Substrate processing and substrate processing apparatus

Abstract

To provide a substrate processing method capable of efficiently dissolving dissolved gas into the processing solution.SOLUTION: A substrate processing method includes a processing solution supplying step for supplying the processing solution to a substrate W, and a dissolved gas supplying process for dissolving the divided dissolved gas into the processing solution by introducing it into a plurality of passages 51h of splitter 51 in a condition where the surface of the splitter 51, which includes a plurality of passages 51h opened on its surface, is in contact with at least one of the processing solution in contact with the substrate W and the processing solution prior to contact with the substrate W.SELECTED DRAWING: Figure 8

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 that a substrate is placed in a processing chamber filled with ozone gas, and the substrate is heated in a state in which a liquid film of sulfuric acid is formed on the main surface of the substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-034828 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 efficiently dissolve dissolved gas in a processing liquid. [Means for solving the problem]

[0005] One embodiment of the present invention provides a substrate processing method including: a processing liquid supply step of supplying a processing liquid to a substrate; and a dissolved gas supply step of dissolving dissolved gas split by entering the plurality of passages of a splitter into the processing liquid, while the surface of the splitter includes a plurality of passages opening on its surface and the surface is in contact with at least one of the processing liquid in contact with the substrate and the processing liquid before contacting the substrate.

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

[0007] The dissolved gas supply process includes a process in which the contact portion of the surface of the splitter is in contact with at least one of the processing liquid in contact with the substrate and the processing liquid before contacting the substrate, and the non-contact portion of the surface of the splitter is separated from the processing liquid, and the dissolved gas is caused to flow from the non-contact portion into the multiple passages, thereby releasing the split dissolved gas from the contact portion into the processing liquid.

[0008] The dissolved gas supplying step includes a step of filling a gas region, which is a region on the opposite side of the disrupter from the processing liquid, with the dissolved gas.

[0009] The substrate processing method further includes a cleaning liquid supplying step of supplying a cleaning liquid to the substrate after supplying the processing liquid to the substrate, and a splitter cleaning step of bringing the contact portion of the surface of the splitter into contact with the cleaning liquid that is in contact with the substrate.

[0010] The splitter cleaning process includes a process of contacting the contact portion of the surface of the splitter with the cleaning liquid in contact with the substrate, while flowing cleaning gas from the non-contact portion of the surface of the splitter into the multiple passages, thereby releasing the split cleaning gas from the contact portion into the cleaning liquid.

[0011] The substrate processing method further includes, after the splitter cleaning step, a splitter drying step in which, while the contact portion of the surface of the splitter is separated from the cleaning liquid in contact with the substrate, the cleaning gas is caused to flow from the non-contact portion of the surface of the splitter into the plurality of passages, thereby releasing the split cleaning gas from the contact portion.

[0012] The dissolved gas supply process includes a process of dissolving the dissolved gas, which has been split by entering the multiple passages of the splitter, into the processing liquid while the surface of the splitter is in contact with the processing liquid in the tank, and the processing liquid supply process includes a process of supplying the processing liquid supplied from the tank to the substrate.

[0013] The processing liquid supply process includes a process of increasing the air pressure in the tank to a value at which the processing liquid in the tank is discharged from the tank toward the substrate by supplying an inert gas into the tank after the dissolved gas has dissolved in the processing liquid in the tank.

[0014] The disrupter is a porous body.

[0015] Another embodiment of the present invention provides a substrate processing apparatus comprising: a processing liquid nozzle for supplying a processing liquid to a substrate; a splitter including a plurality of passages opening at its surface; a dissolved gas pipe for discharging dissolved gas into the plurality of passages of the splitter; and a dissolved gas supply unit for supplying the dissolved gas to the dissolved gas pipe, wherein the dissolved gas supply unit supplies the dissolved gas to the dissolved gas pipe while the surface of the splitter is in contact with at least one of the processing liquid in contact with the substrate and the processing liquid before contacting the substrate. The dissolved gas supply unit may be a dissolved gas generator for generating dissolved gas to be supplied to the dissolved gas pipe, or fluidic equipment in contact with the dissolved gas to be supplied to the dissolved gas pipe, or may include at least one of a dissolved gas generator and fluidic equipment. The fluidic equipment may include at least one of a pipe, a valve, a joint, and a tank, or may include other components. At least one of the features described above regarding the substrate processing method may be added to the substrate processing apparatus. [Brief explanation of the drawings]

[0016] [Figure 1A] 1 is a schematic plan view showing a layout of a substrate processing apparatus according to an embodiment of the present invention. [Figure 1B] FIG. 2 is a schematic side view of the substrate processing apparatus. [Figure 2]FIG. 2 is a schematic diagram showing the interior of the processing unit as viewed horizontally. [Figure 3] FIG. 2 is a schematic diagram showing the interior of the processing unit as viewed horizontally. [Figure 4] FIG. 2 is an enlarged schematic view of a portion of the processing unit. [Figure 5] FIG. 1 is a schematic diagram showing a first example of a disruptor disposed within a tank. [Figure 6] FIG. 10 is a schematic diagram showing a second example of a disruptor disposed within a tank. [Figure 7] FIG. 10 is a schematic view showing a state in which sulfuric acid in a tank is being supplied to a substrate. [Figure 8] FIG. 10 is a schematic diagram for explaining a phenomenon that is expected to occur when dissolved gas is supplied to the disrupter while the disrupter is in contact with the treatment liquid. [Figure 9] 10 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus. [Figure 10A-C] 1 is a schematic view for explaining an example of substrate processing performed by a substrate processing apparatus. FIG. [Figure 10D-F] 1 is a schematic view for explaining an example of substrate processing performed by a substrate processing apparatus. FIG. [Figure 10G-I] 1 is a schematic view for explaining an example of substrate processing performed by a substrate processing apparatus. FIG. [Figure 10J-L] 1 is a schematic view for explaining an example of substrate processing performed by a substrate processing apparatus. FIG. [Figure 10M-N] 1 is a schematic view for explaining an example of substrate processing performed by a substrate processing apparatus. FIG. [Figure 11] 10A and 10B are schematic diagrams showing other examples of the blocking member. [Figure 12] FIG. 10 is a schematic diagram showing another example of the chamber. [Figure 13] FIG. 10 is a schematic diagram showing another example of the chamber. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0018] Fig. 1A is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment of the present invention, and Fig. 1B is a schematic side view of the substrate processing apparatus 1.

[0019] 1A, 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 multiple substrates W, such as FOUPs (Front-Opening Unified Pods), multiple 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 multiple processing units 2, an outer wall 1a that forms an enclosed space that houses the multiple processing units 2 and the transfer system TS, and a control device 3 that controls the substrate processing apparatus 1.

[0020] 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 (left and right directions on the paper surface of FIG. 1A) in a plan view. In a plan view, the two rows face each other via a transport path TP.

[0021] The transport system TS includes an indexer robot IR and a center robot CR. The indexer robot IR transports substrates W between the carriers CA on the load port LP and the center robot CR. The center robot CR transports substrates W between a plurality of processing units 2. The indexer robot IR is disposed between the load port LP and the center robot CR in a plan view. The center robot CR is disposed on the transport path TP.

[0022] The indexer robot IR includes one or more hands Hi that support a substrate W horizontally. The hands Hi can move parallel in 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.

[0023] The center robot CR includes one or more hands Hc that support the substrate W horizontally. The hands Hc can move parallel in 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.

[0024] The control device 3 controls the electric 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 CPU (central processing unit) 3c that processes information such as executing a program, and a memory 3m that stores information such as the program to be executed by the CPU 3c. The control device 3 controls the substrate processing apparatus 1 to transport and process the substrate W, which will be described later. In other words, the control device 3 is programmed to transport and process the substrate W, which will be described later.

[0025] Next, the processing unit 2 will be described.

[0026] 2 and 3 are horizontal schematic views of the interior of the processing unit 2. Fig. 2 shows a state in which the blocking member 41 is located in a lower position and the substrate W is supported by a plurality of chuck pins 11. Fig. 3 shows a state in which the blocking member 41 is located in an upper position and the substrate W is supported by a plurality of chuck pins 11. As shown in Fig. 2, the processing unit 2 includes a chamber 4 that accommodates the substrate W, and a spin chuck 10 that holds one substrate W horizontally within the chamber 4 and rotates the substrate W about a vertical rotation axis A1 that passes through the center of the substrate W.

[0027] Chamber 4 includes a box-shaped partition wall 5 with a passage opening through which substrates W pass, and a door 6 for opening and closing the passage opening. An FFU 7 (fan filter unit) is disposed above an air outlet provided at the top of partition wall 5. The FFU 7 constantly supplies clean air (air filtered by a filter) into chamber 4 through the air outlet. Gas within chamber 4 is exhausted from chamber 4 through an exhaust duct 8 connected to the bottom of processing cup 31. This constantly creates a downflow of clean air within chamber 4. The flow rate of exhaust air discharged into exhaust duct 8 is changed according to the opening of exhaust valve 9 disposed within exhaust duct 8.

