature of the cold water is above 0°C and below room temperature. The temperature of the cold water may be 5 to 10°C. The substrate W may be at room temperature, or at a temperature higher or lower than room temperature before the cold water comes into contact with the substrate W. IPA is an example of a pretreatment liquid. If the cold water is at a lower temperature than the IPA, the IPA may be at room temperature, or at a temperature higher or lower than room temperature. The same applies to the sublimable substance-containing liquid. In the following, it is assumed that the IPA and the sublimable substance-containing liquid are at room temperature before being supplied to the substrate W.

[0144] 10, cold water, an example of a cooling substance, is discharged from the lower nozzle 71 (see FIG. 2) toward the lower surface of the substrate W while at least one of the pre-treatment liquid and the sublimable substance-containing liquid is present on the upper surface of the substrate W. Therefore, the pre-treatment liquid supplying step includes a first substrate cooling step of bringing the cooling substance into contact with the lower surface of the substrate W while the pre-treatment liquid is present on the upper surface of the substrate W, and the sublimable substance-containing liquid supplying step includes a second substrate cooling step of bringing the cooling substance into contact with the lower surface of the substrate W while the sublimable substance-containing liquid is present on the upper surface of the substrate W. The solidified film forming step may include a third substrate cooling step of bringing the cooling substance into contact with the lower surface of the substrate W while at least one of the sublimable substance-containing liquid and the solidified film SF is present on the upper surface of the substrate W. In other words, the discharge of cold water may be stopped while the solidified film SF is being formed or after all of the sublimable substance-containing liquid on the substrate W has been converted into the solidified film SF.

[0145] 10 shows an example in which the second substrate cooling step is continuous with the first substrate cooling step. In other words, FIG. 10 shows an example in which the pretreatment liquid and the sublimable substance-containing liquid are sequentially supplied to the upper surface of the substrate W while cold water is supplied to the lower surface of the substrate W. The discharge of cold water to the lower surface of the substrate W may be temporarily stopped before the supply of the sublimable substance-containing liquid to the upper surface of the substrate W is started. In other words, the period during which the discharge of cold water to the lower surface of the substrate W is stopped may be between the first substrate cooling step and the second substrate cooling step. This also applies when the solidified film formation step includes a third substrate cooling step.

[0146] 11A, when the cold water comes into contact with the lower surface of the substrate W, the substrate W is cooled. The pretreatment liquid on the substrate W is cooled by the cold water through the substrate W. The temperatures of the substrate W and the pretreatment liquid decrease to the same or nearly the same as the temperature of the cold water. As shown in FIG. 11B, the sublimable substance-containing liquid is discharged toward the upper surface of the substrate W covered with a liquid film of the pretreatment liquid, while the cold water is being discharged toward the lower surface of the substrate W.

[0147] The sublimable substance-containing liquid flows along the upper surface of the substrate W while mixing with the pretreatment liquid on the substrate W. As a result, a liquid containing at least one of the sublimable substance-containing liquid and the pretreatment liquid is discharged from the upper surface of the substrate W. As shown in FIG. 11C, when the supply of the sublimable substance-containing liquid continues, the pretreatment liquid on the substrate W is replaced by the sublimable substance-containing liquid, and the entire upper surface of the substrate W is covered with a liquid film of the sublimable substance-containing liquid. Thereafter, as shown in FIG. 11D, the liquid film of the sublimable substance-containing liquid on the substrate W turns into a solidified film SF that covers the upper surface of the substrate W.

[0148] When the sublimable substance-containing liquid comes into contact with the pretreatment liquid on the substrate W, the cooling of the sublimable substance-containing liquid begins. The sublimable substance-containing liquid mixes with the pretreatment liquid on the substrate W, increasing the contact area between the sublimable substance-containing liquid and the pretreatment liquid. Furthermore, the sublimable substance-containing liquid diffuses in the pretreatment liquid on the substrate W, further increasing the contact area between the sublimable substance-containing liquid and the pretreatment liquid. This allows the sublimable substance-containing liquid on the substrate W to be efficiently cooled. In particular, since the substrate W and the pretreatment liquid are cooled by cold water while the thickness of the liquid film of the pretreatment liquid on the substrate W is increased, the cooling ability of the pretreatment liquid is enhanced compared to when the liquid film is thin. In other words, the total amount of heat that the pretreatment liquid can absorb is increased. This allows the sublimable substance-containing liquid on the substrate W to be rapidly cooled.

