Substrate processing apparatus and substrate processing method

Abstract

To provide a substrate processing apparatus that can reduce the time required to clean the flow paths that guide the processing fluid to be supplied to the substrate.SOLUTION: A substrate processing apparatus 1 has a water flow path that guides water toward the substrate W and a solvent flow path 33x that guides organic solvent, a liquid with lower surface tension than water, toward the substrate W. The water flow path includes a concave-convex surface 72 that includes a concave 72u at least partially filled with air and a convex 72h that is in contact with water that is in contact with air in the concave 72u. The solvent flow path 33x includes a mirror surface 71 in contact with the organic solvent.SELECTED DRAWING: Figure 5A-B

Description

[Technical field]

[0001] The present invention relates to a substrate processing apparatus and a substrate processing method 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 pipes in a substrate processing apparatus installed in a factory are washed with a cleaning liquid before the apparatus is put into use. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-155649 A Summary of the Invention [Problem to be solved by the invention]

[0004] Since the substrate cannot be processed in the substrate processing apparatus while the pipes are being cleaned, it is preferable to clean the members forming the flow passages, such as the pipes, for a short period of time. In addition, it is preferable to clean the members infrequently.

[0005] An embodiment of the present invention provides a substrate processing apparatus and a substrate processing method capable of shortening the time required to clean a flow path that guides a processing liquid to be supplied to a substrate.

[0006] Moreover, one embodiment of the present invention provides a substrate processing apparatus and a substrate processing method that can reduce the frequency of cleaning a flow path that guides a processing liquid to be supplied to a substrate. [Means for solving the problem]

[0007] One embodiment of the present invention provides a substrate processing apparatus comprising: a substrate holder for holding a substrate; a water flow path for guiding water toward the substrate held in the substrate holder; and a solvent flow path for guiding an organic solvent, which is a liquid having a lower surface tension than water, toward the substrate held in the substrate holder, wherein the water flow path includes an uneven surface including a recess at least partially filled with air and a convex portion in contact with the water which is in contact with the air in the recess, and the solvent flow path includes a mirror surface in contact with the organic solvent.

[0008] In the above embodiment, at least one of the following features may be added to the substrate processing apparatus.

[0009] The uneven surface is made of a fluororesin.

[0010] The water flow path includes a water tank that stores the water and a water pipe that guides the water supplied from the water tank, and the uneven surface is provided on an inner surface of the water tank.

[0011] The solvent flow path includes a solvent tank that stores the organic solvent, and a solvent pipe that guides the organic solvent supplied from the solvent tank, and the mirror surface is provided on an inner surface of the solvent tank.

[0012] The uneven surface is provided at a bent portion of the water flow path.

[0013] The substrate processing apparatus further includes a high-temperature chemical flow path that guides a high-temperature chemical liquid that is hotter than room temperature toward the substrate held in the substrate holder, and the high-temperature chemical flow path includes an uneven surface that includes a recess at least partially filled with air and a protrusion in contact with the high-temperature chemical liquid that is in contact with the air in the recess.

[0014] The uneven surface of the high-temperature chemical liquid is made of a fluororesin.

[0015] The high-temperature chemical liquid flow path includes a high-temperature chemical liquid tank for storing the high-temperature chemical liquid, and a high-temperature chemical liquid piping for guiding the high-temperature chemical liquid supplied from the high-temperature chemical liquid tank, and the uneven surface of the high-temperature chemical liquid flow path is provided on the inner surface of the high-temperature chemical liquid tank.

[0016] The high-temperature chemical liquid flow path includes a high-temperature chemical liquid piping that guides the high-temperature chemical liquid, and a high-temperature chemical liquid nozzle that discharges the high-temperature chemical liquid guided by the high-temperature chemical liquid piping, and the uneven surface of the high-temperature chemical liquid flow path is provided on the inner surface of the high-temperature chemical liquid nozzle.

[0017] The uneven surface is provided at a bent portion of the high-temperature chemical liquid flow path.

[0018] Another embodiment of the present invention provides a substrate processing method including: a water supplying step of guiding water toward a substrate held by a substrate holder through a water flow path including the uneven surface in a state where at least a portion of the concaves of the uneven surface are filled with air and the convex portions of the uneven surface are in contact with water that is in contact with the air in the concaves, and a solvent supplying step of guiding the organic solvent toward the substrate held by the substrate holder through a solvent flow path including the mirror surface before or after the water supplying step in a state where the mirror surface is in contact with an organic solvent, which is a liquid having a lower surface tension than the water. The following features may be added to this embodiment, and at least one of the features described above regarding the substrate processing apparatus may be added to the substrate processing method.

[0019] The substrate processing method further includes a high-temperature chemical supplying step of guiding a high-temperature chemical liquid that is hotter than room temperature toward a substrate held in a substrate holder, and the high-temperature chemical supplying step includes a step of circulating the high-temperature chemical liquid through a high-temperature chemical liquid flow path including the uneven surface in a state in which at least a portion of the recesses of the uneven surface are filled with air and the convex portions of the uneven surface are in contact with the high-temperature chemical liquid that is in contact with the air in the recesses.

[0020] Yet another embodiment of the present invention provides a substrate processing apparatus comprising: a substrate holder for holding a substrate; and a high-temperature chemical flow path for guiding a high-temperature chemical liquid that is hotter than room temperature toward the substrate held in the substrate holder, wherein the high-temperature chemical flow path includes an uneven surface including a recess at least partially filled with air and a protrusion in contact with the high-temperature chemical liquid that is in contact with the air in the recess.

[0021] In the above embodiment, at least one of the following features may be added to the substrate processing apparatus.

[0022] The substrate processing apparatus further includes a solvent flow path that guides an organic solvent, which is a liquid having a lower surface tension than the high-temperature chemical liquid, toward the substrate held by the substrate holder, and the solvent flow path includes a mirror surface that contacts the organic solvent.

[0023] The uneven surface is made of a fluororesin.

[0024] The high-temperature chemical liquid flow path includes a high-temperature chemical liquid tank for storing the high-temperature chemical liquid, and a high-temperature chemical liquid piping for guiding the high-temperature chemical liquid supplied from the high-temperature chemical liquid tank, and the uneven surface is provided on the inner surface of the high-temperature chemical liquid tank.

[0025] The high-temperature chemical flow path includes a high-temperature chemical piping that guides the high-temperature chemical liquid, and a high-temperature chemical nozzle that discharges the high-temperature chemical liquid guided by the high-temperature chemical piping, and the uneven surface is provided on the inner surface of the high-temperature chemical nozzle.

[0026] The uneven surface is provided at a bent portion of the high-temperature chemical liquid flow path.

[0027] Yet another embodiment of the present invention provides a substrate processing method including a high-temperature chemical supplying step of guiding a high-temperature chemical liquid that is higher than room temperature toward a substrate held by a substrate holder, the high-temperature chemical supplying step including a step of circulating the high-temperature chemical liquid through a high-temperature chemical flow path including the uneven surface in a state in which at least a portion of the concave portions of the uneven surface are filled with air and the convex portions of the uneven surface are in contact with the high-temperature chemical liquid that is in contact with the air in the concave portions. The following features may be added to this embodiment, and at least one of the features described above regarding the substrate processing apparatus may be added to the substrate processing method.

[0028] The substrate processing method further includes a solvent supplying step of guiding the organic solvent, which is a liquid having a lower surface tension than the high-temperature chemical liquid, toward the substrate held by the substrate holder through a solvent flow path including the mirror surface, before or after the high-temperature chemical liquid supplying step, while the mirror surface is in contact with the organic solvent, which is a liquid having a lower surface tension than the high-temperature chemical liquid. [Brief description of the drawings]

[0029] [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] 1 is a schematic side view of a substrate processing apparatus; [Diagram 2] 1 is a schematic diagram showing the inside of a processing unit provided in a substrate processing apparatus as viewed horizontally. [Diagram 3] 2 is a block diagram showing an electrical configuration of the substrate processing apparatus; FIG. [Figure 4] 5A to 5C are process diagrams illustrating an example of substrate processing performed by the substrate processing apparatus. [Figure 5A-B] 1 is a schematic diagram of a processing liquid supply system of a substrate processing apparatus that supplies a processing liquid to a substrate. [Figure 6] 1 is a schematic cross-sectional view showing an example of a droplet contacting a smooth surface. [Figure 7] FIG. 1 is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in a Wenzel state. [Figure 8] FIG. 1 is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in a Cassie-Baxter state. [Figure 9] 4 is a schematic cross-sectional view showing an example of a boundary between a liquid contact portion and a liquid. FIG. [Figure 10] 4 is a schematic diagram showing an example of a cross section of a bent portion of a chemical liquid pipe. FIG. [Figure 11] 11 is a schematic diagram showing an example of a cross section of a bent portion taken along line XI-XI shown in FIG. [Figure 12] FIG. 2 is a schematic diagram showing an example of a cross section of a mold for manufacturing a chemical liquid pipe. [Figure 13] 13 is a schematic diagram showing an example of a cross section of a mold taken along line XIII-XIII shown in FIG. 12. [Figure 14] FIG. 11 is a schematic cross-sectional view showing a substrate processing apparatus according to another embodiment of the present invention. [Figure 15] 11 is a schematic view showing another configuration example of the processing unit provided in the substrate processing apparatus. FIG. [Figure 16] 16 is a process diagram illustrating an example of substrate processing using the processing unit of FIG. 15. [Figure 17] 1 is a schematic diagram of a supply system for a processing liquid including a high-temperature chemical liquid. [Figure 18] FIG. 2 is a cross-sectional view for explaining an example of the structure of a high-temperature chemical liquid pipe. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0031] Fig. 1A is a schematic plan view showing a 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.