[0028] 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, and a spin motor 13 that rotates the spin base 12 and the plurality of chuck pins 11 about a rotation axis A1. The spin chuck 10 is not limited to a clamping type chuck that brings the plurality of chuck pins 11 into contact with 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 formation surface, to an upper surface 12u of the spin base 12. When the spin chuck 10 is a clamping type chuck, the plurality of chuck pins 11 correspond to a substrate holder. When the spin chuck 10 is a vacuum type chuck, the spin base 12 corresponds to a substrate holder.

[0029] The processing unit 2 includes a cylindrical processing cup 31 that receives the processing liquid splashed from the substrate W. The processing cup 31 includes a plurality of guards 34 that receive the processing liquid discharged outward from the substrate W held on the spin chuck 10, a plurality of cups 33 that receive the processing liquid guided downward by the plurality of guards 34, and a cylindrical outer wall 32 that surrounds the plurality of guards 34 and the plurality of cups 33. Figure 2 shows an example in which two guards 34 and two cups 33 are provided, and the outer cup 33 is integrated with the inner guard 34.

[0030] The guard 34 includes a cylindrical portion 35 that surrounds the spin chuck 10 and an annular ceiling portion 36 that extends obliquely upward from the upper end of the cylindrical portion 35 toward the rotation axis A1. The multiple ceiling portions 36 are stacked one on top of the other, and the multiple cylindrical portions 35 are arranged concentrically. The upper end of the annular ceiling portion 36 corresponds to the upper end of the guard 34 that surrounds the substrate W and the spin base 12 in a plan view. The multiple cups 33 are respectively arranged below the multiple cylindrical portions 35. The cups 33 form annular grooves that receive the processing liquid guided downward by the guard 34.

[0031] The processing unit 2 includes lifting actuators 34a that individually raise and lower the multiple guards 34. The lifting actuators 34a stationary the guards 34 at any position within a range from the upper position to the lower position. FIG. 2 shows a state in which the outer guards 34 are positioned in the upper position and the inner guards 34 are positioned in the lower position. The upper position is a position in which the upper ends of the guards 34 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 of the guards 34 are positioned below the holding position.

[0032] 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.

[0033] The processing unit 2 includes a plurality of nozzles that discharge processing fluids such as processing liquids and processing gases toward the substrate W positioned above the spin chuck 10. The plurality of nozzles include a first chemical liquid nozzle 21 that discharges a first chemical liquid toward the upper surface of the substrate W positioned above the spin chuck 10, a second chemical liquid nozzle 22 that discharges a second chemical liquid toward the upper surface of the substrate W positioned above the spin chuck 10, and a rinse liquid nozzle 23 that discharges a rinse liquid toward the upper surface of the substrate W positioned above the spin chuck 10. FIG. 2 shows an example in which the first chemical liquid is sulfuric acid (H2SO4), the second chemical liquid is SC1, and the rinse liquid is deionized water (DIW).

[0034] First chemical liquid nozzle 21 is connected to first chemical liquid pipe 21p that guides the first chemical liquid. When first chemical liquid valve 21v attached to first chemical liquid pipe 21p is opened, the outlet of first chemical liquid nozzle 21 continuously discharges the first chemical liquid downward. Similarly, second chemical liquid nozzle 22 is connected to second chemical liquid pipe 22p that guides the second chemical liquid. When second chemical liquid valve 22v attached to second chemical liquid pipe 22p is opened, the outlet of second chemical liquid nozzle 22 continuously discharges the second chemical liquid downward.

[0035] The first chemical liquid may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, hydrogen peroxide, organic acid (e.g., citric acid, oxalic acid, etc.), organic alkali (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and corrosion inhibitor, or may be a liquid other than these. The same applies to the second chemical liquid. The first chemical liquid may be a chemical liquid having the same composition as the second chemical liquid but different from the second chemical liquid in at least one of concentration and temperature.

[0036] Although not shown, first chemical liquid valve 21v 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 21v, etc.

[0037] The rinse liquid nozzle 23 is connected to a rinse liquid pipe 23p that guides the rinse liquid. When a rinse liquid valve 23v attached to the rinse liquid pipe 23p is opened, the outlet of the rinse liquid nozzle 23 continuously discharges the rinse liquid downward. The rinse liquid may be any of pure water (deionized water: DIW), 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 any other liquid.

[0038] First chemical liquid nozzle 21 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 3 shows an example in which first chemical liquid nozzle 21, second chemical liquid nozzle 22, and rinse liquid nozzle 23 are scan nozzles.

[0039] 3, first chemical liquid nozzle 21 is connected to first nozzle actuator 21a which moves first chemical liquid nozzle 21 in at least one of the vertical and horizontal directions. Second chemical liquid nozzle 22 is connected to second nozzle actuator 22a which moves second chemical liquid nozzle 22 in at least one of the vertical and horizontal directions. Rinse liquid nozzle 23 is connected to third nozzle actuator 23a which moves rinse liquid nozzle 23 in at least one of the vertical and horizontal directions.

[0040] First nozzle actuator 21a moves first chemical liquid nozzle 21 horizontally between a processing position where the chemical liquid discharged from first chemical liquid nozzle 21 is supplied to the upper surface of substrate W and a standby position where first chemical liquid nozzle 21 is positioned around processing cup 31 in a plan view. The same applies to second nozzle actuator 22a and the rinse liquid actuator. Figure 3 shows a state where first chemical liquid nozzle 21 is arranged at the processing position.

[0041] The processing unit 2 includes a hot plate 14, which is an example of a heater that heats the substrate W located above the spin chuck 10. The hot plate 14 is disposed between the substrate W and the spin base 12. The hot plate 14 includes a heating element (not shown) that generates Joule heat when current is applied, and an outer case that houses the heating element. The heating element and the outer case are disposed below the substrate W. The heating element is connected to wiring (not shown) that supplies power to the heating element. The temperature of the heating element is changed by the control device 3. When the control device 3 causes the heating element to generate heat, the entire substrate W is heated uniformly.

[0042] The outer case of the hot plate 14 includes a disk-shaped base portion disposed below the substrate W and multiple hemispherical protrusions protruding upward from the upper surface of the base portion. The upper surface of the base portion is parallel to the lower surface of the substrate W and has an outer diameter smaller than the diameter of the substrate W. The multiple protrusions contact the lower surface of the substrate W at positions spaced above the upper surface of the base portion. The multiple protrusions are disposed at multiple positions within the upper surface of the base portion so that the substrate W is supported horizontally. The substrate W is supported horizontally with the lower surface of the substrate W spaced above the upper surface of the base portion.

[0043] The hot plate 14 is supported horizontally by a support shaft 14s extending downward from the center of the hot plate 14. A plurality of chuck pins 11 are arranged around the hot plate 14. The center line of the hot plate 14 is aligned with the rotation axis A1 of the substrate W. Even when the spin chuck 10 rotates, the hot plate 14 does not rotate. The outer diameter of the hot plate 14 is smaller than the diameter of the substrate W.

[0044] The hot plate 14 is movable up and down in parallel relative to the spin base 12. The hot plate 14 is connected to a lifting actuator 14a via a support shaft 14s. The lifting actuator 14a raises and lowers the hot plate 14 vertically between an upper position (the position shown in FIG. 4) and a lower position (the position shown in FIGS. 2 and 3). The upper position is a contact position where the hot plate 14 contacts the lower surface of the substrate W. The lower position is a proximity position where the hot plate 14 is spaced apart from the substrate W and is positioned between the lower surface of the substrate W and the upper surface of the spin base 12.

[0045] The hot plate 14 is an example of a substrate holder. The lifting actuator 14a stops the hot plate 14 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 hot plate 14 is raised to the upper position while the substrate W is released from the support, the substrate W is lifted by the hot plate 14 and moves upward away from the multiple chuck pins 11. When the hot plate 14 is lowered to the lower position in this state, the substrate W on the hot plate 14 is placed on the multiple chuck pins 11, and the hot plate 14 moves downward away from the substrate W.

[0046] The processing unit 2 includes a blocking member 41 disposed above the spin chuck 10. The blocking member 41 is disposed within the chamber 4. The blocking member 41 includes a horizontally held disk-shaped disk portion 41p and a cylindrical portion 41t extending downward from the outer periphery of the disk portion 41p. The disk portion 41p is also referred to as a blocking plate. The lower surface of the disk portion 41p corresponds to the lower surface of the blocking member 41. The center of the disk portion 41p is disposed on the rotation axis A1 of the substrate W. The inner diameter of the cylindrical portion 41t is smaller than the outer diameter of the spin base 12. The outer diameter of the cylindrical portion 41t is smaller than the inner diameter of the upper end of the guard 34.