[0149] When the liquid containing a sublimable substance is a solution, a decrease in the temperature of the liquid containing a sublimable substance reduces the solubility of the sublimable substance in the solvent of the liquid containing a sublimable substance. When the decrease in the temperature of the liquid containing a sublimable substance causes the concentration of the sublimable substance in the liquid containing a sublimable substance to exceed the saturated concentration, the sublimable substance precipitates from the liquid containing a sublimable substance.

[0150] The temperature of the cooling substance, such as cold water, is equal to or lower than the temperature at which the sublimable substance precipitates from the sublimable substance-containing liquid. If the concentration of the sublimable substance in the sublimable substance-containing liquid changes, the temperature at which the sublimable substance precipitates from the sublimable substance-containing liquid also changes. Therefore, the temperature of the cooling substance can be set according to the concentration of the sublimable substance in the sublimable substance-containing liquid. Alternatively, the concentration of the sublimable substance in the sublimable substance-containing liquid can be set according to the temperature of the cooling substance.

[0151] If the sublimable substance-containing liquid on the substrate W is not cooled with a cooling substance during the period from when the supply of the pretreatment liquid onto the upper surface of the substrate W starts until the liquid film of the sublimable substance-containing liquid changes into a solidified film SF, the temperature of the substrate W will drop to a value below room temperature due to evaporation of the sublimable substance-containing liquid when the liquid film of the sublimable substance-containing liquid changes into a solidified film SF. In this case, the temperature of the cooling substance may be lower than the temperature of the substrate W when the solidified film SF is formed.

[0152] The sublimable substance-containing liquid is supplied to the upper surface of the substrate W covered with a film of the pretreatment liquid in a state where the temperatures of the substrate W and the pretreatment liquid have been reduced. The temperature of the pretreatment liquid on the substrate W is not strictly uniform, but decreases toward the upper surface of the substrate W. The temperature of the pretreatment liquid on the substrate W is lowest on the inner surface of the recess Q1 of the pattern PA. Therefore, deposition of the sublimable substance is likely to begin in the recess Q1.

[0153] As shown in FIG. 11E, the sublimable substance-containing liquid enters the recess Q1. The hexagonal shapes in FIG. 11F and FIG. 11G represent crystals of the sublimable substance. When a crystal nucleus of the sublimable substance is generated in the recess Q1, the sublimable substance contained in the sublimable substance-containing liquid precipitates on the surface of the crystal nucleus, and the crystal nucleus gradually grows. The crystal of the sublimable substance in the recess Q1 may combine with another crystal of the sublimable substance in the recess Q1. This increases the volume of the portion of the area in the recess Q1 that is occupied by the solid (crystal of the sublimable substance). In other words, as the solid is generated and grows in the recess Q1, the liquid (liquid containing the sublimable substance) in the recess Q1 decreases.

[0154] Because the sublimable substance-containing liquid is cooled on the substrate W before the solidified film formation process is started, the above-mentioned crystals of the sublimable substance are generated and grow in the recess Q1 before the solidified film formation process is started. When the solidified film formation process is started, the airflow flowing along the upper surface of the substrate W becomes stronger, accelerating evaporation of the sublimable substance-containing liquid from the surface of the sublimable substance-containing liquid on the substrate W. This further reduces the temperature of the sublimable substance-containing liquid on the substrate W. Accordingly, the crystals of the sublimable substance generated before the solidified film formation process grow further or combine with the crystals of the sublimable substance generated after the solidified film formation process. As a result, the liquid film of the sublimable substance-containing liquid is transformed into a solidified film SF, as shown in FIG. 11H.

[0155] Bottom-up growth is defined as the process in which crystals of a sublimable substance are generated in the recess Q1 and then grow toward the entrance of the recess Q1. Bottom-up growth can be generated by cooling the sublimable substance-containing liquid through the substrate W, and a solidified film SF can be formed on the substrate W with no or almost no liquid remaining in the recess Q1.