[0032] The substrate processing apparatus 1 is a single-wafer type 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 a carrier CA that accommodates a substrate W, a plurality of processing units 2 that process the substrate W transferred from the carrier CA on the load port LP with a processing fluid such as a processing liquid or a processing gas, a transfer system TS that transfers the substrate W between the carrier 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.

[0033] 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 vertically. 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 via a transport path TP.

[0034] The transport system TS includes an indexer robot IR that transports substrates W between a carrier CA on a load port LP and the multiple processing units 2, and a center robot CR that transports substrates W between the indexer robot IR and the multiple 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.

[0035] The indexer robot IR includes one or more hands Hi that horizontally support a substrate W. 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 the substrate W to and from the carriers CA on any of the load ports LP, and can transfer the substrate W to and from the center robot CR.

[0036] The center robot CR includes one or more hands Hc that horizontally support the substrate W. 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.

[0037] Next, the processing unit 2 will be described.

[0038] 2 is a horizontal schematic diagram of the inside of a processing unit 2 provided in the substrate processing apparatus 1. The processing unit 2 includes a box-shaped chamber 4 having an internal space, a spin chuck 10 that holds one substrate W horizontally in the chamber 4 and rotates the substrate W about 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 about the rotation axis A1.

[0039] The chamber 4 includes a box-shaped partition 5 having an inlet / outlet 5b through which the substrate W passes, and a door 7 for opening and closing the inlet / outlet 5b. The FFU 6 (fan filter unit) is disposed above an air outlet 5a disposed on the upper portion of the partition 5. The FFU 6 constantly supplies clean air (air filtered by a filter) into the chamber 4 from 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 degree of an exhaust valve 9 disposed within the exhaust duct 8.

[0040] The spin chuck 10 includes a disk-shaped spin base 12 held horizontally, a number of chuck pins 11 that hold the substrate W horizontally above the spin base 12, a spin shaft 13 extending downward from the center of the spin base 12, and a spin motor 14 that rotates the spin base 12 and the number of chuck pins 11 by rotating the spin shaft 13.

[0041] 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 be a vacuum type chuck that holds the substrate W horizontally by adsorbing the back surface (lower surface) of the substrate W, which is a surface on which no devices are formed, to an 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 a substrate holder. When the spin chuck 10 is a vacuum type chuck, the spin base 12 corresponds to a substrate holder.

[0042] Processing cup 21 includes a plurality of guards 24 that receive processing liquid discharged outward from substrate W, a plurality of cups 23 that receive 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. Fig. 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.

[0043] The guard 24 includes a cylindrical portion 25 surrounding the spin chuck 10, and an annular ceiling portion 26 extending 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 annular upper end of the ceiling portion 26 corresponds to an upper end 24u of the guard 24 surrounding 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.

[0044] The processing unit 2 includes a guard lifting unit 27 that raises and lowers the multiple guards 24 individually. The guard lifting unit 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 disposed at the upper position and the remaining two guards 24 are disposed at the lower position. The upper position is a position where the upper end 24u of the guard 24 is disposed above the holding position where the substrate W held by the spin chuck 10 is disposed. The lower position is a position where the upper end 24u of the guard 24 is disposed below the holding position.

[0045] The processing unit 2 includes a plurality of nozzles that discharge processing fluids toward the substrate W held by the spin chuck 10. The plurality of nozzles includes a chemical liquid nozzle 31 that discharges a chemical liquid toward the upper surface of the substrate W, and a rinsing liquid nozzle 32 that discharges a rinsing liquid toward the upper surface of the substrate W. The plurality of nozzles further includes a solvent nozzle 33 that discharges an organic solvent toward the upper surface of the substrate W. FIG. 2 shows an example in which the rinsing liquid nozzle 32 discharges DIW (Deionized Water) and the solvent nozzle 33 discharges IPA (Isopropyl Alcohol). DIW stands for pure water (deionized water). The organic solvent stands for organic solvent liquid unless otherwise specified. The same applies to IPA.

[0046] The chemical nozzle 31 is connected to a chemical pipe 31p that guides the chemical. When a chemical valve 31v attached to the chemical pipe 31p is opened, the chemical is continuously discharged downward from a discharge port 31d of the chemical nozzle 31. The chemical 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, an organic acid (e.g., citric acid, oxalic acid, etc.), an organic alkali (e.g., TMAH: tetramethylammonium hydroxide, etc.), a surfactant, and a corrosion inhibitor, or may be another liquid.

[0047] Although not shown, the chemical liquid valve 31v includes a valve body provided 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 or an electric actuator, or may be an actuator other than these. The control device 3 opens and closes the chemical liquid valve 31v, etc. by controlling the actuator.

[0048] The rinse liquid nozzle 32 is connected to a rinse liquid pipe 32p that guides the rinse liquid. When a rinse liquid valve 32v attached to the rinse liquid pipe 32p is opened, the rinse liquid is continuously discharged downward from a discharge port 32d of the rinse liquid nozzle 32. The rinse liquid may be any one of pure water, carbonated water, electrolytic ion 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.

[0049] The solvent nozzle 33 is connected to a solvent pipe 33p that guides the organic solvent. When a solvent valve 33v attached to the solvent pipe 33p is opened, the organic solvent is continuously discharged downward from a discharge port 33d of the solvent nozzle 33. The organic solvent may be an alcohol other than IPA, or an organic solvent other than alcohol, such as HFE (hydrofluoroether). IPA has a higher vapor pressure than water and a lower surface tension than water.

[0050] The chemical liquid nozzle 31 may be a scan nozzle that moves the collision position of the chemical liquid with respect to the substrate W within the upper surface of the substrate W, or may be a fixed nozzle that cannot move the collision position of the chemical liquid with respect to the substrate W. The same applies to the other nozzles. Fig. 2 shows an example in which the chemical liquid nozzle 31 and the solvent nozzle 33 are scan nozzles and the rinsing liquid nozzle 32 is a fixed nozzle.

[0051] Chemical liquid nozzle 31 is connected to nozzle movement unit 31m which moves chemical liquid nozzle 31 in at least one of the vertical and horizontal directions. Nozzle movement unit 31m moves chemical liquid nozzle 31 horizontally between a processing position (position shown in FIG. 2) where the chemical liquid discharged from chemical liquid nozzle 31 is supplied to the upper surface of substrate W and a standby position where chemical liquid nozzle 31 is positioned around processing cup 21 in a plan view.

[0052] Solvent nozzle 33 is connected to a nozzle moving unit 33m that moves solvent nozzle 33 in at least one of the vertical and horizontal directions. Nozzle moving unit 33m moves solvent nozzle 33 horizontally between a processing position (position shown in FIG. 2) where the organic solvent discharged from solvent nozzle 33 is supplied to the upper surface of substrate W and a standby position where solvent nozzle 33 is positioned around processing cup 21 in a plan view.

[0053] Next, the electrical configuration of the substrate processing apparatus 1 will be described.

[0054] 3 is a block diagram showing an electrical configuration of the substrate processing apparatus 1. The control device 3 includes at least one computer. The computer includes a computer main body 3a and a peripheral device 3d connected to the computer main body 3a. The computer main body 3a includes a CPU 3b (central processing unit) that executes various commands and a memory 3c that stores information. The peripheral device 3d includes a storage 3e that stores information such as a program P, a reader 3f that reads information from a removable medium RM, and a communication device 3g that communicates with other devices such as a host computer.

[0055] The control device 3 is connected to an input device and a display device. The input device is operated when an operator such as a user or a maintenance person inputs information to the substrate processing apparatus 1. The information is displayed on the screen of the display device. The input device 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 and the display device.

[0056] 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, may be one that has been sent from the removable medium RM to the storage 3e via the reader 3f, or may be one that has been sent from an external device such as a host computer to the storage 3e via the communication device 3g.

[0057] 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.

[0058] The storage 3e stores a plurality of recipes. A recipe is information that specifies the processing content, processing conditions, and processing procedure of the substrate W. The plurality of recipes differ from each other in at least one of the processing content, processing conditions, and processing procedure of the substrate W. The control device 3 controls the substrate processing apparatus 1 so that the substrate W is processed according to the recipe specified by the host computer. The control device 3 is programmed to execute each of the following steps.

[0059] Next, an example of processing of the substrate W will be described.

[0060] 4 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. 1A, 2, and 4.

[0061] When processing a substrate W, the indexer robot IR takes the substrate W out of the carrier CA on one of the load ports LP. The center robot CR carries the substrate W taken out by the indexer robot IR into one of the processing units 2 and places it on the spin chuck 10. Then, a plurality of chuck pins 11 are pressed horizontally against the edge surface of the substrate W, and the spin motor 14 starts to rotate. This starts the rotation of the substrate W.