[0047] Shielding member 41 is connected to lifting actuator 41a, which moves shielding member 41 up and down in parallel. Lifting actuator 41a stops shielding member 41 at any position within a range from the upper position (position shown in FIG. 3) to the lower position (position shown in FIG. 2). The lower position is a proximity position where the lower surface of shielding member 41 is close to the upper surface of substrate W to a height where a scan nozzle such as first chemical liquid nozzle 21 cannot enter between substrate W and shielding member 41. The upper position is a standby position where shielding member 41 has retracted to a height where a scan nozzle can enter between shielding member 41 and substrate W.

[0048] 2, when the lifting actuator 41a places the blocking member 41 in the lower position, the lower end of the cylindrical portion 41t of the blocking member 41 is positioned below the substrate W held by the spin chuck 10, and the substrate W is surrounded by the cylindrical portion 41t. The same applies when the hot plate 14 supports the substrate W instead of the spin chuck 10. The multiple chuck pins 11 are positioned inside the cylindrical portion 41t.

[0049] When the lifting actuator 41a places the blocking member 41 in the lower position, the gap between the cylindrical portion 41t and the spin base 12 may or may not be sealed. In the former case, the cylindrical portion 41t may be pressed directly against the spin base 12, or may be pressed against the spin base 12 via a rubber or resin seal ring. FIG. 2 shows an example in which the cylindrical portion 41t is pressed directly against the spin base 12. When the blocking member 41 is placed in the lower position, the space inside the blocking member 41 is sealed.

[0050] Next, the splitter 51 disposed above the substrate W will be described.

[0051] FIG. 4 is a schematic diagram enlarging a portion of the processing unit 2. FIG. 4 shows a state in which the blocking member 41 is positioned in the lower position and the substrate W is supported by the hot plate 14. The processing unit 2 includes a splitter 51 that splits gases such as dissolution gas, a dissolution gas pipe 44p that guides the dissolution gas to be supplied to the splitter 51, and an inert gas pipe 45p that guides the dissolution gas to be supplied to the splitter 51. FIG. 4 shows an example in which the dissolution gas is ozone gas (O3) and the inert gas is nitrogen gas (N2). When the dissolution gas is ozone gas, the processing unit 2 includes an ozone generator 44g that generates ozone gas to be supplied to the dissolution gas pipe 44p. The ozone generator 44g is an example of a dissolution gas supply unit and a dissolution gas supply source.

[0052] Dissolved gas valve 44v is attached to dissolved gas pipe 44p. Inert gas valve 45v is attached to inert gas pipe 45p. Opening dissolved gas valve 44v means that dissolved gas valve 44v is switched to an open state. Closing dissolved gas valve 44v means that dissolved gas valve 44v is switched to a closed state. The same is true for inert gas valve 45v.

[0053] The open state of the dissolved gas valve 44v is a state in which the dissolved gas in the dissolved gas pipe 44p is supplied to the splitter 51. The closed state of the dissolved gas valve 44v is a state in which the dissolved gas in the dissolved gas pipe 44p is not supplied to the splitter 51. Similarly, the open state of the inert gas valve is a state in which the inert gas in the inert gas pipe 45p is supplied to the splitter 51. The open state of the inert gas valve is a state in which the inert gas in the inert gas pipe 45p is not supplied to the splitter 51.

[0054] As will be described later, ozone gas is supplied to sulfuric acid via a splitter 51. Sulfuric acid is an example of a processing liquid. The first chemical liquid nozzle 21 (see FIG. 3) is an example of a processing liquid nozzle that discharges a processing liquid toward the substrate W. When ozone gas dissolves in sulfuric acid, SOM (Sulfuric acid and Ozone Mixture), which is sulfuric acid containing ozone, is produced. Unless otherwise specified, SOM refers to a liquid. The sulfuric acid used to produce an SOM is concentrated sulfuric acid (aqueous sulfuric acid solution with a sulfuric acid concentration of 90% or more). If there is no interference with etching of the etching target, an SOM may be produced using an aqueous sulfuric acid solution with a sulfuric acid concentration lower than that of concentrated sulfuric acid.

[0055] The combination of the processing liquid and the dissolving gas may be other than sulfuric acid and ozone gas. For example, the combination of the processing liquid and the dissolving gas may be any of water and ammonia gas, water and fluorine gas, and hydrogen peroxide solution and ammonia gas, or may be other than these. When ammonia gas dissolves in water, ammonia water is produced. When fluorine gas dissolves in water, hydrofluoric acid (hydrofluoric acid) is produced. When ammonia gas dissolves in hydrogen peroxide solution, SC1, a mixture of ammonia, hydrogen peroxide, and water, is produced.

[0056] The separator 51 is a tangible object including a plurality of passages that open on the surface of the separator 51. The separator 51 may be a tangible object that can be considered rigid, or it may be a tangible object that has flexibility. The separator 51 may be a tangible object (such as a porous body or sponge) with a plurality of irregular passages that open at both ends on the surface of the separator 51, or a tangible object (such as a honeycomb structure or a perforated plate) with a plurality of passages that penetrate the separator 51 in the same direction. If both ends of the passages open on the surface of the separator 51, the passages may be long passages whose centerline length is longer than the width or diameter of the passage (the length in a direction perpendicular to the centerline of the passage), or short passages whose centerline length is equal to or shorter than the width or diameter of the passage. The cross section of the passage perpendicular to the centerline of the passage may be polygonal, circular, elliptical, or other. If the cross section of the passage is circular, the diameter of the passage may be less than 1 mm.

[0057] FIG. 4 shows an example in which the splitter 51 is disposed inside the blocking member 41 and fixed to the blocking member 41. The splitter 51 moves together with the blocking member 41. In this example, the splitter 51 is a horizontal disk-shaped device having an outer diameter equal to the inner diameter of the cylindrical portion 41t. The splitter 51 divides the space inside the blocking member 41, i.e., the space inside the cylindrical portion 41t, into an upper space SP1 above the splitter 51 and a lower space SP2 below the splitter 51. The upper space SP1 is the space between the disk portion 41p and the splitter 51.

[0058] 4, a plurality of gas supply ports 42 for discharging gas are open on the underside of the disk portion 41p of the blocking member 41, and a plurality of exhaust ports 43 for sucking gas are open on the inner peripheral surface of the cylindrical portion 41t of the blocking member 41. The plurality of gas supply ports 42 are arranged at a plurality of positions at different distances from the center of the disk portion 41p. The plurality of exhaust ports 43 are arranged at a plurality of positions spaced apart in the circumferential direction of the blocking member 41. The plurality of exhaust ports 43 are arranged below the splitter 51. The plurality of exhaust ports 43 may be arranged at the same height as the substrate W supported by the plurality of chuck pins 11 or the hot plate 14, or may be arranged above or below the substrate W.

[0059] The aforementioned dissolved gas pipe 44p and inert gas pipe 45p are connected to a plurality of gas supply ports 42. When the dissolved gas valve 44v is opened, ozone gas is discharged from the plurality of gas supply ports 42. Similarly, when the inert gas valve 45v is opened, nitrogen gas is discharged from the plurality of gas supply ports 42. The plurality of exhaust ports 43 are connected to an exhaust pipe 46p that transmits suction force. When the exhaust valve 46v attached to the exhaust pipe 46p is opened, gas is discharged from the space inside the blocking member 41 to the plurality of exhaust ports 43.

[0060] When the multiple gas supply ports 42 discharge dissolved gas such as ozone gas, the dissolved gas diffuses within the upper space SP1 of the blocking member 41 and flows from the upper space SP1 to the lower space SP2 via the splitter 51. The same applies when the multiple gas supply ports 42 discharge nitrogen gas. The upper space SP1 of the blocking member 41 is an example of a gas region filled with gas.

[0061] When the shutoff member 41 is positioned in the lower position and the space inside the shutoff member 41 is sealed, the air pressure in the upper space SP1 and the lower space SP2 increases when the multiple gas supply ports 42 discharge dissolved gas. The same occurs when the multiple gas supply ports 42 discharge nitrogen gas. The multiple exhaust ports 43 suck in the gas in the lower space SP2. This decreases the air pressure in the upper space SP1 and the lower space SP2.

[0062] Next, the splitter 51 disposed in the tank 52 will be described.

[0063] Fig. 5 is a schematic diagram showing a first example of a divider 51 arranged in the tank 52. Fig. 6 is a schematic diagram showing a second example of a divider 51 arranged in the tank 52. Fig. 7 is a schematic diagram showing a state in which sulfuric acid in the tank 52 is being supplied to the substrate W.