[0156] After the solidified film formation process, the sublimation process (step S10 in FIG. 9) is performed. The sublimation process includes an airflow formation process that forms an airflow that flows along the upper surface of the substrate W. The airflow formation process may be either the substrate rotation process or the gas discharge process described above, or may be both the substrate rotation process and the gas discharge process. FIG. 10 shows an example of the latter. In this example, the blocking member 51 is positioned in the lower position, and nitrogen gas is discharged from the central nozzle 55 at a sublimation flow rate while the rotation speed of the substrate W is increased from the solidified film formation speed V6 to the sublimation speed V7. The sublimation flow rate may be equal to or different from the solidified film formation flow rate. FIG. 10 shows an example of the former.

[0157] Since the central nozzle 55 ejects nitrogen gas toward the upper surface of the substrate W, a flow of nitrogen gas is formed that flows radially from the center of the upper surface of the substrate W to the outer periphery of the upper surface of the substrate W, similar to the solidified film formation process. Furthermore, when the rotation speed of the substrate W increases to sublimation speed V7, a stronger airflow is formed on the upper surface of the substrate W than when the substrate W is rotating at solidified film formation speed V6. This causes the solidified film SF on the substrate W to begin to sublimate. After a certain amount of time has passed since the start of sublimation, all of the solidified film SF is removed from the substrate W, as shown in FIG. 11I. Thereafter, the rotation of the substrate W is stopped, and the substrate W is unloaded from the chamber 4 (see FIG. 2).

[0158] When the discharge of cold water onto the underside of the substrate W begins, not only is the substrate W cooled, but the cold water also falls from the underside of the substrate W. If the rotation speed of the substrate W is equal to or greater than a certain value, the cold water not only falls from the underside of the substrate W, but also splashes from the outer periphery of the underside of the substrate W. Therefore, a mist of cold water is dispersed in the space in which the substrate W is placed, increasing the humidity in the space. In contrast, when the discharge of cold water onto the underside of the substrate W is stopped, the amount of cold water that falls or splashes from the substrate W decreases. Therefore, the humidity in the space in which the substrate W is placed decreases. In other words, by starting or stopping the discharge of cold water onto the underside of the substrate W, the humidity in the space in which the substrate W is placed can be increased or decreased.

[0159] As described above, when the pretreatment liquid on the substrate W is replaced with the sublimable substance-containing liquid or when the sublimable substance-containing liquid is on the upper surface of the substrate W, cold water is discharged toward the lower surface of the substrate W, and the humidity in the space in which the substrate W is placed is relatively high. Therefore, the surface of the sublimable substance-containing liquid on the substrate W is unlikely to dry. If the humidity in the space in which the substrate W is placed is relatively high when forming the solidified film SF, the possibility of film-like crystals of the sublimable substance forming only on the surface of the sublimable substance-containing liquid can be reduced. If the solidified film SF contains water, evaporation of water from the solidified film SF can be promoted by relatively lowering the humidity in the space in which the substrate W is placed when sublimating the solidified film SF.

[0160] Next, the effects of this embodiment will be described.

[0161] In this embodiment, the upper surface of the substrate W, on which a pattern PA including a plurality of convex portions P1 and a plurality of concave portions Q1 is formed, is covered with a liquid film of the pretreatment liquid, while a cooling substance is brought into contact with the lower surface of the substrate W. The pretreatment liquid is cooled by the cooling substance via the substrate W. After the temperature of the pretreatment liquid has been reduced, the pretreatment liquid on the upper surface of the substrate W is replaced with a sublimable substance-containing liquid, thereby covering the upper surface of the substrate W with a liquid film of the sublimable substance-containing liquid, while bringing the cooling substance into contact with the lower surface of the substrate W. Since the pretreatment liquid is cooled, cooling of the sublimable substance-containing liquid begins when the sublimable substance-containing liquid comes into contact with the pretreatment liquid on the substrate W.

[0162] The sublimable substance-containing liquid supplied to the upper surface of the substrate W mixes with the pretreatment liquid on the substrate W. The temperature of the pretreatment liquid on the substrate W is not strictly uniform, but decreases toward the upper surface of the substrate W. The temperature of the pretreatment liquid on the substrate W is lowest on the inner surface of the recess Q1 of the pattern PA. Therefore, precipitation of the sublimable substance is likely to begin in the recess Q1. When a crystal nucleus of the sublimable substance is generated in the recess Q1, the sublimable substance contained in the sublimable substance-containing liquid precipitates on the surface of the crystal nucleus, gradually increasing the size of the crystal nucleus. The sublimable substance crystals in the recess Q1 may combine with other sublimable substance crystals in the recess Q1. This increases the volume of the portion of the recess Q1 occupied by the solid (crystals of the sublimable substance). In other words, as the solid is generated and grows in the recess Q1, the liquid (liquid containing the sublimable substance) in the recess Q1 decreases.