[0062] When the substrate W starts to rotate, the chemical liquid valve 31v is opened and the chemical liquid nozzle 31 discharges the chemical liquid toward the upper surface of the rotating substrate W. This forms a liquid film of the chemical liquid covering the entire upper surface of the substrate W (step S1 in FIG. 4: an example of a water supplying step). When the chemical liquid nozzle 31 is discharging the chemical liquid, the nozzle moving unit 31m may move the chemical liquid nozzle 31 so that the collision position of the chemical liquid with the upper surface of the substrate W passes through the center and the outer periphery, or may stop the chemical liquid nozzle 31 so that the collision position stops at the center. Whether or not to move the collision position is the same for other processing liquids.

[0063] When a predetermined time has elapsed since the chemical liquid valve 31v was opened, the chemical liquid valve 31v is closed, and the rinsing liquid valve 32v is opened. In response to this, the rinsing liquid nozzle 32 discharges pure water, which is an example of a rinsing liquid, toward the upper surface of the rotating substrate W. As a result, the chemical liquid on the substrate W is replaced with the pure water, and a liquid film of the pure water is formed covering the entire upper surface of the substrate W (step S2 in FIG. 4: an example of a water supplying step). Thereafter, the rinsing liquid valve 32v is closed, and the solvent valve 33v is opened. In response to this, the solvent nozzle 33 discharges IPA, which is an example of an organic solvent, toward the upper surface of the rotating substrate W. As a result, the pure water on the substrate W is replaced with IPA, and a liquid film of IPA is formed covering the entire upper surface of the substrate W (step S3 in FIG. 4: an example of a solvent supplying step). Thereafter, the solvent valve 33v is closed.

[0064] When the solvent valve 33v is closed, the spin motor 14 rotates the substrate W held by the multiple chuck pins 11 at a high rotation speed (e.g., several thousand rpm). This removes the liquid from the substrate W, and the substrate W is dried (step S4 in FIG. 4). After the substrate W is dried, the spin motor 14 stops, and the multiple chuck pins 11 move away from the edge surface of the substrate W. This stops the rotation of the substrate W, and the substrate W is released from its hold. Thereafter, the center robot CR takes the substrate W out of the processing unit 2. The indexer robot IR takes the substrate W taken out by the center robot CR into the carrier CA on one of the load ports LP.

[0065] In this manner, one substrate W is treated with a treatment liquid such as a chemical liquid, a rinse liquid, etc. The control device 3 controls the indexer robot IR and the like to cause the substrate treating apparatus 1 to repeat the above-described series of operations. In this manner, a plurality of substrates W are treated one by one.

[0066] Next, a processing liquid supply system of the substrate processing apparatus 1 will be described.

[0067] 5A is a schematic diagram of a chemical supply system of a substrate processing apparatus 1 that supplies a chemical liquid to a substrate W. The substrate processing apparatus 1 includes a chemical liquid nozzle 31, a chemical liquid pipe 31p, and a chemical liquid valve 31v, as well as a chemical liquid tank 31t that stores the chemical liquid to be supplied to the chemical liquid nozzle 31. The substrate processing apparatus 1 further includes a chemical liquid pump 31P that sends the chemical liquid in the chemical liquid tank 31t toward the chemical liquid nozzle 31, and a chemical liquid filter 31F that removes foreign matter from the chemical liquid sent out from the chemical liquid tank 31t. An upstream end of the chemical liquid pipe 31p is connected to the chemical liquid tank 31t. A downstream end of the chemical liquid pipe 31p is connected to the chemical liquid nozzle 31.

[0068] 5B is a schematic diagram of a solvent supply system of the substrate processing apparatus 1 that supplies an organic solvent to the substrate W. The substrate processing apparatus 1 includes a solvent tank 33t that stores the organic solvent to be supplied to the solvent nozzle 33, in addition to the solvent nozzle 33, the solvent pipe 33p, and the solvent valve 33v. The substrate processing apparatus 1 further includes a solvent pump 33P that sends the organic solvent in the solvent tank 33t toward the solvent nozzle 33, and a solvent filter 33F that removes foreign matter from the organic solvent sent out from the solvent tank 33t. The upstream end of the solvent pipe 33p is connected to the solvent tank 33t. The downstream end of the solvent pipe 33p is connected to the solvent nozzle 33.

[0069] The chemical solution is an aqueous solution of a chemical. 2 "O" represents the water contained in the chemical solution. The surface tension of the chemical solution is 2 The surface tension of the chemical is higher than that of organic solvents such as IPA. In the following explanation, water is referred to as water (H2O) unless otherwise specified. 2 A liquid with a concentration of 100% or nearly 100% O or with a surface tension of water (H 2 If these conditions are met, then water is called water (H 2 O) may be included. A rinse liquid such as pure water is an example of water. A chemical liquid is another example of water.

[0070] The organic solvent is water (H2 Water (H O) is a liquid with a lower surface tension. 2 The organic solvent may be a single-substance liquid or a multi-substance liquid, so long as it has a lower surface tension than water (H2O). In the latter case, the organic solvent is 2 O). The organic solvent may be a liquid such that, when the organic solvent is brought into contact with the uneven surface 72 described below, the concave portions 72u are filled with the organic solvent and the convex portions 72h are in contact with the organic solvent. Hereinafter, water and the organic solvent may be collectively referred to as the treatment liquid.

[0071] The path through which the chemical liquid passes before being discharged from the discharge port 31d of the chemical liquid nozzle 31 corresponds to one continuous chemical liquid flow path 31x from the start position to the goal position. The path through which the organic solvent passes before being discharged from the discharge port 33d of the solvent nozzle 33 corresponds to one continuous solvent flow path 33x from the start position to the goal position. Although not shown, the path through which the rinsing liquid passes before being discharged from the discharge port 32d of the rinsing liquid nozzle 32 corresponds to one continuous rinsing liquid flow path from the start position to the goal position.

[0072] The chemical liquid flow path 31x is an example of a single water flow path that is continuous from the start position to the goal position. The rinse liquid flow path is also an example of a water flow path. The structure of the rinse liquid flow path is similar to that of the chemical liquid flow path 31x, except that pure water is supplied from a utility pipe installed in a factory in which the substrate processing apparatus 1 is installed, rather than from a tank such as the chemical liquid tank 31t. Therefore, a description of the rinse liquid flow path will be omitted below.

[0073] The chemical tank 31t corresponds to the start position of the chemical flow path 31x. The outlet 31d of the chemical nozzle 31 corresponds to the goal position of the chemical flow path 31x. Similarly, the solvent tank 33t corresponds to the start position of the solvent flow path 33x. The outlet 33d of the solvent nozzle 33 corresponds to the goal position of the solvent flow path 33x. When the processing liquid is supplied to the chemical flow path 31x or the solvent flow path 33x from a utility pipe provided in a factory where the substrate processing apparatus 1 is installed, the start position may be the upstream end of the chemical pipe 31p or the solvent pipe 33p instead of the chemical tank 31t or the solvent tank 33t, or may be a joint that connects the chemical pipe 31p or the solvent pipe 33p to the utility pipe.

[0074] There may be only one start position in one chemical liquid flow path 31x, or there may be multiple goal positions in one chemical liquid flow path 31x. Similarly, there may be only one goal position in one chemical liquid flow path 31x, or there may be multiple goal positions in one chemical liquid flow path 31x. For example, the processing liquid supplied from one start position may be discharged from multiple goal positions. When discharging a mixture of a first component liquid and a second component liquid, the chemical liquid flow path 31x may include a start position for the first component liquid, a start position for the second component liquid, and one or more goal positions for discharging the first component liquid and the second component liquid mixed downstream of the two start positions. The same applies to the start position and goal position of the solvent flow path 33x.

[0075] The liquid chemical flow path 31x includes a liquid chemical nozzle 31 provided with a discharge port 31d for discharging the liquid chemical, and a liquid chemical pipe 31p for guiding the liquid chemical toward the liquid chemical nozzle 31. The liquid chemical flow path 31x may further include fluid devices other than the liquid chemical nozzle 31 and the liquid chemical pipe 31p.

[0076] Specifically, instead of or in addition to at least one of chemical liquid valve 31v, chemical liquid tank 31t, chemical liquid pump 31P, and chemical liquid filter 31F, chemical liquid flow path 31x may further include at least one of a circulation pipe for circulating the chemical liquid in chemical liquid tank 31t upstream of chemical liquid piping 31p, a flow control valve for changing the flow rate of the chemical liquid supplied to chemical liquid nozzle 31, a flow meter for measuring the flow rate of the chemical liquid supplied to chemical liquid nozzle 31, a fitting for connecting two or more pipes, a manifold for connecting three or more pipes, a heater for heating the chemical liquid, and a cooler for cooling the chemical liquid.

[0077] Like the chemical liquid flow path 31x, the solvent flow path 33x includes a solvent nozzle 33 having an outlet 33d for discharging an organic solvent, and a solvent pipe 33p for guiding the organic solvent toward the solvent nozzle 33. The solvent flow path 33x may further include fluidic devices such as a solvent valve 33v other than the solvent nozzle 33 and the solvent pipe 33p. Specific examples of the fluidic devices are the same as those described above.