[0064] As shown in Figures 5 and 6, substrate processing apparatus 1 includes tank 52 that stores sulfuric acid, which is an example of a first chemical liquid to be supplied to first chemical liquid nozzle 21, and splitter 51 disposed in tank 52. The structure, materials, etc. of splitter 51 shown in Figures 5 and 6 are similar to those of splitter 51 shown in Figures 2 to 4, except for the size and shape. Figure 5 shows an example in which splitter 51 divides the interior of tank 52 into two regions, that is, a gas region filled with gas and a liquid region filled with sulfuric acid. Figure 6 shows an example in which splitter 51 is disposed entirely in the sulfuric acid in tank 52.

[0065] In the example shown in FIG. 5 , the region above the splitter 51 corresponds to the gas region, and the region below the splitter 51 corresponds to the liquid region. The splitter 51 is disposed at the boundary between the gas region and the liquid region. The upper surface of the splitter 51 is in contact with the gas in the tank 52, and the lower surface of the splitter 51 is in contact with the sulfuric acid in the tank 52. The splitter 51 floats on the surface of the sulfuric acid in the tank 52. When the surface of the sulfuric acid moves up and down in the tank 52, the splitter 51 also moves up and down in the tank 52 accordingly. This maintains the splitter 51 in contact with the surface of the sulfuric acid in the tank 52. The splitter 51 may be fixed to the tank 52. In this case, the splitter 51 may be maintained in contact with the surface of the sulfuric acid in the tank 52 by refilling the tank 52 with sulfuric acid.

[0066] In the example shown in Figure 6, the region above the surface of the sulfuric acid is a gas region, and the region below the surface of the sulfuric acid is a liquid region. The splitter 51 is located below the surface of the sulfuric acid in the tank 52. Therefore, the entire surface of the splitter 51 is in contact with the sulfuric acid. The splitter 51 is supported by the dissolved gas pipe 54p. Even if the surface of the sulfuric acid moves up and down in the tank 52, at least a portion of the surface of the splitter 51 remains in contact with the sulfuric acid. The downstream end of the dissolved gas pipe 54p is located inside the splitter 51. Ozone gas exits the dissolved gas pipe 54p through a hole opened at the downstream end of the dissolved gas pipe 54p. As a result, the ozone gas passes through the splitter 51 and is released from the surface of the splitter 51 into the sulfuric acid.

[0067] As shown in FIGS. 5 and 6, the substrate processing apparatus 1 includes a dissolution gas pipe 54p that supplies ozone gas, an example of a dissolution gas, into the tank 52, and an inert gas pipe 55p that supplies nitrogen gas, an example of an inert gas, into the tank 52. When the dissolution gas valve 54v is opened, ozone gas generated by the ozone generator 54g is supplied into the tank 52 via the dissolution gas pipe 54p. When the inert gas valve 55v is opened, nitrogen gas is supplied into the tank 52 via the inert gas pipe 55p. The dissolution gas valve 54v switches between an open state and a closed state. The same applies to the inert gas valve 55v. In both of the examples shown in FIGS. 5 and 6, the downstream end of the inert gas pipe 55p is located above the surface of the sulfuric acid in the tank 52.

[0068] The substrate processing apparatus 1 includes a pressure control valve 53 that maintains the air pressure in the tank 52 below a set value by reducing the air pressure in the tank 52 when the air pressure in the tank 52 reaches a set value higher than atmospheric pressure. Although not shown, the pressure control valve 53 includes an annular valve seat through which gas discharged from the tank 52 passes, a valve element movable relative to the valve seat, and an electric actuator that changes the cross-sectional area of ​​the flow path between the valve seat and the valve element by moving the valve element relative to the valve seat. The pressure control valve 53 also includes a pressure sensor that detects air pressure upstream of the valve seat, and a valve controller that maintains the value detected by the pressure sensor below a set value by causing the electric actuator to move the valve element based on the value detected by the pressure sensor. The valve controller maintains the air pressure in the tank 52 below a set value specified by the control device 3.

[0069] In the example shown in FIG. 5, when the dissolution gas valve 54v is opened, ozone gas is supplied to the gas region of the tank 52, and the air pressure inside the tank 52 rises to a value below the set value. The ozone gas in the gas region is supplied to the sulfuric acid in the tank 52 through the splitter 51. As a result, the ozone gas comes into contact with the sulfuric acid in the tank 52 and dissolves in the sulfuric acid. Furthermore, the ozone gas forms many bubbles in the sulfuric acid in the tank 52. As a result, the ozone gas further dissolves in the sulfuric acid in the tank 52.

[0070] In the example shown in FIG. 6, when the dissolution gas valve 54v is opened, ozone gas is released from the surface of the splitter 51 into the sulfuric acid without passing through the gas region. As a result, the ozone gas comes into contact with the sulfuric acid in the tank 52 and dissolves in the sulfuric acid. Furthermore, the ozone gas forms a large number of bubbles in the sulfuric acid in the tank 52. As a result, the ozone gas further dissolves in the sulfuric acid in the tank 52. The ozone gas bubbles are released from the surface of the sulfuric acid in the tank 52 into the gas region. As a result, the air pressure in the tank 52 rises to a value below the set value.

[0071] Tank 52 is sealed. The upstream end of first chemical liquid pipe 21p is located below the surface of the sulfuric acid in tank 52. The sulfuric acid in tank 52 is supplied to first chemical liquid nozzle 21 via first chemical liquid pipe 21p. Control device 3 may send the sulfuric acid in tank 52 to first chemical liquid nozzle 21 by increasing the air pressure in tank 52. In this case, control device 3 may increase the air pressure in tank 52 by supplying ozone gas or nitrogen gas into tank 52, or may increase the air pressure in tank 52 by supplying ozone gas and nitrogen gas into tank 52.

[0072] 7 shows an example in which nitrogen gas is supplied into tank 52 to send sulfuric acid in tank 52 to first chemical nozzle 21. In this case, control device 3 supplies ozone gas into tank 52 while first chemical valve 21v is closed. This causes the ozone gas to dissolve in the sulfuric acid. Thereafter, control device 3 closes dissolution gas valve 54v and opens inert gas valve 55v. This causes nitrogen gas to be supplied to tank 52 from inert gas valve 55v.

[0073] When nitrogen gas is supplied after ozone gas is supplied, the ozone gas in the gas region of tank 52 is replaced with nitrogen gas while the pressure inside tank 52 is maintained at a value higher than atmospheric pressure but lower than a set value. Controller 3 opens first chemical liquid valve 21v while the pressure inside tank 52 is high. As a result, sulfuric acid in tank 52 is sent to first chemical liquid pipe 21p by the pressure of the nitrogen gas and discharged from first chemical liquid nozzle 21. Therefore, sulfuric acid in which ozone gas is dissolved can be supplied from first chemical liquid nozzle 21 to substrate W while reducing the amount of ozone gas discharged from first chemical liquid nozzle 21.

[0074] Next, a phenomenon that is expected to occur when dissolved gas is supplied to the splitter 51 in a state where the splitter 51 is in contact with the treatment liquid will be described.

[0075] FIG. 8 is a schematic diagram for explaining this phenomenon. FIG. 8 shows an example in which the upper surface of a pattern formed on the upper surface of a substrate W is covered with a resist film RF, which is an example of an object to be etched. In this example, the splitter 51 is a porous body. In the example shown in FIG. 8, the upper surface of the splitter 51 is a non-contact portion 51n that does not contact the processing liquid, and the lower surface of the splitter 51 is a contact portion 51c that contacts the processing liquid. The upper and lower surfaces of the splitter 51 are part of the surface of the splitter 51. The contact portion 51c is separated from the upper surface of the substrate W.

[0076] The multiple passages 51h of the splitter 51 are open at the contact portion 51c and the non-contact portion 51n of the splitter 51. Therefore, when dissolved gas is supplied to the splitter 51, the dissolved gas passes through the splitter 51 and exits the splitter 51 from the surface of the splitter 51. By entering the multiple passages 51h, the dissolved gas is split into multiple masses of dissolved gas that are separated from each other. Each mass of dissolved gas may be spherical, linear, or other shapes.

[0077] The pressure of the dissolved gas applied to the splitter 51 sends the multiple dissolved gas masses in the multiple passages 51h toward the processing liquid in contact with the surface of the splitter 51. When the dissolved gas is supplied to the splitter 51 with the surface of the splitter 51 in contact with the processing liquid, the multiple dissolved gas masses are released into the processing liquid from the multiple passages 51h. This generates a large number of dissolved gas bubbles in the processing liquid.