[0163] When the sublimable substance-containing liquid on the substrate W is cooled by a cooling substance, this phenomenon occurs in the multiple recesses Q1, and crystals of the sublimable substance are generated in each of the multiple recesses Q1. As a result, the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate W changes into a solidified film SF, which is a solid film containing one or more crystals of the sublimable substance. As the crystals of the sublimable substance in the recesses Q1 grow, some of the crystals escape from the recesses Q1 through the entrances of the recesses Q1. The sublimable substance contained in the sublimable substance-containing liquid precipitates on the surface of the crystals. The crystals of the sublimable substance generated outside the recesses Q1 may also bond with the same part. In these cases, the solidified film SF includes a lower layer disposed in the multiple recesses Q1 and an upper layer supported by the lower layer and the multiple protrusions P1.

[0164] After the liquid film of the sublimable substance-containing liquid on the substrate W is transformed into a solidified film SF containing the sublimable substance, the solidified film SF is sublimated and removed from the upper surface of the substrate W. If the solidified film SF is sublimated when the recess Q1 is not fully filled with the solidified film SF, the surface of the liquid (interface between gas and liquid) that is spread over the side surfaces s2 (see FIG. 8) of two adjacent protrusions P1 may be formed within the recess Q1. In this case, the surface tension of the liquid acts on the two adjacent protrusions P1. If the force acting on the protrusions P1 is strong or if the strength of the protrusions P1 is low, the protrusions P1 will collapse. As described above, because all or almost all of the recess Q1 is filled with the solidified film SF, collapse of the pattern PA (collapse of the protrusions P1) can be reduced compared to when the solidified film SF is sublimated when the recess Q1 is not fully filled with the solidified film SF.

[0165] Since the sublimable substance-containing liquid on the substrate W is cooled, when the liquid film of the sublimable substance-containing liquid on the substrate W is changed into a solidified film SF, the evaporation rate of the sublimable substance-containing liquid can be reduced and the sublimable substance-containing liquid can continue to evaporate. If the sublimable substance-containing liquid evaporates rapidly on the surface of the sublimable substance-containing liquid, film-like crystals of the sublimable substance may occur only on the surface of the sublimable substance-containing liquid, significantly reducing the evaporation rate of the sublimable substance-containing liquid. In this case, most of the liquid film of the sublimable substance-containing liquid excluding the surface layer may not change into a solidified film SF, and the recess Q1 may remain filled with liquid.

[0166] If the sublimable substance-containing liquid is supplied to the cooled substrate W and the pretreatment liquid, cooling of the sublimable substance-containing liquid begins at the same time as the sublimable substance-containing liquid is supplied to the substrate W. Furthermore, since the sublimable substance-containing liquid mixes with the cooled pretreatment liquid on the substrate W, the sublimable substance-containing liquid can be cooled efficiently. If the sublimable substance-containing liquid on the substrate W is cooled in this manner, the period during which the sublimable substance-containing liquid rapidly evaporates on the surface of the sublimable substance-containing liquid can be eliminated or shortened, and it is possible to prevent film-like crystals of the sublimable substance from being generated only on the surface of the sublimable substance-containing liquid.

[0167] In this embodiment, the pretreatment liquid is discharged toward the upper surface of the substrate W while the substrate W is being rotated. As the rotation speed of the substrate W increases, the amount of pretreatment liquid discharged from the upper surface of the substrate W increases. As the rotation speed of the substrate W decreases, the amount of pretreatment liquid discharged from the upper surface of the substrate W decreases. The contact of the cooling substance with the lower surface of the substrate W begins simultaneously with or after the rotation speed of the substrate W begins to decrease. Therefore, the amount of pretreatment liquid discharged from the upper surface of the substrate W after being cooled can be reduced, and the pretreatment liquid on the substrate W can be efficiently cooled.