[0078] The liquid medicine flow path 31x includes an internal space in which a flowing or stationary liquid medicine is placed, and a cylindrical inner surface 31y that surrounds the entire periphery of the internal space. The internal space of the liquid medicine flow path 31x is a sealed space that is open only at the goal position of the liquid medicine flow path 31x. In other words, the internal space of the liquid medicine flow path 31x is in contact with the space outside the liquid medicine flow path 31x only at the goal position of the liquid medicine flow path 31x.

[0079] Similar to the chemical flow path 31x, the solvent flow path 33x includes an internal space in which a flowing or stationary organic solvent is disposed, and a cylindrical inner surface 33y that surrounds the entire periphery of the internal space. The internal space of the solvent flow path 33x is a sealed space that is open only at the goal position of the solvent flow path 33x. In other words, the internal space of the solvent flow path 33x is in contact with the space outside the solvent flow path 33x only at the goal position of the solvent flow path 33x.

[0080] The inner surface 31y of the chemical liquid flow path 31x and the inner surface 33y of the solvent flow path 33x are made of a resin such as a fluororesin. The fluororesin may be PTFE (Polytetrafluoroethylene) or PFA (Perfluoroalkoxy alkane), or may be other than these. The entire inner surface 31y of the chemical liquid flow path 31x may be made of the same material, or a part of the inner surface 31y of the chemical liquid flow path 31x may be made of a material different from the remaining part of the inner surface 31y of the chemical liquid flow path 31x. The same applies to the inner surface 33y of the solvent flow path 33x.

[0081] As shown in an enlarged view on the right side of Fig. 5B, the inner surface 33y of the solvent flow path 33x includes a mirror surface 71 that contacts the organic solvent in the solvent flow path 33x. The mirror surface 71 is a surface that has been subjected to a mirror finish to reduce surface roughness. The mirror finish may be a polishing process or may be a process other than this.

[0082] 5A, inner surface 31y of chemical solution flow path 31x includes uneven surface 72 that comes into contact with the chemical solution in chemical solution flow path 31x. Uneven surface 72 is a rough surface having a larger surface roughness than mirror surface 71. In other words, mirror surface 71 is a smooth surface having a smaller surface roughness than uneven surface 72.

[0083] The entire inner surface 31y of the chemical liquid flow path 31x may be the uneven surface 72, or only a part of the inner surface 31y of the chemical liquid flow path 31x may be the uneven surface 72. The same applies to the mirror surface 71. Fig. 5A shows an example in which all or a part of the inner surface of the chemical liquid tank 31t is the uneven surface 72. Fig. 5B shows an example in which all or a part of the inner surface of the solvent tank 33t is the mirror surface 71.

[0084] The uneven surface 72 is a water-repellent surface that has been subjected to a water-repellent treatment that increases the contact angle of water with chemicals, rinse liquids, etc. The water-repellent treatment may be at least one of cutting, laser processing, plastic processing, extrusion molding, blasting, and etching, or may be other than these.

[0085] The cutting process may be at least one of lathe processing and milling processing, or may be other than these. The blasting process is a process in which solid particles are collided with the surface of the object (shot blasting, etc.). The etching process is a process in which the surface of the object is corroded with a chemical. The water-repellent process may be a process in which the unevenness of the surface of a mold is transferred to the object. In this case, the water-repellent process may be at least one of plastic processing and extrusion molding, or may be other than these.

[0086] As shown in Fig. 5A, the uneven surface 72 is a solid surface provided with a plurality of recesses 72u and a plurality of protrusions 72h. The recesses 72u are recessed from tips 72d of the protrusions 72h. The protrusions 72h protrude from a bottom 72b of the recesses 72u. The bottom 72b of the recesses 72u corresponds to the base of the protrusions 72h. The tips 72d of the protrusions 72h correspond to the opening ends of the recesses 72u. The tips 72d of two adjacent protrusions 72h form the entrance of the recess 72u located between them.

[0087] The convex portion 72h may be linear with a depth longer than the width, or may be dot-shaped with a depth equal to or approximately equal to the width, or may be other than these. The same applies to the concave portion 72u. The cross section of the convex portion 72h may be any of a rectangle, a square, a triangle, an inverted triangle, a trapezoid, an inverted trapezoid, and a semicircle, or may be other than these. The same applies to the cross section of the concave portion 72u. FIG. 5A shows an example in which the cross sections of the convex portion 72h and the concave portion 72u are rectangular. The height of the convex portion 72h (length in the left-right direction in FIG. 5A) may be uniform or may be non-uniform. The same applies to the depth of the concave portion 72u. The height of the convex portion 72h may be equal to or different from the width of the convex portion 72h (length in the up-down direction in FIG. 5A). The depth of the concave portion 72u may be equal to or different from the width of the concave portion 72u.

[0088] When the contact angle of water is less than 90 degrees, the solid surface is said to be hydrophilic. When the contact angle of water is 90 degrees or more, the solid surface is said to be water repellent or hydrophobic. When the contact angle of water is 150 degrees or more, the solid surface is said to be super water repellent. The contact angle of water with a smooth surface made of fluororesin may be more than 90 degrees or may be less than 90 degrees. The contact angle of water with a smooth surface made of PTFE is said to be 104 to 114 degrees. The contact angle of water with a smooth surface made of PFA is said to be 105 to 118 degrees. The contact angle of water with the uneven surface 72 may be 119 degrees or more, preferably 150 degrees or more. The contact angle of water with the mirror surface 71 may be less than 100 degrees.

[0089] Next, contact between the droplet and the uneven surface 72 and the mirror surface 71 will be described.

[0090] Fig. 6 is a schematic cross-sectional view showing an example of a droplet contacting a smooth surface. Fig. 7 is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in the Wenzel state. Fig. 8 is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in the Cassie-Baxter state. Fig. 9 is a schematic cross-sectional view showing an example of the boundary between the liquid contact portion and the liquid.

[0091] 8, the uneven surface 72 is a surface where, when a water droplet is placed on the horizontal uneven surface 72 under a normal temperature and pressure environment (room temperature and 1 atmospheric pressure), the tips 72d of the protrusions 72h come into contact with the water droplet with the bottoms 72b of the recesses 72u separated from the water droplet. In other words, the uneven surface 72 is a surface that is in a Cassie-Baxter state when a water droplet is placed on the horizontal uneven surface 72 under a normal temperature and pressure environment. Room temperature is, for example, a constant or approximately constant temperature within a range of 10 to 30°C.

[0092] The Cassie-Baxter model and the Wenzel model are models used to explain the wetting of rough surfaces. As shown in Fig. 7, in the Wenzel state (hereinafter also referred to as the W state), a water droplet on a horizontal rough surface penetrates into the depressions. In contrast, as shown in Fig. 8, in the Cassie-Baxter state (hereinafter also referred to as the CB state), the depressions 72u are filled with air, and the water droplets are supported by the tips 72d of the projections 72h.

[0093] Whether a water droplet on a rough surface adopts the W or CB state depends on factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface texture of the rough surface. It is believed that the higher the surface tension of the liquid and the lower the surface free energy of the rough surface (the higher the water repellency of the rough surface), the more likely the water droplet on the rough surface will adopt the CB state.

[0094] The inner surface 31y of the liquid medicine flow path 31x is made of a water-repellent material that has a contact angle of water with respect to a horizontal smooth surface of more than 90 degrees. Therefore, if the surface properties of the uneven surface 72 satisfy the conditions, the water droplet will contact the horizontal uneven surface 72 in the CB state. In other words, when a water droplet is placed on the horizontal uneven surface 72 in an environment of normal temperature and normal pressure, the tip 72d of the convex portion 72h will contact the water droplet with the bottom 72b of the concave portion 72u separated from the water droplet. If the water droplet contacts the horizontal uneven surface 72 in the CB state in an environment of normal temperature and normal pressure, the liquid medicine in the liquid medicine flow path 31x may contact all or a part of the uneven surface 72 in the W state.

[0095] 7 and 8, when comparing the case where a water droplet contacts the horizontal uneven surface 72 in the CB state with the case where the water droplet contacts the horizontal uneven surface 72 in the W state, the contact area between the water droplet and the uneven surface 72 is smaller when the water droplet contacts the horizontal uneven surface 72 in the CB state. Furthermore, the contact angle of water with the uneven surface 72 is larger when the water droplet contacts the horizontal uneven surface 72 in the CB state.

[0096] The solvent flow path 33x is a flow path that comes into contact with an organic solvent such as IPA. The inner surface 33y of the solvent flow path 33x is made of a water-repellent material that has a contact angle of water with respect to a horizontal smooth surface of more than 90 degrees. However, since the surface tension of the organic solvent is low, even if the inner surface 33y of the solvent flow path 33x is a rough surface, the organic solvent in the solvent flow path 33x comes into contact with the inner surface 33y of the solvent flow path 33x in the W state. As can be seen by comparing FIG. 6 and FIG. 7, when the inner surface 33y of the solvent flow path 33x is a mirror surface 71 and when the inner surface 33y of the solvent flow path 33x is a rough surface, the contact area between the organic solvent droplet and the inner surface 33y of the solvent flow path 33x is a mirror surface 71 is smaller.

[0097] FIG. 9 shows an example of an image of the boundary between the liquid-contacting part and the liquid. The large circles in FIG. 9 represent fluororesin molecules. The small black circles in FIG. 9 represent impurities. FIG. 9 shows an example in which the impurities are smaller than the fluororesin molecules. The size of the impurities is not limited to this.