[0078] The multiple dissolved gas masses come into contact with the processing liquid at the surface of the splitter 51. If the processing liquid enters the multiple passages 51h from the surface of the splitter 51, the multiple dissolved gas masses come into contact with the processing liquid inside the splitter 51. Bubbles of dissolved gas generated in the processing liquid also come into contact with the processing liquid. At least one of these contacts dissolves the dissolved gas into the processing liquid. If the dissolved gas contains a substance that reacts with the processing liquid, the dissolved gas reacts with the processing liquid.

[0079] For the same volume of dissolved gas, when the dissolved gas splits, the surface area of ​​the dissolved gas increases compared to when the dissolved gas does not split. When dissolved gas is not supplied to the splitter 51, i.e., when the air pressure in the multiple passages 51h is not rising, the surface tension of the treatment liquid forms a hemispherical surface at the end or within the multiple passages 51h, as shown enlarged within the two-dot chain line frame in Figure 8. This increases the contact area between the treatment liquid and the dissolved gas. The increased contact area between the treatment liquid and the dissolved gas promotes the dissolution of the dissolved gas into the treatment liquid. If the dissolved gas contains a substance that reacts with the treatment liquid, this increase promotes the reaction between the dissolved gas and the treatment liquid.

[0080] When the processing solution and dissolving gas are sulfuric acid and ozone gas, the ozone gas dissolves in the sulfuric acid to produce ozone-containing sulfuric acid (SOM). The sulfuric acid contained in the SOM dissociates into hydrogen ions and hydrogen sulfate ions. SOM contains not only sulfuric acid but also ozone molecules. The hydrogen sulfate ions and ozone molecules in the SOM react with each other to produce water and peroxodisulfate ions. When the SOM is heated, thermal energy is applied to the peroxodisulfate ions in the SOM. This converts the peroxodisulfate ions into sulfate ion radicals, also known as sulfate radicals. When ozone gas is brought into contact with the sulfuric acid through a splitter 51 while the sulfuric acid is heated, the concentration of active species in the SOM, such as sulfate ion radicals, increases. This allows the SOM to efficiently remove etching targets such as resist films (RF).

[0081] Next, an example of processing the substrate W will be described.

[0082] Fig. 9 is a flowchart for explaining an example of processing of a substrate W performed by the substrate processing apparatus 1. Figs. 10A to 10N are schematic views for explaining the same example. Below, an etching process for removing a resist film RF, which is an example of an etching target, from the upper surface of the substrate W shown in Fig. 8 will be described. Below, Figs. 9 and 3 will be referenced. Figs. 10A to 10N will be referenced as appropriate.

[0083] 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.

[0084] Specifically, with all guards 34 in the lower position, all scan nozzles in the standby position, the blocking member 41 in the upper position, the hot plate 14 in the lower position, and the chuck pins 11 in the open 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. With the chuck pins 11 in the open position, the center robot CR places the substrate W on the hand Hc on the chuck pins 11 with the front surface of the substrate W facing upward. The center robot CR then retracts the hand Hc from the interior of the chamber 4. After the substrate W is placed on the chuck pins 11, the lifting actuator 14a moves the hot plate 14 from the lower position to the upper position. As a result, the substrate W is lifted by the hot plate 14 and moves upward away from the chuck pins 11, as shown in FIG. 10A.

[0085] After the substrate W is supported by the hot plate 14, a first chemical liquid supplying step is performed in which SOM, which is an example of a first chemical liquid, is supplied onto the upper surface of the substrate W.

[0086] The first chemical liquid supply process includes a first liquid film formation process (step S2 in FIG. 9) of forming a liquid film of sulfuric acid on the upper surface of the substrate W, and a first gas supply process (step S3 in FIG. 9) of supplying ozone gas to a splitter 51 in contact with the sulfuric acid on the substrate W while heating the sulfuric acid on the substrate W.

[0087] When the first liquid film forming step is performed, first nozzle actuator 21a moves first chemical liquid nozzle 21 from the standby position to the processing position with blocking member 41 in the upper position. Then, first chemical liquid valve 21v is opened. As a result, first chemical liquid nozzle 21 starts discharging sulfuric acid, as shown in FIG. 10B . Before discharging sulfuric acid starts, lifting actuator 34a lifts at least one guard 34 from the lower position to the upper position.

[0088] The sulfuric acid discharged from first chemical liquid nozzle 21 collides with the upper surface of substrate W supported on hot plate 14, and then spreads along the upper surface of substrate W. As a result, the entire upper surface of substrate W supported on hot plate 14 is covered with a liquid film of sulfuric acid. Thereafter, first chemical liquid valve 21v is closed, and first chemical liquid nozzle 21 stops discharging sulfuric acid. First nozzle actuator 21a moves first chemical liquid nozzle 21 from the processing position to the standby position while first chemical liquid nozzle 21 is not discharging sulfuric acid.

[0089] When the first gas supply step is performed, the lifting actuator 41a moves the blocking member 41 from the upper position to the lower position while the entire upper surface of the substrate W is covered with a liquid film of sulfuric acid. This closes the gap between the cylindrical portion 41t of the blocking member 41 and the spin base 12 of the spin chuck 10, sealing the space inside the blocking member 41 (the space inside the cylindrical portion 41t). When the blocking member 41 is placed in the lower position, the distance from the lower surface of the separator 51 to the upper surface of the substrate W decreases from a value greater than the thickness of the liquid film of sulfuric acid to a value less than that thickness. This brings the lower surface of the separator 51 fixed to the blocking member 41 into contact with the liquid film of sulfuric acid on the substrate W.

[0090] The hot plate 14 heats the substrate W while supporting it. This heats the sulfuric acid in contact with the substrate W. When the hot plate 14 heats the substrate W, the temperature of the sulfuric acid on the substrate W rises to a value higher than room temperature (e.g., 20 to 30°C) and lower than the boiling point of sulfuric acid. The temperature of the sulfuric acid while the hot plate 14 is heating the substrate W may be 100°C or 200°C or higher, or may be lower than 100°C or 200°C. The hot plate 14 may start generating heat simultaneously with the supply of sulfuric acid to the substrate W, or may start generating heat before or after the supply of sulfuric acid to the substrate W.

[0091] As shown in FIG. 10C , the space inside the shielding member 41 is sealed, the lower surface of the splitter 51 is in contact with the sulfuric acid liquid film on the substrate W, and the hot plate 14 is heating the substrate W. The dissolution gas valve 44v is then opened. This causes the multiple gas supply ports 42 of the shielding member 41 to start discharging ozone gas. The ozone gas discharged from the multiple gas supply ports 42 fills the upper space SP1 of the shielding member 41 and travels from the upper space SP1 of the shielding member 41 to the lower space SP2 of the shielding member 41 via the splitter 51. This causes the ozone gas to dissolve in the sulfuric acid liquid film on the substrate W, and the sulfuric acid liquid film on the substrate W changes into a liquid film of SOM. The SOM reacts with the resist film RF (see FIG. 8 ) formed on the upper surface of the substrate W. This removes the resist film RF from the substrate W.

[0092] After SOM has been supplied to the entire upper surface of the substrate W, a purge step (step S4 in FIG. 9) is performed in which the space inside the blocking member 41 is filled with an inert gas.

[0093] Specifically, when a predetermined time has elapsed since the multiple gas supply ports 42 of the blocking member 41 began to discharge ozone gas, the dissolution gas valve 44v is closed, and the multiple gas supply ports 42 of the blocking member 41 stop discharging ozone gas. Thereafter, as shown in FIG. 10D , with the blocking member 41 in the lower position, the inert gas valve 45v is opened. If the exhaust valve 46v is closed, the exhaust valve 46v is opened simultaneously with or after the inert gas valve 45v is opened. As a result, the ozone gas remaining in the space inside the blocking member 41 is replaced with the inert gas.

[0094] After the space inside the blocking member 41 is filled with the inert gas, a first rinsing liquid supplying step (step S5 in FIG. 9) is performed in which pure water, which is an example of a rinsing liquid, is supplied to the upper surface of the substrate W.

[0095] Specifically, the lifting actuator 41a moves the blocking member 41 from the lower position to the upper position. This moves the lower surface of the separator 51 upward away from the SOM on the substrate W. Then, with the substrate W supported on the hot plate 14 and the blocking member 41 in the upper position, the third nozzle actuator 23a moves the rinse liquid nozzle 23 from the standby position to the processing position. Then, the rinse liquid valve 23v is opened. As a result, as shown in FIG. 10E, the rinse liquid nozzle 23 starts to discharge pure water. Before the discharge of pure water starts, the lifting actuator 34a may vertically move at least one guard 34 to switch the guard 34 that receives the liquid discharged from the substrate W. This also applies to the second chemical liquid supplying step, the second rinse liquid supplying step, and the third rinse liquid supplying step, which will be described later.