[0168] In this embodiment, the pretreatment liquid is discharged toward the upper surface of the substrate W. As a result, the pretreatment liquid is supplied to the upper surface of the substrate W, and the upper surface of the substrate W is covered with a liquid film of the pretreatment liquid. The cooling substance comes into contact with the lower surface of the substrate W while the discharge of the pretreatment liquid toward the upper surface of the substrate W is stopped and the upper surface of the substrate W is covered with a liquid film of the pretreatment liquid. Because the discharge of the pretreatment liquid is stopped, the amount of pretreatment liquid discharged from the upper surface of the substrate W is reduced. Since the pretreatment liquid on the substrate W is cooled in this state, the amount of pretreatment liquid discharged from the upper surface of the substrate W after cooling can be reduced.

[0169] In this embodiment, a puddle of the pretreatment liquid is formed on the upper surface of the substrate W. That is, by reducing the rotation speed of the substrate W, the amount of pretreatment liquid discharged from the upper surface of the substrate W is reduced. This increases the thickness of the liquid film of the pretreatment liquid on the upper surface of the substrate W. In this state, a cooling substance is brought into contact with the lower surface of the substrate W. The puddle of the pretreatment liquid is cooled by the cooling substance through the substrate W. The sublimable substance-containing liquid is discharged toward the upper surface of the substrate W in a cooled state, with the thickness of the liquid film of the pretreatment liquid on the substrate W having increased. This replaces the pretreatment liquid on the substrate W with the sublimable substance-containing liquid. Since the pretreatment liquid is cooled with an increased amount of pretreatment liquid on the substrate W, the cooling ability of the pretreatment liquid is improved compared to when there is a small amount of pretreatment liquid on the substrate W. This allows the sublimable substance-containing liquid on the substrate W to be cooled quickly.

[0170] In this embodiment, the rotation speed of the substrate W is reduced to paddle speed V3 (see FIG. 10) while the upper surface of the substrate W is covered with a film of the pretreatment liquid. As a result, the amount of pretreatment liquid discharged from the upper surface of the substrate W decreases, and the amount of pretreatment liquid on the substrate W increases. The cooling substance comes into contact with the lower surface of the substrate W while the amount of pretreatment liquid on the substrate W increases. The sublimable substance-containing liquid is discharged toward the upper surface of the substrate W while the rotation speed of the substrate W is maintained at paddle speed V3. Therefore, the time until the pretreatment liquid on the substrate W is replaced with the sublimable substance-containing liquid can be made longer compared to when the substrate W is rotating at a high speed. This increases the time that the sublimable substance-containing liquid is in contact with the pretreatment liquid, thereby efficiently cooling the sublimable substance-containing liquid on the substrate W.

[0171] In this embodiment, the airflow flowing along the upper surface of the substrate W is strengthened while the cooling substance is not in contact with the lower surface of the substrate W. This airflow promotes evaporation of the sublimable substance-containing liquid on the substrate W. This further reduces the temperature of the sublimable substance-containing liquid on the substrate W. As a result, the sublimable substance crystals grow further or combine with other sublimable substance crystals. This transforms the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate W into a solidified film SF. Because the sublimable substance-containing liquid on the substrate W is cooled in advance and the evaporation rate of the sublimable substance-containing liquid is reduced, it is possible to prevent the formation of film-like crystals of the sublimable substance only on the surface of the sublimable substance-containing liquid. Furthermore, because the solidified film SF is formed while cooling of the substrate W by the cooling substance is stopped, it is possible to eliminate or reduce water that adheres to the substrate W due to condensation during and after the formation of the solidified film SF.

[0172] Next, another embodiment will be described.

[0173] The chemical liquid, rinse liquid, pretreatment liquid, and sublimable substance-containing liquid may not be ejected from separate nozzles, but two or more of these may be ejected from a single nozzle.

[0174] When cooling the pretreatment liquid on the substrate W, instead of or in addition to a cooling liquid such as cold water, a cooling substance other than the cooling liquid may be brought into contact with the underside of the substrate W. In this case, either the cooling gas discharged from the gas flow path 82 or the heating / cooling plate 92 may be brought into contact with the underside of the substrate W. The same applies to cooling the sublimable substance-containing liquid on the substrate W.