[0098] An inner surface 31y (see FIG. 8) of the chemical liquid flow path 31x and an inner surface 33y (see FIG. 6) of the solvent flow path 33x are liquid-contacting parts that come into contact with the liquid. The inner surface of the rinsing liquid flow path is also included in the liquid-contacting parts. The liquid-contacting parts are made of resin such as fluororesin. As shown in FIG. 9, fluororesin may contain impurities (small black circles in FIG. 9) different from fluororesin. Such impurities may dissolve from the liquid-contacting parts into the liquid. To prevent this, when the substrate processing apparatus 1 is started up, that is, when the substrate processing apparatus 1 is being prepared for use in a factory such as a semiconductor manufacturing factory, the liquid-contacting parts are washed with a washing liquid. Such washing is also called flushing.

[0099] However, even after cleaning, impurities move from inside the fluororesin to the surface of the fluororesin. If the substrate processing apparatus 1 does not process the substrate W for a long period (a period during which the liquid does not flow along the liquid contacting portion), many impurities accumulate in the liquid contacting portion and dissolve from the liquid contacting portion into the liquid when processing of the substrate W is resumed. Therefore, if the substrate processing apparatus 1 has not processed the substrate W for a long period, cleaning must be performed before processing of the substrate W is resumed.

[0100] Cleaning requires not only cleaning fluid but also energy such as electricity. If the time required for cleaning is long, the amount of energy consumed and the amount of cleaning fluid used will increase. The same is true if cleaning is performed many times. In order to reduce cleaning costs and the burden on the environment, it is desirable to reduce the time required for cleaning and the number of times cleaning is performed.

[0101] On the other hand, even when the substrate processing apparatus 1 continues to process substrates W or when the period during which the substrate processing apparatus 1 does not process substrates W is short, contaminants such as impurities may leach into the liquid from the liquid contact part. For example, in an area where the liquid has low fluidity (an area where the liquid stagnates or accumulates), many impurities may accumulate in the liquid contact part and leach into the liquid from the liquid contact part at an unexpected time. It is also possible that foreign matter contained in the liquid may accumulate in an area where the liquid has low fluidity and flow downstream together with the liquid at an unexpected time.

[0102] The uneven surface 72 of the chemical liquid flow path 31x is a surface that contacts the tip 72d of the convex portion 72h when water such as a chemical liquid is separated from the bottom 72b of the recess 72u. Therefore, the contact area between the water and the uneven surface 72 can be reduced compared to when the water contacts the bottom 72b of the recess 72u. Furthermore, since the water does not contact or is unlikely to contact the bottom 72b of the recess 72u, the area where the water contacts the uneven surface 72 can be limited. This narrows the area to be cleaned, thereby shortening the cleaning time. Furthermore, when the contact area between the water and the chemical liquid flow path 31x is reduced, the amount of impurities dissolved per unit time from the chemical liquid flow path 31x into the water is reduced, so the concentration of impurities in the water can be reduced. Since the amount of foreign matter transferred from the water to the uneven surface 72 is also reduced, even if such foreign matter peels off from the uneven surface 72, the concentration of foreign matter in the water can be reduced.

[0103] The mirror surface 71 of the solvent flow path 33x is a surface with a reduced contact area with the organic solvent. That is, when the inner surface 33y of the solvent flow path 33x is a mirror surface 71 as shown in FIG. 6 and a rough surface as shown in FIG. 7, the contact area between the organic solvent and the solvent flow path 33x is smaller when the inner surface 33y of the solvent flow path 33x is a mirror surface 71. When the contact area between the organic solvent and the solvent flow path 33x is reduced, the amount of impurities dissolved from the solvent flow path 33x into the organic solvent per unit time is reduced, so that the concentration of impurities in the organic solvent can be reduced. Furthermore, compared to when the inner surface 33y of the solvent flow path 33x is a rough surface, foreign matter contained in the organic solvent is less likely to adhere to the solvent flow path 33x, and the amount of foreign matter moving from the organic solvent to the solvent flow path 33x is reduced. Therefore, even if foreign matter adhered to the solvent flow path 33x is peeled off, the concentration of foreign matter in the organic solvent can be reduced.

[0104] Next, the flow of liquid at the bent portion 74 of the liquid medicine flow path 31x will be described.

[0105] Fig. 10 is a schematic diagram showing an example of a cross section of a bent portion 74 of chemical liquid pipe 31p. Fig. 11 is a schematic diagram showing an example of a cross section of bent portion 74 along line XI-XI shown in Fig. 10. Fig. 12 is a schematic diagram showing an example of a cross section of a mold 75 for manufacturing chemical liquid pipe 31p. Fig. 13 is a schematic diagram showing an example of a cross section of mold 75 along line XIII-XIII shown in Fig. 12.

[0106] As shown in Fig. 11, the inner peripheral surface of the chemical liquid pipe 31p includes a striped surface 73 including a plurality of linear protrusions 73h and a plurality of linear grooves 73u that form a striped pattern extending in the axial direction of the chemical liquid pipe 31p (the direction along the center line 31L of the chemical liquid pipe 31p). The striped surface 73 is one form of the uneven surface 72 (see Fig. 8). The linear protrusions 73h are one form of the convex portions 72h (see Fig. 8), and the linear grooves 73u are one form of the concave portions 72u (see Fig. 8).

[0107] The linear protrusions 73h are arranged at intervals in the circumferential direction of the chemical liquid pipe 31p (the direction around the center line 31L of the chemical liquid pipe 31p). The same is true for the linear grooves 73u. Each linear groove 73u is formed between two linear protrusions 73h that are closest in the circumferential direction of the chemical liquid pipe 31p. FIG. 11 shows an example in which the striped surface 73 is endless and surrounds the center line 31L of the chemical liquid pipe 31p. Only a portion of the inner circumferential surface of the chemical liquid pipe 31p in the circumferential direction of the chemical liquid pipe 31p may be the striped surface 73.

[0108] The linear grooves 73u and the linear projections 73h extend in a direction parallel to the center line 31L of the chemical liquid pipe 31p. In a portion where the center line 31L of the chemical liquid pipe 31p is linear, the linear grooves 73u and the linear projections 73h are also linear. In a portion where the center line 31L of the chemical liquid pipe 31p is curved, the linear grooves 73u and the linear projections 73h are also curved. The width of the linear grooves 73u is shorter than the length of the linear grooves 73u. The width of the linear projections 73h is shorter than the length of the linear projections 73h. The width of the linear projections 73h may be equal to or different from the width of the linear grooves 73u.

[0109] 12 and 13 show an example of a cross section of a mold 75 for manufacturing the liquid medicine pipe 31p by melt extrusion, which is one of the extrusion molding methods. The mold 75 is a mold for molding a resin pipe such as the liquid medicine pipe 31p. The mold 75 may be a mold for molding a molten pipe material called a die or a die, or may be a mold for finishing the shape of the pipe that has passed through the die or a die, which is called sizing. The mold 75 includes a core 75c for molding the inner peripheral surface of the pipe and a ring 75r for molding the outer peripheral surface of the pipe. FIG. 13 shows the appearance of the core 75c.

[0110] A resin pipe material such as the chemical liquid pipe 31p is supplied to a cylindrical space 75s between the core 75c and the ring 75r, and is continuously extruded from the space 75s. This forms the pipe. At this time, irregularities having the same or nearly the same shape as the irregularities provided on the outer peripheral surface of the core 75c are formed on the inner peripheral surface of the pipe. This forms the striped surface 73. The pipe extruded from the mold 75 is straight. When the pipe is provided with a bent portion 74, the straight pipe may be temporarily softened by heating and bent. When the pipe is flexible, it is sufficient to bend the pipe without heating it.

[0111] FIG. 10 shows an example in which the bent portion 74 includes a linear upstream portion 74u, a linear downstream portion 74d inclined at a certain angle with respect to the upstream portion 74u, and an arc-shaped corner portion 74c extending from the upstream portion 74u to the downstream portion 74d. In this example, the bent portion 74 is bent by 90 degrees. In other words, the upstream portion 74u and the downstream portion 74d are arranged on two straight lines that are perpendicular to each other. The upstream portion 74u, the corner portion 74c, and the downstream portion 74d are all cylindrical. The linear grooves 73u and the linear protrusions 73h of the striped surface 73 are bent at the bent portion 74.

[0112] The spiral curves in FIG. 10 represent areas where liquid stagnation or retention occurs. Since the striped surface 73 is provided on the inner peripheral surface of the bent portion 74, the contact area between the water and the bent portion 74 can be reduced, and the area where the water comes into contact with the bent portion 74 can be limited. Furthermore, since the resistance applied to the water from the inner peripheral surface of the bent portion 74 is reduced, the decrease in the water speed at the bent portion 74 can be reduced, and the area where stagnation or retention occurs can be reduced. Therefore, impurities and foreign matter that accumulate in such areas can be reduced, and contaminants that move from the inner peripheral surface of the bent portion 74 to the water flowing inside the bent portion 74 can be reduced.

[0113] Next, the effects of this embodiment will be described.