[0096] The pure water discharged from the rinse liquid nozzle 23 collides with the upper surface of the substrate W supported on the hot plate 14, and then spreads along the upper surface of the substrate W. As a result, the SOM on the substrate W is replaced with the pure water, and the entire upper surface of the substrate W supported on the hot plate 14 is covered with a liquid film of pure water. Thereafter, the rinse liquid valve 23v is closed, and the rinse liquid nozzle 23 stops discharging the pure water. The third nozzle actuator 23a moves the rinse liquid nozzle 23 from the processing position to the standby position while the rinse liquid nozzle 23 is not discharging the pure water.

[0097] The hot plate 14 stops generating heat before the SOM on the substrate W is replaced with pure water. The hot plate 14 may stop generating heat at the same time as the multiple gas supply ports 42 of the blocking member 41 stop discharging ozone gas, or may stop generating heat before or after the multiple gas supply ports 42 of the blocking member 41 stop discharging ozone gas. The hot plate 14 may stop generating heat after the SOM on the substrate W is replaced with pure water. As described below, the substrate W is transferred from the hot plate 14 to the multiple chuck pins 11. The hot plate 14 may stop generating heat at the same time as the substrate W is transferred to the multiple chuck pins 11, or may stop generating heat before or after the substrate W is transferred to the multiple chuck pins 11.

[0098] After the SOM on the substrate W is replaced with pure water, a second chemical liquid supplying step (step S6 in FIG. 9) is performed in which SC1, which is an example of the second chemical liquid, is supplied to the upper surface of the substrate W.

[0099] Specifically, with substrate W supported on hot plate 14 and blocking member 41 in the upper position, second nozzle actuator 22a moves second chemical liquid nozzle 22 from the standby position to the processing position. Then, second chemical liquid valve 22v is opened. As a result, as shown in FIG. 10F , second chemical liquid nozzle 22 starts discharging SC1. After colliding with the upper surface of substrate W supported on hot plate 14, SC1 spreads along the upper surface of substrate W. As a result, the pure water on substrate W is replaced with SC1, and the entire upper surface of substrate W supported on hot plate 14 is covered with a liquid film of SC1. Then, second chemical liquid valve 22v is closed, and second chemical liquid nozzle 22 stops discharging SC1. Then, second nozzle actuator 22a moves second chemical liquid nozzle 22 from the processing position to the standby position while second chemical liquid nozzle 22 is not discharging SC1.

[0100] After the pure water on the substrate W is replaced with SC1, a first splitter cleaning step (step S7 in FIG. 9) is performed in which the splitter 51 is cleaned with SC1, which is an example of a cleaning liquid, and nitrogen gas, which is an example of a cleaning gas.

[0101] Specifically, with the entire upper surface of the substrate W covered with the liquid film of SC1, the lifting actuator 41a moves the blocking member 41 from the upper position to the lower position. As a result, as shown in Fig. 10G, the space inside the blocking member 41 is sealed, and the lower surface of the splitter 51 comes into contact with the liquid film of SC1 on the substrate W. When the lower surface of the splitter 51 comes into contact with the liquid film of SC1 on the substrate W, residues such as particles and SOM adhering to the lower surface of the splitter 51 are removed by the SC1.

[0102] After the shutoff member 41 moves to the lower position, the inert gas valve 45v is opened, and the multiple gas supply ports 42 of the shutoff member 41 start discharging nitrogen gas. As a result, the upper space SP1 of the shutoff member 41 is filled with nitrogen gas, and the nitrogen gas flows from the upper space SP1 to the lower space SP2 through the splitter 51. If any residue remains in the splitter 51, the nitrogen gas flowing out from the lower surface of the splitter 51 expels the residue outside the splitter 51. As a result, the residue is removed from the splitter 51.

[0103] After the plurality of gas supply ports 42 of the blocking member 41 start discharging nitrogen gas, a first splitter drying step (step S8 in FIG. 9) for removing liquid from the splitter 51 is carried out.

[0104] Specifically, when the entire upper surface of the substrate W is covered with a liquid film of SC1, the blocking member 41 is in the lower position, and the multiple gas supply ports 42 of the blocking member 41 are discharging nitrogen gas, the lifting actuator 41a moves the blocking member 41 from the lower position to the upper position. As a result, as shown in FIG. 10H, the lower surface of the splitter 51 moves upward away from the liquid film of SC1 on the substrate W. The nitrogen gas flowing out from the lower surface of the splitter 51 causes the SC1 adhering to the lower surface of the splitter 51 to fall onto the SC1 on the substrate W. If any SC1 remains in the splitter 51, the nitrogen gas expels the SC1 out of the splitter 51 and causes it to fall onto the SC1. This removes liquid such as SC1 from the splitter 51. After the liquid is removed from the splitter 51, the splitter 51 may be dry, or may be wet to the extent that liquid does not fall from the splitter 51.

[0105] SC1 is an example of a cleaning liquid for cleaning the substrate W and the splitter 51. The cleaning liquid may be a chemical liquid other than SC1, or a rinse liquid such as pure water. Nitrogen gas is an example of a cleaning gas for cleaning the splitter 51. The cleaning gas may be an inert gas other than nitrogen gas, or a gas other than an inert gas such as clean air.

[0106] Next, a second rinsing liquid supplying step (step S9 in FIG. 9) is performed in which pure water, which is an example of a rinsing liquid, is supplied to the upper surface of the substrate W.

[0107] Specifically, with the substrate W supported on the hot plate 14 and the blocking member 41 in the upper position, the third nozzle actuator 23a moves the rinse liquid nozzle 23 from the standby position to the processing position. Then, the rinse liquid valve 23v is opened. As a result, the rinse liquid nozzle 23 starts to discharge the rinse liquid, as shown in FIG. 10I. The rinse liquid discharged from the rinse liquid nozzle 23 collides with the upper surface of the substrate W supported on the hot plate 14 and then spreads along the upper surface of the substrate W. As a result, the SC1 on the substrate W is replaced with the pure water, and the entire upper surface of the substrate W supported on the hot plate 14 is covered with a liquid film of pure water. Then, the rinse liquid valve 23v is closed, and the rinse liquid nozzle 23 stops discharging the pure water. With the rinse liquid nozzle 23 not discharging the pure water, the third nozzle actuator 23a moves the rinse liquid nozzle 23 from the processing position to the standby position.

[0108] Next, a second splitter cleaning step (step S10 in FIG. 9) is performed in which the splitter 51 is cleaned with pure water, which is another example of a cleaning liquid, and nitrogen gas, which is an example of a cleaning gas.

[0109] Specifically, in a state where the entire upper surface of the substrate W is covered with a liquid film of pure water, the lifting actuator 41a moves the blocking member 41 from the upper position to the lower position. As a result, the space inside the blocking member 41 is sealed, and the lower surface of the splitter 51 comes into contact with the liquid film of pure water on the substrate W, as shown in FIG.

[0110] After the shutoff member 41 moves to the lower position, the inert gas valve 45v is opened and the multiple gas supply ports 42 of the shutoff member 41 start discharging nitrogen gas. As a result, the upper space SP1 of the shutoff member 41 is filled with nitrogen gas, and the nitrogen gas flows from the upper space SP1 to the lower space SP2 via the splitter 51.

[0111] After the plurality of gas supply ports 42 of the blocking member 41 start discharging nitrogen gas, a second splitter drying step (step S11 in FIG. 9) for removing liquid from the splitter 51 is carried out.

[0112] Specifically, when the entire upper surface of the substrate W is covered with a liquid film of pure water, the blocking member 41 is in the lower position, and the multiple gas supply ports 42 of the blocking member 41 are discharging nitrogen gas, the lifting actuator 41a moves the blocking member 41 from the lower position to the upper position. As a result, as shown in FIG. 10K, the lower surface of the splitter 51 moves upward away from the liquid film of pure water on the substrate W. The nitrogen gas flowing out from the lower surface of the splitter 51 causes the pure water adhering to the lower surface of the splitter 51 to fall onto the pure water on the substrate W. If pure water remains in the splitter 51, the nitrogen gas expels the pure water out of the splitter 51 and causes it to fall onto the pure water. This removes liquid such as pure water from the splitter 51. After the liquid is removed from the splitter 51, the splitter 51 may be dry, or may be wet to the extent that liquid does not fall from the splitter 51.

[0113] After the blocking member 41 is moved to the upper position, a substrate transfer step (step S12 in FIG. 9) is performed in which the substrate W is moved from the hot plate 14 to the plurality of chuck pins 11.

[0114] Specifically, with the blocking member 41 in the upper position and the chuck pins 11 open, the lifting actuator 14a moves the hot plate 14 from the upper position to the lower position. As a result, as shown in FIG. 10L, the substrate W is placed on the chuck pins 11, and the hot plate 14 moves downward away from the substrate W. Thereafter, the chuck pins 11 are closed, and the spin motor 13 starts to rotate. As a result, the substrate W held by the chuck pins 11 starts to rotate.