[0175] The cooling substance that comes into contact with the lower surface of the substrate W when cooling the pretreatment liquid on the substrate W may be the same as or different from the cooling substance that comes into contact with the lower surface of the substrate W when cooling the sublimable substance-containing liquid on the substrate W. For example, when the cooling liquid discharged from the lower surface nozzle 71 is brought into contact with the lower surface of the substrate W when cooling the pretreatment liquid on the substrate W, in addition to the cooling liquid, a cooling gas discharged from the gas flow path 82 may be brought into contact with the lower surface of the substrate W when cooling the sublimable substance-containing liquid on the substrate W.

[0176] When forming the solidified film SF, a cooling substance may be brought into contact with the underside of the substrate W instead of or in addition to strengthening the airflow flowing along the upper surface of the substrate W. In this case, any of the cooling liquid discharged from the lower nozzle 71, the cooling gas discharged from the gas flow path 82, and the heating / cooling plate 92 may be brought into contact with the underside of the substrate W.

[0177] When sublimating the solidified film SF, the substrate W may be heated instead of or in addition to strengthening the airflow flowing along the upper surface of the substrate W. In this case, any of the heating liquid discharged from the lower nozzle 71, the heating gas discharged from the gas flow path 82, and the heating / cooling plate 92 may be brought into contact with the lower surface of the substrate W. The heating liquid and the heating gas are examples of a heating fluid and a heating substance that heat the substrate W. The heating / cooling plate 92 is another example of a heating substance.

[0178] The substrate processing apparatus 1 is not limited to an apparatus for processing a disk-shaped substrate W, but may be an apparatus for processing a polygonal substrate W.

[0179] Any two or more of the above-described configurations may be combined. Any two or more of the above-described steps may be combined.

[0180] Although the embodiments of the present invention have been described in detail, these are merely examples used to clarify the technical contents of the present invention, and the present invention should not be construed as being limited to these examples. The spirit and scope of the present invention are limited only by the appended claims. [Explanation of symbols]

[0181] 1: substrate processing apparatus, 10: spin chuck, 11: chuck pin, 12: spin base, 14: spin motor, 42: sublimable substance-containing liquid pipe, 43: sublimable substance-containing liquid valve, 44: pre-treatment liquid pipe, 45: pre-treatment liquid valve, 51: blocking member, 55: central nozzle, 55a: first tube, 55b: second tube, 55c: third tube, 55d: casing, 56: inert gas pipe, 57: inert gas valve, 58: flow rate adjustment valve, 61: central opening, 62: Gas flow path, 63: inert gas piping, 64: inert gas valve, 65: flow rate adjustment valve, 71: bottom nozzle, 72: rinse liquid piping, 73: rinse liquid valve, 74: Peltier element, 81: central opening, 82: gas flow path, 83: inert gas piping, 84: inert gas valve, 85: flow rate adjustment valve, 86: Peltier element, 92: heating / cooling plate, 93: Peltier element, 98: lifting actuator, P1: convex portion, PA: pattern, Q1: concave portion, SF: solidified film, W: substrate

Claims

1. A substrate processing method for processing a substrate having a pattern including a plurality of convex portions and a plurality of concave portions formed on an upper surface thereof, comprising: a pretreatment liquid supplying step of covering the upper surface of the substrate with a liquid film of a pretreatment liquid having a temperature higher than that of the cooling substance while bringing the cooling substance into contact with the lower surface of the substrate; a sublimable substance-containing liquid supplying step of replacing the pretreatment liquid on the upper surface of the substrate with a sublimable substance-containing liquid, thereby covering the upper surface of the substrate with a liquid film of the sublimable substance-containing liquid having a higher temperature than the cooling substance while bringing the cooling substance into contact with the lower surface of the substrate; a solidified film forming step of changing the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into a solidified film containing a sublimable substance; a sublimation step of removing the solidified film from the upper surface of the substrate by sublimating the solidified film.

2. 2. The substrate processing method according to claim 1, wherein the pretreatment liquid supplying step includes: reducing a rotation speed of the substrate while ejecting the pretreatment liquid toward the upper surface of the substrate; and starting to bring the cooling material into contact with the lower surface of the substrate after the rotation speed of the substrate starts to decrease.

3. 3. The substrate processing method according to claim 1, wherein the pretreatment liquid supplying step includes: a step of discharging the pretreatment liquid toward the upper surface of the substrate; and a step of contacting the cooling material with the lower surface of the substrate while the discharging of the pretreatment liquid toward the upper surface of the substrate is stopped and the upper surface of the substrate is covered with a liquid film of the pretreatment liquid.