[0114] In this embodiment, water is guided toward the substrate W through the water flow path, and an organic solvent, which is a liquid having a lower surface tension than water, is guided toward the substrate W through the solvent flow path 33x. The chemical liquid flow path 31x and the rinsing liquid flow path are examples of water flow paths, and the chemical liquid and the rinsing liquid are examples of water. The water flow path includes an uneven surface 72 that contacts the water. The solvent flow path 33x includes a mirror surface 71 that contacts the organic solvent.

[0115] The uneven surface 72 of the chemical solution flow path 31x includes a recess 72u at least partially filled with air, and a protrusion 72h in contact with the water that is in contact with the air in the recess 72u. Because at least a portion of the recess 72u is filled with air, the contact area between the water and the uneven surface 72 is reduced compared to when the entire recess 72u is filled with water. Furthermore, because the water does not or does not easily contact the inner surface of the recess 72u, the area in which the water contacts the uneven surface 72 can be limited. This narrows the area to be cleaned with the cleaning liquid, thereby shortening the cleaning time.

[0116] The mirror surface 71 of the solvent flow path 33x is a smooth surface that comes into contact with the organic solvent. Since the surface tension of the organic solvent is low, even if the inner surface 33y of the solvent flow path 33x is rough, the organic solvent in the solvent flow path 33x enters the grooves of the rough surface. In this case, if the surface roughness of the rough surface is reduced, the contact area between the organic solvent and the solvent flow path 33x also decreases. If the surface roughness is made extremely small, the rough surface becomes the mirror surface 71. Therefore, by providing the mirror surface 71 on the inner surface 33y of the solvent flow path 33x, the area to be cleaned with the cleaning liquid can be narrowed compared to when the inner surface 33y of the solvent flow path 33x is rough, and the cleaning time can be shortened.

[0117] In this embodiment, all or a part of the uneven surface 72 is made of fluororesin. Fluororesin is a highly water-repellent material. Whether a liquid droplet on a rough surface adopts the Wenzel state or the Cassie-Baxter state depends on factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface properties of the rough surface. By making the uneven surface 72 from a highly water-repellent material, it is possible to maintain a state in which at least a part of the recesses 72u is filled with air. This makes it possible to reduce the contact area between the water and the uneven surface 72 while limiting the area in which the water comes into contact with the uneven surface 72.

[0118] In this embodiment, the chemical liquid is guided from the chemical liquid tank 31t to the chemical liquid piping 31p. The chemical liquid tank 31t and the chemical liquid piping 31p correspond to a water tank and a water piping. The uneven surface 72 is provided on the inner surface of the chemical liquid tank 31t. The time during which the chemical liquid contacts the chemical liquid tank 31t is longer than the time during which the chemical liquid contacts the chemical liquid piping 31p. Therefore, by reducing the contact area between the chemical liquid and the chemical liquid tank 31t, it is possible to effectively reduce contaminants transferred from the chemical liquid tank 31t to the chemical liquid.

[0119] In this embodiment, the organic solvent is guided from the solvent tank 33t to the solvent pipe 33p. The mirror surface 71 is provided on the inner surface of the solvent tank 33t. The time that the organic solvent is in contact with the solvent tank 33t is longer than the time that the organic solvent is in contact with the solvent pipe 33p. Therefore, by reducing the contact area between the organic solvent and the solvent tank 33t, it is possible to effectively reduce the amount of contaminants transferred from the solvent tank 33t to the organic solvent.

[0120] In this embodiment, an uneven surface 72 is provided on the inner surface of a bent portion 74 of a liquid medicine flow path 31x, which is an example of a water flow path. In the bent portion 74, a region where the liquid has low fluidity (a region where the liquid stagnates or accumulates) may occur. In such a case, it is considered that contaminants such as particles accumulate in the bent portion 74 and flow together with the liquid medicine at an unexpected timing. When the uneven surface 72 is provided on the inner surface of the bent portion 74, the resistance applied to the liquid medicine from the inner surface of the bent portion 74 is reduced, so that the decrease in the speed of the liquid medicine at the bent portion 74 can be reduced, and the region where the liquid medicine stagnates or accumulates can be reduced. Therefore, impurities and foreign matter that accumulate in such a region can be reduced, and the contaminants that move from the inner surface of the bent portion 74 to the liquid medicine flowing inside the bent portion 74 can be reduced.

[0121] Next, another embodiment will be described.

[0122] Instead of providing the uneven surface 72 or the striped surface 73 on the liquid chemical tank 31t and the bent portion 74, the uneven surface 72 or the striped surface 73 may be provided only on the liquid chemical tank 31t or only on the bent portion 74.

[0123] The striped surface 73 may be provided on a part of the inner surface 31y of the chemical flow path 31x other than the inner peripheral surface of the chemical pipe 31p, such as the inner surface of the chemical tank 31t. In this case, the direction of the linear protrusions 73h and the linear grooves 73u does not have to be parallel to the flow direction of the chemical liquid.

[0124] The substrate processing apparatus 1 is not limited to an apparatus for processing a disk-shaped substrate W, and may be an apparatus for processing a polygonal substrate W. The substrate processing apparatus 1 may be a batch-type apparatus for processing a plurality of substrates W collectively.

[0125] 14, the batch-type substrate processing apparatus 1 includes a lifter 81 that moves up and down between an upper position and a lower position while holding a plurality of substrates W, and an inner bath 82 that stores a processing liquid in which the plurality of substrates W held by the lifter 81 located at the lower position are immersed. The batch-type substrate processing apparatus 1 further includes a nozzle 87 that supplies the processing liquid into the inner bath 82, an outer bath 83 that stores the processing liquid that overflows from the inner bath 82, a circulation pipe 84 that guides the processing liquid from the outer bath 83 to the nozzle 87, a pump 85 that sends the processing liquid from the outer bath 83 to the nozzle 87 through the circulation pipe 84, and a filter 86 that removes foreign matter from the processing liquid flowing through the circulation pipe 84. The lifter 81 corresponds to a substrate holder.

[0126] The processing liquid supplied to the inner tank 82 may be water such as a chemical liquid or a rinse liquid, or may be an organic solvent. The outer tank 83 corresponds to the start position of the water flow path or the solvent flow path 33x. The inner tank 82 corresponds to the goal position of the water flow path or the solvent flow path 33x. When the processing liquid is water, the uneven surface 72 is provided on the inner surface of at least one of the inner tank 82, the outer tank 83, the circulation pipe 84, the pump 85, the filter 86, and the nozzle 87. When the processing liquid is an organic solvent, the mirror surface 71 is provided on the inner surface of at least one of the inner tank 82, the outer tank 83, the circulation pipe 84, the pump 85, the filter 86, and the nozzle 87.

[0127] Figure 15 is a schematic diagram showing another configuration example of the processing unit 2, and shows the configuration when the inside of the processing unit 2 is viewed horizontally, similar to Figure 2. In Figure 15, parts corresponding to those in Figure 2 are given the same reference numerals, and the configuration and operation are substantially similar to those in Figure 2, so their explanation will be omitted.

[0128] This configuration example differs from the configuration example shown in FIG. 2 in the processing liquid supply system and the substrate processing, and therefore these will be mainly described.

[0129] The processing unit 2 includes a plurality of nozzles that discharge a processing fluid toward the substrate W held by the spin chuck 10. The plurality of nozzles include a first chemical liquid nozzle 131 that discharges a first chemical liquid toward the upper surface of the substrate W, a second chemical liquid nozzle 132 that discharges a second chemical liquid toward the upper surface of the substrate W, and a rinsing liquid nozzle 134 (first rinsing liquid nozzle) that discharges a rinsing liquid toward the upper surface of the substrate W. The plurality of nozzles also includes a third chemical liquid nozzle 133 that discharges a third chemical liquid toward the upper surface of the substrate W. FIG. 15 shows a case where the first chemical liquid is DHF (dilute hydrofluoric acid), which is an example of an acid, the second chemical liquid is a sulfuric acid-hydrogen peroxide mixture (so-called SPM (sulfuric acid-hydrogen peroxide mixture)) having an effect of removing organic matter such as resist, and the third chemical liquid is an ammonia-hydrogen peroxide mixture (so-called SC1: Standard Clean1), which is an example of an alkali. FIG. 15 also shows a case where the rinsing liquid discharged from the rinsing liquid nozzle 134 is DIW (deionized water). As mentioned above, the rinsing liquid may be something other than DIW.

[0130] The multiple nozzles further include a rinse liquid nozzle 32 (second rinse liquid nozzle) that discharges a rinse liquid toward the upper surface of the substrate W, and a solvent nozzle 33 that discharges an organic solvent toward the upper surface of the substrate W, similar to the configuration example of FIG. 2. FIG. 15 shows an example in which the rinse liquid nozzle 32 discharges DIW and the solvent nozzle 33 discharges IPA (isopropyl alcohol), similar to the case of FIG. 2. The type of rinse liquid discharged from the rinse liquid nozzle 32 and the type of organic solvent discharged from the solvent nozzle 33 are as described above. In addition, the configuration of the rinse liquid supply system to the rinse liquid nozzle 32 and the configuration of the supply system of the organic solvent to the solvent nozzle 33 are also as described above and are the same as the configuration example of FIG. 2.

[0131] 15, a shield plate may be provided facing from above the upper surface of the substrate W held by the spin chuck 10. In this case, the rinsing liquid nozzle 32 and the solvent nozzle 33 may be attached to the shield plate and disposed so as to eject liquid from the center of the shield plate toward the center of the substrate W.