[0115] After the substrate W is placed on the chuck pins 11, a third rinse liquid supplying step (step S13 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.

[0116] Specifically, with the blocking member 41 in the upper position, the third nozzle actuator 23a moves the rinse liquid nozzle 23 from the standby position to the processing position, and the rinse liquid valve 23v is opened. As a result, as shown in Fig. 10M, the pure water on the substrate W is replaced with new pure water, and the entire upper surface of the substrate W held by the multiple chuck pins 11 is covered with a liquid film of pure water. Thereafter, the rinse liquid valve 23v is closed, and the third nozzle actuator 23a moves the rinse liquid nozzle 23 from the processing position to the standby position.

[0117] After the pure water on the substrate W is replaced with new pure water, a drying step (step S14 in FIG. 9) is performed in which the substrate W is dried by rotating the substrate W at high speed.

[0118] Specifically, with the discharge of the rinse liquid from the rinse liquid nozzle 23 stopped, the spin motor 13 accelerates the substrate W in the rotation direction. As a result, the substrate W rotates at a drying speed that is higher than the rinse liquid supply speed, which is the rotation speed of the substrate W when the rinse liquid is supplied to the substrate W. As shown in FIG. 10N, the liquid is removed from the substrate W by rotating at the drying speed, and the substrate W dries. Thereafter, the spin motor 13 stops rotating. As a result, the rotation of the substrate W is stopped while the substrate W is held by the multiple chuck pins 11.

[0119] After the rotation of the substrate W has stopped, an unloading step (step S15 in FIG. 9) of unloading the substrate W from the chamber 4 is performed.

[0120] Specifically, the multiple chuck pins 11 are switched from a closed state to an open state. As a result, the substrate W is released from the multiple chuck pins 11 while remaining supported by the multiple chuck pins 11. Simultaneously with or before or after the substrate W is released from the support, the lifting actuators 34a lower all of the guards 34 to the lower position. Thereafter, the center robot CR (see FIG. 1A) causes the hand Hc to enter the chamber 4. The center robot CR receives the substrate W from the multiple chuck pins 11 and supports it with the hand Hc. Thereafter, the center robot CR moves the hand Hc out of the chamber 4 while supporting the substrate W with the hand Hc. As a result, the processed substrate W is unloaded from the chamber 4.

[0121] Next, the effects of this embodiment will be described.

[0122] In this embodiment, the surface of the splitter 51 is brought into contact with at least one of the processing liquid in contact with the substrate W and the processing liquid before contacting the substrate W. In this state, dissolved gas is introduced into the multiple passages of the splitter 51. The dissolved gas enters the multiple passages of the splitter 51 and is split into multiple, separate dissolved gas masses. Because the multiple passages open on the surface of the splitter 51, the multiple dissolved gas masses exit the splitter 51 from the surface of the splitter 51. As a result, the multiple dissolved gas masses come into contact with the processing liquid and dissolve. Because the dissolved gas is split, the contact area between the processing liquid and the dissolved gas is increased compared to when the dissolved gas is brought into contact with the processing liquid without being split. This allows the dissolved gas to be efficiently dissolved in the processing liquid, and the processing liquid in which the dissolved gas has dissolved can be supplied to the substrate W.

[0123] In this embodiment, the contact portion 51c (see FIG. 8) on the surface of the splitter 51 is in contact with the treatment liquid, and the non-contact portion 51n (see FIG. 8) on the surface of the splitter 51 is separated from the treatment liquid, and dissolved gas is supplied to the non-contact portion 51n of the splitter 51. The dissolved gas enters the splitter 51 from the non-contact portion 51n of the splitter 51 and exits into the treatment liquid from the contact portion 51c of the splitter 51. Compared to when the entire surface of the splitter 51 is in contact with the treatment liquid, the area over which dissolved gas can be supplied to the splitter 51 is larger. This allows dissolved gas to be supplied to the splitter 51 at a high flow rate.

[0124] In this embodiment, the dissolved gas is filled in the gas region, which is the region on the opposite side of the splitter 51 from the treatment liquid. The non-contact portion 51n of the splitter 51 is part of the boundary of the gas region. Therefore, compared to when the dissolved gas is not filled in the gas region, the contact area between the dissolved gas and the non-contact portion 51n can be increased, and the flow rate of the dissolved gas entering the splitter 51 from the non-contact portion 51n of the splitter 51 can be increased.

[0125] In this embodiment, after the processing liquid is supplied to the substrate W, a cleaning liquid such as SC1 is supplied to the substrate W. Furthermore, the contact portion 51c on the surface of the splitter 51 is brought into contact with the cleaning liquid in contact with the substrate W. If the processing liquid adheres to the contact portion 51c of the splitter 51, the processing liquid is transferred to the cleaning liquid. This removes the processing liquid from the contact portion 51c of the splitter 51. Since the substrate W and the splitter 51 are cleaned with the same cleaning liquid, the amount of cleaning liquid used can be reduced. Furthermore, since the substrate W and the splitter 51 are cleaned simultaneously, the time required to clean the substrate W and the splitter 51 can be shortened.

[0126] In this embodiment, while the contact portion 51c on the surface of the splitter 51 is brought into contact with the cleaning liquid in contact with the substrate W, a cleaning gas such as nitrogen gas is made to flow from the non-contact portion 51n on the surface of the splitter 51 into the multiple passages of the splitter 51. As a result, the split cleaning gas is released into the cleaning liquid from the contact portion 51c. If residues such as processing liquid or particles are present in the multiple passages of the splitter 51, the cleaning gas expels these residues from the splitter 51. As a result, not only the contact portion 51c of the splitter 51 but also the inside of the splitter 51 can be cleaned.

[0127] In this embodiment, after cleaning the splitter 51, cleaning gas is flowed from the non-contact portion 51n of the surface of the splitter 51 into the multiple passages of the splitter 51 while the contact portion 51c of the surface of the splitter 51 is separated from the cleaning liquid in contact with the substrate W. If liquid such as a processing liquid adheres to the contact portion 51c of the splitter 51, the cleaning gas flowing out from the contact portion 51c of the splitter 51 removes this liquid from the contact portion 51c of the splitter 51. If liquid remains in the splitter 51, the cleaning gas flowing out from the contact portion 51c of the splitter 51 discharges this liquid outside the splitter 51. This reduces the amount of liquid adhering to the splitter 51.

[0128] In this embodiment, the surface of the splitter 51 is brought into contact with the processing liquid in the tank 52. In this state, dissolved gas is caused to flow into the multiple passages of the splitter 51. The dissolved gas that has entered the multiple passages of the splitter 51 exits the splitter 51 from the surface of the splitter 51 and dissolves in the processing liquid in the tank 52. This processing liquid is supplied to the substrate W. Because the dissolved gas is dissolved in the processing liquid within the tank 52, the diffusion range of the dissolved gas can be limited within the tank 52, and the amount of dissolved gas used can be reduced. If the air pressure within the tank 52 is increased by supplying the dissolved gas, the dissolved gas can be more efficiently dissolved in the processing liquid.

[0129] In this embodiment, after the dissolved gas has dissolved in the processing liquid in the tank 52, an inert gas is supplied into the tank 52. This increases the air pressure in the tank 52 to a value at which the processing liquid in the tank 52 is discharged from the tank 52 toward the substrate W. Therefore, compared to when the processing liquid in the tank 52 is pumped by supplying the dissolved gas, the amount of dissolved gas used can be reduced, and the amount of dissolved gas emitted from the tank 52 can be reduced. If the dissolved gas is a reactive gas such as ozone gas, the dissolved gas emitted from the tank 52 can be suppressed or prevented from reacting with components in the chamber 4 that accommodates the substrate W. Furthermore, since the processing liquid can be sent from the tank 52 to the substrate W without using a pump, corrosion of the pump by dissolved gas such as ozone gas can be prevented.

[0130] In this embodiment, the surface of a porous body, which is an example of a splitter 51, is brought into contact with the treatment liquid. Dissolved gas is supplied to the porous body in this state. The porous body has multiple irregular passages formed inside it that open at the surface of the porous body. When dissolved gas is supplied to the porous body, the split dissolved gas flows out from the surface of the porous body. The surface of the porous body is an uneven surface. If the contour shape and size are the same, an uneven surface has a larger surface area than a flat surface. Therefore, the contact area between the treatment liquid and the porous body can be increased, and the contact area between the treatment liquid and the dissolved gas can be increased.

[0131] Next, another embodiment will be described.

[0132] When the blocking member 41 having the cylindrical portion 41t is placed in the lower position, the plurality of chuck pins 11 may be placed outside the cylindrical portion 41t.