4. the pretreatment liquid supplying step includes a puddling step of increasing a thickness of the liquid film of the pretreatment liquid on the upper surface of the substrate by reducing a rotation speed of the substrate, and a step of bringing the cooling material into contact with the lower surface of the substrate in a state where the thickness has increased; 3. The substrate processing method according to claim 1, wherein the sublimable substance-containing liquid supplying step includes a sublimable substance-containing liquid discharging step of discharging the sublimable substance-containing liquid toward the upper surface of the substrate in a state where the thickness has increased, thereby replacing the pretreatment liquid on the upper surface of the substrate with the sublimable substance-containing liquid.

5. the puddling step includes a step of reducing a rotation speed of the substrate to a puddle speed in a state in which the upper surface of the substrate is covered with the liquid film of the pretreatment liquid, 5. The substrate processing method according to claim 4, wherein the sublimable substance-containing liquid ejection step includes the step of ejecting the sublimable substance-containing liquid toward the upper surface of the substrate while maintaining a rotation speed of the substrate at the paddle speed.

6. 3. The substrate processing method according to claim 1, wherein the solidified film forming step includes a step of changing the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into the solidified film by strengthening an airflow flowing along the upper surface of the substrate while the cooling substance is not in contact with the lower surface of the substrate.

7. a substrate holder that holds a substrate having a pattern including a plurality of protrusions and a plurality of recesses formed on an upper surface thereof; a cooler that cools the substrate by bringing a cooling substance into contact with a bottom surface of the substrate held by the substrate holder; at least one liquid nozzle configured to individually eject a plurality of processing liquids, including a pre-processing liquid having a temperature higher than that of the cooling substance and a sublimable substance-containing liquid having a temperature higher than that of the cooling substance, toward the upper surface of the substrate held by the substrate holder; at least one liquid valve that causes the at least one liquid nozzle to individually eject the plurality of treatment liquids; at least one gas nozzle that ejects gas toward the upper surface of the substrate held by the substrate holder; at least one gas valve that causes the at least one gas nozzle to discharge the gas; a spin motor that rotates the substrate held by the substrate holder.

8. the at least one liquid valve and the spin motor cause the at least one liquid nozzle to eject the pretreatment liquid toward the upper surface of the substrate while reducing the rotation speed of the substrate; The substrate processing apparatus of claim 7 , wherein the cooler starts to bring the cooling substance into contact with the lower surface of the substrate after the rotation speed of the substrate starts to decrease.

9. the at least one liquid valve causes the at least one liquid nozzle to eject the pretreatment liquid toward the upper surface of the substrate; 9. The substrate processing apparatus according to claim 7, wherein the cooler brings the cooling substance into contact with the lower surface of the substrate while the discharge of the pretreatment liquid onto the upper surface of the substrate is stopped and the upper surface of the substrate is covered with a liquid film of the pretreatment liquid.

10. the spin motor performs a puddle process of increasing a thickness of the liquid film of the pretreatment liquid on the upper surface of the substrate by reducing a rotation speed of the substrate; the cooler contacts the cooling material with the lower surface of the substrate in the increased thickness state; 9. The substrate processing apparatus according to claim 7, wherein the at least one liquid valve performs a sublimable-substance-containing-liquid ejecting step of replacing the pretreatment liquid on the upper surface of the substrate with the sublimable-substance-containing liquid by ejecting the sublimable-substance-containing liquid from the at least one liquid nozzle toward the upper surface of the substrate in a state where the thickness is increased.

11. the puddling step includes a step of reducing a rotation speed of the substrate to a puddle speed in a state in which the upper surface of the substrate is covered with the liquid film of the pretreatment liquid, The substrate processing apparatus according to claim 10 , wherein the sublimable substance-containing liquid ejection step includes the step of ejecting the sublimable substance-containing liquid toward the upper surface of the substrate while maintaining a rotation speed of the substrate at the paddle speed.

12. 9. The substrate processing apparatus according to claim 7, wherein one or both of the at least one gas valve and the spin motor change the liquid film of the sublimable substance-containing liquid on the upper surface of the substrate into a solidified film containing the sublimable substance by strengthening the airflow flowing along the upper surface of the substrate while the cooling substance is not in contact with the lower surface of the substrate.

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