[0132] First chemical liquid nozzle 131, second chemical liquid nozzle 132, and rinsing liquid nozzle 134 are connected to nozzle moving unit 38. Nozzle moving unit 38 changes the landing position (i.e., the distance of the landing position from rotation axis A1) of the liquid discharged from first chemical liquid nozzle 131, second chemical liquid nozzle 132, and rinsing liquid nozzle 134 in the radial direction (radial direction centered on rotation axis A1) on substrate W. As a result, first chemical liquid nozzle 131, second chemical liquid nozzle 132, and rinsing liquid nozzle 134 have the form of a scan nozzle in which the landing position changes in the radial direction on substrate W. For example, nozzle moving unit 38 may be a turning unit that turns first chemical liquid nozzle 131, second chemical liquid nozzle 132, and rinsing liquid nozzle 134 along a horizontal arc-shaped path passing near rotation axis A1. Third chemical liquid nozzle 133 is connected to nozzle moving unit 133m. Nozzle moving unit 133m changes the radial landing position on substrate W of the liquid discharged from third chemical liquid nozzle 133. As a result, third chemical liquid nozzle 133 has the form of a scan nozzle in which the landing position changes radially on substrate W. For example, nozzle moving unit 133m may be a turning unit that turns third chemical liquid nozzle 133 along an arc-shaped horizontal path passing near rotation axis A. One or more of first chemical liquid nozzle 131, second chemical liquid nozzle 132, third chemical liquid nozzle 133, and rinsing liquid nozzle 134 may be fixed nozzles fixed within processing unit 2.

[0133] First chemical liquid nozzle 131 is connected to first chemical liquid pipe 131p that guides DHF toward first chemical liquid nozzle 131. Rinse liquid nozzle 134 is connected to rinse liquid pipe 134p that guides pure water toward rinse liquid nozzle 134. When first chemical liquid valve 131v provided in first chemical liquid pipe 131p is opened, DHF is supplied from first chemical liquid pipe 131p to first chemical liquid nozzle 131 and is continuously discharged downward from first chemical liquid nozzle 131. When rinse liquid valve 134v provided in rinse liquid pipe 134p is opened, pure water is supplied from rinse liquid pipe 134p to rinse liquid nozzle 134 and is continuously discharged downward from rinse liquid nozzle 134. The temperature of the pure water discharged from rinse liquid nozzle 134 may be room temperature or may be higher than room temperature.

[0134] Second chemical liquid nozzle 132 is connected to sulfuric acid piping 132p that guides sulfuric acid toward second chemical liquid nozzle 132, and hydrogen peroxide solution piping 135p that guides hydrogen peroxide solution toward second chemical liquid nozzle 132. Sulfuric acid valve 132v and flow rate adjustment valve 132f are provided in sulfuric acid piping 132p. Hydrogen peroxide solution valve 135v and flow rate adjustment valve 135f are provided in hydrogen peroxide solution piping 135p.

[0135] When sulfuric acid valve 132v is opened, sulfuric acid is supplied from sulfuric acid pipe 132p to second chemical liquid nozzle 132 at a flow rate corresponding to the opening of flow rate adjustment valve 132f. When hydrogen peroxide valve 135v is opened, hydrogen peroxide is supplied from hydrogen peroxide pipe 135p to second chemical liquid nozzle 132 at a flow rate corresponding to the opening of flow rate adjustment valve 135f. When sulfuric acid valve 132v and hydrogen peroxide valve 135v are opened, sulfuric acid and hydrogen peroxide are mixed to generate SPM. Then, this SPM is continuously discharged downward from second chemical liquid nozzle 132 toward the upper surface of substrate W.

[0136] The flow rate of SPM discharged from second chemical liquid nozzle 132 and the mixture ratio of sulfuric acid and hydrogen peroxide solution (the ratio of the flow rate of sulfuric acid to the flow rate of hydrogen peroxide solution) are changed by flow rate adjustment valve 132f and flow rate adjustment valve 135f. The temperature of SPM discharged from second chemical liquid nozzle 132 is changed depending on the mixture ratio of sulfuric acid and hydrogen peroxide solution, the temperature of sulfuric acid before mixing, and the temperature of hydrogen peroxide solution before mixing.

[0137] The mixing ratio of sulfuric acid and hydrogen peroxide solution (the ratio of the flow rate of sulfuric acid to the flow rate of hydrogen peroxide solution) is, for example, 2 or more. When sulfuric acid and hydrogen peroxide solution are mixed, high-temperature SPM is generated due to the heat of dilution of the sulfuric acid. The temperature of the SPM discharged from the second chemical liquid nozzle 132 is, for example, higher than 100° C. The temperature of the sulfuric acid before being mixed with the hydrogen peroxide solution is higher than room temperature, for example, higher than 100° C. The substrate processing apparatus 1 is provided with a heater 34h that heats the sulfuric acid supplied to the second chemical liquid nozzle 132. The temperature of the hydrogen peroxide solution before being mixed with the sulfuric acid is, for example, room temperature (for example, 20 to 30° C.). The temperature of the hydrogen peroxide solution before being mixed with the sulfuric acid may be higher than room temperature.

[0138] Third chemical liquid nozzle 133 is connected to third chemical liquid piping 133p that guides SC1 toward third chemical liquid nozzle 133. When third chemical liquid valve 133v interposed in third chemical liquid piping 133p is opened, SC1 is supplied from third chemical liquid piping 133p to third chemical liquid nozzle 133 and is continuously discharged downward from third chemical liquid nozzle 133.

[0139] Next, an example of processing of the substrate W will be described.

[0140] Fig. 16 is a process diagram for explaining an example of processing of a substrate W performed by the substrate processing apparatus 1. Fig. 16 shows an example in which processing liquids are supplied to the substrate W in the following order: DHF, pure water, SPM, pure water, SC1, and IPA.

[0141] The substrate W to be processed is, for example, a semiconductor wafer such as a silicon wafer. The surface of the substrate W corresponds to a device formation surface on which devices such as transistors and capacitors are formed. An example of resist removal in which an unnecessary resist mask is removed from the substrate W by supplying SPM, which is an example of a resist removing liquid and a resist stripping liquid, to the upper surface of the substrate W will be described below. The processing of the substrate W may be other than resist removal.

[0142] When processing a substrate W, the indexer robot IR takes the substrate W out of the carrier CA on one of the load ports LP. The center robot CR carries the substrate W taken out by the indexer robot IR into one of the processing units 2 and places it on the spin chuck 10. Then, a plurality of chuck pins 11 are pressed horizontally against the edge surface of the substrate W, and the spin motor 14 starts to rotate. This starts the rotation of the substrate W.

[0143] When the rotation of the substrate W is started, the first chemical liquid valve 131v is opened, and the first chemical liquid nozzle 131 discharges DHF toward the upper surface of the rotating substrate W. As a result, the entire upper surface of the substrate W is treated with DHF (an example of step S11: water supply step). This treatment may be a pre-cleaning treatment in which the surface of the substrate W is lightly etched (for example, etching of a native oxide film) to remove foreign matter. When the first chemical liquid nozzle 131 is discharging DHF, the nozzle moving unit 38 may move the first chemical liquid nozzle 131 so that the collision position of the DHF with the upper surface of the substrate W passes through the center and the outer periphery, or may stop the first chemical liquid nozzle 131 so that the collision position stops at the center. Whether or not to move the collision position is the same for other processing liquids (pure water, SPM, SC1, IPA).

[0144] When a predetermined time has elapsed since the first chemical liquid valve 131v was opened, the first chemical liquid valve 131v is closed, and the rinsing liquid valve 134v is opened. In response to this, the rinsing liquid nozzle 134 ejects pure water, which is an example of a rinsing liquid, toward the upper surface of the rotating substrate W. As a result, the DHF on the substrate W is replaced with the pure water, and the DHF is removed from the entire upper surface of the substrate W (Step S12: an example of a water supplying step). Before the rinsing process with pure water, a solvent rinsing step (an example of a solvent supplying step) may be performed in which IPA is supplied to the substrate W from the solvent nozzle 33.

[0145] After the deionized water rinsing process for a predetermined time, the rinsing liquid valve 134v is closed. Then, the SPM process is started (step S13: an example of a high-temperature chemical supply process). That is, the sulfuric acid valve 132v and the hydrogen peroxide valve 135v are opened, whereby the sulfuric acid and the hydrogen peroxide are mixed in the second chemical nozzle 132 to generate SPM, which is then discharged from the second chemical nozzle 132 toward the substrate W. As a result, the entire upper surface of the substrate W is processed by the SPM. By this SPM process, the resist on the upper surface of the substrate W is peeled off and removed outside the substrate W.

[0146] After a predetermined time, the sulfuric acid valve 132v and the hydrogen peroxide valve 135v are closed to end the SPM process. Next, the rinsing liquid valve 134v is opened. In response to this, the rinsing liquid nozzle 134 ejects pure water, which is an example of a rinsing liquid, toward the upper surface of the rotating substrate W. As a result, the SPM on the substrate W is replaced with the pure water, and the SPM is removed from the entire upper surface of the substrate W (Step S14: an example of a water supplying step).