[0133] The substrate W may be heated while being rotated in a state where the upper surface of the substrate W is covered with a liquid film of the processing liquid. Specifically, the substrate W may be heated by the hot plate 14 while being rotated and held by the multiple chuck pins 11 in a state where the upper surface of the substrate W is covered with a liquid film of the processing liquid and the hot plate 14 is spaced below the substrate W.

[0134] The dissolved gas may be supplied via the splitter 51 to only one of the processing liquid in contact with the substrate W and the processing liquid before contacting the substrate W. In other words, the splitter 51 may be disposed only above the substrate W or only within the tank 52.

[0135] When the splitter 51 is disposed only in the tank 52, in addition to or instead of heating the substrate W and the processing liquid with the hot plate 14, the substrate W and the processing liquid may be heated by irradiating the processing liquid on the substrate W with light from a lamp, which is an example of a heater. The processing liquid in the circulation path that circulates the processing liquid in the tank 52 may be heated by a circulation heater, which is an example of a heater. If there is no need to heat the processing liquid, at least one of the hot plate 14, the lamp, and the circulation heater may be omitted.

[0136] As shown in FIG. 11, when the dissolved gas is supplied to the processing liquid through the separator 51, the gap between the blocking member 41 and the spin base 12 does not have to be blocked. Specifically, the cylindrical portion 41t (see FIG. 3) may be omitted from the blocking member 41. In this case, the dissolved gas such as ozone gas may be sucked into the exhaust duct 8. Regardless of whether the blocking member 41 has the cylindrical portion 41t or not, the separator 51 may be movable up and down in parallel with the disk portion 41p of the blocking member 41.

[0137] 11 shows an example in which the lifting actuator 51a translates the separator 51 up and down between an upper position (position indicated by a solid line) and a lower position (position indicated by a two-dot chain line). In the upper position, the separator 51 is positioned above and away from the processing liquid on the substrate W. In the lower position, the separator 51 is in contact with the processing liquid on the substrate W. When the blocking member 41 is positioned in the upper position, the separator 51 may be in contact with the disk portion 41p or may be separated from the disk portion 41p. When the separator 51 is positioned in the lower position, a space for diffusing the dissolved gas is formed between the separator 51 and the disk portion 41p, so that the dissolved gas can be supplied uniformly to the separator 51.

[0138] As shown in Figures 12 and 13, the chamber 4 may be a sealed chamber in which an FFU 7 (see Figure 2) is not provided. Figures 12 and 13 show an example in which the chamber 4 includes an upper wall 4u and a lower wall 4L disposed above and below the substrate W, and a cylindrical peripheral wall 4p that surrounds the substrate W along a vertical line. In this example, the peripheral wall 4p is fixed to the lower wall 4L, and the upper wall 4u is vertically movable in parallel relative to the peripheral wall 4p and the lower wall 4L. The opening / closing actuator 4a moves the upper wall 4u vertically in parallel between a lower position (position shown in Figure 12) in which the gap between the upper wall 4u and the peripheral wall 4p is closed, and an upper position (position shown in Figure 13) in which the substrate W can pass between the upper wall 4u and the peripheral wall 4p.

[0139] The hot plate 14 heats the substrate W while holding it horizontally within the chamber 4. As shown in Fig. 13, the substrate W is relayed between the center robot CR (see Fig. 1A) and the hot plate 14 by a plurality of lift pins 15 that support the substrate W horizontally. The lift actuator 15a translates the lift pins 15 up and down between an upper position (position shown in Fig. 13) where the upper ends of the lift pins 15 are located above the upper end of the peripheral wall 4p, and a lower position (position shown in Fig. 12) where the upper ends of the lift pins 15 are located below the hot plate 14.

[0140] First chemical liquid nozzle 21, second chemical liquid nozzle 22, and rinse liquid nozzle 23 are disposed in chamber 4. Figures 12 and 13 show an example in which first chemical liquid nozzle 21, second chemical liquid nozzle 22, and rinse liquid nozzle 23 are fixed nozzles that discharge processing liquid toward the upper surface of substrate W on hot plate 14. As shown in Figure 12, splitter 51 is movable up and down in parallel with upper wall 4u between an upper position (position indicated by a solid line) where splitter 51 is spaced above the processing liquid on substrate W, and a lower position (position indicated by a two-dot chain line) where splitter 51 contacts the processing liquid on substrate W.

[0141] 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.

[0142] Any two or more of the above-mentioned features may be combined. Any two or more of the above-mentioned steps may be combined.

[0143] 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]

[0144] 1: substrate processing apparatus, 10: spin chuck, 11: chuck pin, 14: hot plate, 21: first chemical nozzle, 21a: first nozzle actuator, 21p: first chemical pipe, 21v: first chemical valve, 22: second chemical nozzle, 22a: second nozzle actuator, 22p: second chemical pipe, 22v: second chemical valve, 41: blocking member, 41p: disc portion, 41t: cylindrical portion, 42: gas supply port, 43: exhaust port, 44g: ozone generator, 44p: dissolved gas pipe, 44v: dissolution gas valve, 45p: inert gas piping, 45v: inert gas valve, 46p: exhaust pipe, 46v: exhaust valve, 51: splitter, 51a: lifting actuator, 51c: contact part, 51h: passage, 51n: non-contact part, 52: tank, 53: pressure control valve, 54g: ozone generator, 54p: dissolution gas piping, 54v: dissolution gas valve, 55p: inert gas piping, 55v: inert gas valve, RF: resist film, SP1: upper space, SP2: lower space, W: substrate

Claims

1. a processing liquid supplying step of supplying a processing liquid to the substrate; a dissolved gas supply step of dissolving dissolved gas split into the processing liquid by entering the plurality of passages of the splitter, while the surface of the splitter, which includes a plurality of passages opening on the surface, is in contact with at least one of the processing liquid in contact with the substrate and the processing liquid before contacting the substrate.

2. 2. The substrate processing method according to claim 1, wherein the dissolved gas supply step includes a step of: discharging the split dissolved gas from the contact portion into the processing liquid by causing the dissolved gas to flow from the non-contact portion into the plurality of passages while the contact portion of the surface of the splitter is in contact with at least one of the processing liquid in contact with the substrate and the processing liquid before contacting the substrate, and the non-contact portion of the surface of the splitter is separated from the processing liquid.

3. 3. The substrate processing method according to claim 2, wherein the dissolved gas supply step includes a step of filling a gas region, which is a region on the opposite side of the splitter from the processing liquid, with the dissolved gas.

4. a cleaning liquid supplying step of supplying a cleaning liquid to the substrate after supplying the processing liquid to the substrate; 4. The substrate processing method according to claim 1, further comprising a splitter cleaning step of bringing a contact portion of the surface of the splitter into contact with the cleaning liquid that is in contact with the substrate.

5. 5. The substrate processing method according to claim 4, wherein the splitter cleaning step includes a step of contacting the contact portion of the surface of the splitter with the cleaning liquid in contact with the substrate, while causing cleaning gas to flow from the non-contact portion of the surface of the splitter into the plurality of passages, thereby releasing the split cleaning gas from the contact portion into the cleaning liquid.

6. 6. The substrate processing method according to claim 5, further comprising a splitter drying step, after the splitter cleaning step, in which the cleaning gas is caused to flow from the non-contact portion of the surface of the splitter into the plurality of passages while the contact portion of the surface of the splitter is separated from the cleaning liquid in contact with the substrate, thereby releasing the split cleaning gas from the contact portion.

7. the dissolved gas supply step includes a step of dissolving the dissolved gas, which has been split by entering the plurality of passages of the splitter, into the treatment liquid while the surface of the splitter is in contact with the treatment liquid in the tank, 4. The substrate processing method according to claim 1, wherein the processing liquid supplying step includes a step of supplying the processing liquid supplied from the tank onto the substrate.

8. 8. The substrate processing method of claim 7, wherein the processing liquid supply step includes a step of increasing the air pressure in the tank to a value at which the processing liquid in the tank is discharged from the tank toward the substrate by supplying an inert gas into the tank after the dissolved gas has dissolved in the processing liquid in the tank.

9. 4. The substrate processing method according to claim 1, wherein the splitter is a porous body.

10. a processing liquid nozzle that supplies a processing liquid to the substrate; a disruptor including a plurality of passages opening at a surface thereof; a dissolved gas pipe discharging dissolved gas into the plurality of passages of the splitter; a dissolved gas supply unit that supplies the dissolved gas to the dissolved gas pipe, The dissolved gas supply unit supplies the dissolved gas to the dissolved gas piping while the surface of the splitter is in contact with at least one of the processing liquid in contact with the substrate and the processing liquid before contacting the substrate.

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