[0147] After the deionized water rinsing process for a predetermined time, the rinsing liquid valve 134v is closed. Then, chemical process using SC1 is started (step S15). That is, the third chemical liquid valve 133v is opened, and the third chemical liquid nozzle 133 discharges SC1 toward the upper surface of the rotating substrate W. As a result, the entire upper surface of the substrate W is processed by SC1. This process may be a residue removal process that removes residues remaining on the substrate after the SPM process and the rinsing process.

[0148] After a predetermined time, the third chemical liquid valve 133v is closed, and the chemical liquid processing using SC1 is completed. Next, the solvent valve 33v is opened. In response to this, the solvent nozzle 33 ejects IPA, which is an example of an organic solvent, toward the upper surface of the rotating substrate W. As a result, the SC1 on the substrate W is replaced with IPA, and a liquid film of IPA is formed covering the entire upper surface of the substrate W (Step S16: an example of a solvent supplying step). Thereafter, the solvent valve 33v is closed. Note that after the chemical liquid processing using SC1, a pure water rinse process may be performed before the supply of IPA begins.

[0149] When the solvent valve 33v is closed, the spin motor 14 rotates the substrate W held by the multiple chuck pins 11 at a high rotation speed (e.g., several thousand rpm). This removes the liquid from the substrate W, and the substrate W is dried (step S17). After the substrate W is dried, the spin motor 14 stops, and the multiple chuck pins 11 move away from the edge surface of the substrate W. This stops the rotation of the substrate W, and the substrate W is released from its hold. Thereafter, the center robot CR takes the substrate W out of the processing unit 2. The indexer robot IR takes the substrate W taken out by the center robot CR into a carrier CA on one of the load ports LP.

[0150] In this manner, one substrate W is treated with a treatment liquid such as a chemical liquid, a rinse liquid, etc. The control device 3 controls the indexer robot IR and the like to cause the substrate treating apparatus 1 to repeat the above-described series of operations. In this manner, a plurality of substrates W are treated one by one.

[0151] Next, the processing liquid supply system will be described.

[0152] The first chemical is DHF (dilute hydrofluoric acid) HF / H 2 The composition ratio of O is about 1 / 1000 to 1 / 100 by volume, and the surface tension is the same as that of water (H 2O) and can be treated as an example of water. Therefore, the path through which the DHF passes before reaching the discharge port 131d of the first chemical-liquid nozzle 131 is a single chemical-liquid flow path 131x that is continuous from the start position to the goal position, and is an example of a water flow path. The structure of the chemical-liquid flow path 131x through which the DHF passes is substantially similar to the structure of the chemical-liquid flow path 31x described with reference to FIG. 5A and the like. Therefore, the above description of the structure of the chemical-liquid flow path 31x will be quoted with "chemical" replaced with "DHF" and used instead as an explanation of the flow path structure of the chemical-liquid flow path 131x through which the DHF passes.

[0153] The third chemical solution, SC1 (ammonia-hydrogen peroxide solution mixture), has a composition ratio, by volume, of 1 part ammonia water (28 to 30 wt%), 1 part hydrogen peroxide solution (30 wt%), and 5 parts water, and has a surface tension of water (H 2 O) and can be treated as an example of water. Therefore, the path through which SC1 passes until it reaches the discharge port 133d of the third chemical-liquid nozzle 133 is one continuous chemical-liquid flow path 133x from the start position to the goal position, and is an example of a water flow path. The structure of the chemical-liquid flow path 133x through which SC1 passes is substantially similar to the structure of the chemical-liquid flow path 31x described with reference to FIG. 5A and the like. Therefore, the above description of the structure of the chemical-liquid flow path 31x will be quoted with "chemical liquid" replaced with "SC1" and substituted for the description of the flow path structure of the chemical-liquid flow path 133x through which SC1 passes.

[0154] Next, the path through which the rinsing liquid passes before being discharged from the discharge port 134d of the rinsing liquid nozzle 134 corresponds to one rinsing liquid flow path 134x that is continuous from the start position to the goal position. The structure of this rinsing liquid flow path 134x is similar to that of the rinsing liquid flow path described with respect to the rinsing liquid nozzle 32 in the configuration example of the processing unit 2 in FIG. 2, so a description thereof will be omitted.

[0155] The structure of the rinsing liquid flow path 32x, which is a path through which the rinsing liquid passes before being discharged from the discharge port 32d of the rinsing liquid nozzle 32, is similar to that of the example configuration of the processing unit 2 in Fig. 2. In addition, the structure of the solvent flow path 33x, which is a path through which the organic solvent passes before being discharged from the discharge port 33d of the solvent nozzle 33, is also similar to that of the example configuration of the processing unit 2 in Fig. 2.

[0156] 17 is a schematic diagram of a chemical liquid supply system that supplies SPM as a second chemical liquid to a substrate W. The substrate processing apparatus 1 includes a sulfuric acid tank 132t that stores sulfuric acid (typically concentrated sulfuric acid) and a hydrogen peroxide tank 135t that stores hydrogen peroxide. The sulfuric acid stored in the sulfuric acid tank 132t is, to be precise, a sulfuric acid-containing liquid that contains sulfuric acid. For example, the SPM used to process the substrate W may be collected and, after a necessary regeneration process, introduced into the sulfuric acid tank 132t and used as sulfuric acid (sulfuric acid-containing liquid). The upstream end of a sulfuric acid pipe 132p is connected to the sulfuric acid tank 132t, and the upstream end of a hydrogen peroxide pipe 135p is connected to the hydrogen peroxide tank 135t. The downstream ends of the sulfuric acid pipe 132p and the hydrogen peroxide pipe 135p are connected to the second chemical liquid nozzle 132. The sulfuric acid piping 132p is provided with a sulfuric acid pump 132P that sends sulfuric acid in the sulfuric acid tank 132t toward the second chemical liquid nozzle 132, and a sulfuric acid filter 132F that removes foreign matter from the sulfuric acid sent out from the sulfuric acid tank 132t. The hydrogen peroxide piping 135p is provided with a pump 135P that sends hydrogen peroxide in the hydrogen peroxide tank 135t toward the second chemical liquid nozzle 132, and a filter 135F that removes foreign matter from the hydrogen peroxide sent out from the hydrogen peroxide tank 135t.

[0157] The hydrogen peroxide solution supplied to the second chemical nozzle 132 and mixed with sulfuric acid has a surface tension similar to that of water (H 2O) and may be treated as an example of water when designing the flow path structure. Therefore, the path through which the hydrogen peroxide solution passes before reaching the second chemical solution nozzle 132 is a single chemical solution flow path 135x that is continuous from the start position to the goal position, and is an example of a water flow path. The structure of chemical solution flow path 135x through which the hydrogen peroxide solution passes is substantially similar to the structure of chemical solution flow path 31x described with reference to FIG. 5A etc. Therefore, the above description of the structure of chemical solution flow path 31x will be quoted with "chemical solution" replaced with "hydrogen peroxide solution" and substituted for the description of the flow path structure of chemical solution flow path 135x for hydrogen peroxide solution.

[0158] Meanwhile, sulfuric acid (concentrated sulfuric acid) supplied to the second chemical nozzle 132 and mixed with the hydrogen peroxide solution, and SPM obtained by mixing sulfuric acid and hydrogen peroxide solution, are examples of high-temperature chemical solutions that are hotter than room temperature. Although it is difficult to equate the behavior of sulfuric acid (especially concentrated sulfuric acid) and SPM as liquids with that of water, there is a risk that impurities (especially plasticizers) in the resin material may dissolve into the chemical solution when the high-temperature chemical solution flow path that contacts the sulfuric acid and SPM, which are high-temperature chemical solutions, is made of a resin material such as fluororesin. Therefore, it is preferable to design the high-temperature chemical solution flow path to minimize the contact area with the chemical solution, similar to the water flow path described above.

[0159] The path through which the high-temperature chemical (sulfuric acid or SPM) passes before being discharged from the discharge port 132d of the second chemical nozzle 132 corresponds to one continuous high-temperature chemical flow path 132x from the start position to the goal position. The sulfuric acid tank 132t is an example of a high-temperature chemical tank, and corresponds to the start position of the high-temperature chemical flow path 132x. The second chemical nozzle 132 is an example of a high-temperature chemical nozzle, and its discharge port 132d corresponds to the goal position of the high-temperature chemical flow path 132x.

[0160] The high-temperature chemical flow path 132x includes a second chemical nozzle 132 provided with an outlet 132d for discharging SPM, and a sulfuric acid pipe 132p for guiding sulfuric acid toward the second chemical nozzle 132. The sulfuric acid pipe 132p is an example of a high-temperature chemical pipe. The high-temperature chemical flow path 132x may further include fluid devices other than the second chemical nozzle 132 and the sulfuric acid pipe 132p. In this example, the high-temperature chemical flow path 132x includes a sulfuric acid valve 132v, a flow rate adjustment valve 132f, a sulfuric acid tank 132t, a sulfuric acid pump 132P, a sulfuric acid filter 132F, and a heater 132h. Instead of or in addition to at least one of these, the high-temperature chemical liquid flow path 132x may further include at least one of a circulation pipe for circulating sulfuric acid from downstream of the heater 132h to the sulfuric acid tank 132t, a flow meter for measuring the flow rate of sulfuric acid supplied to the second chemical liquid nozzle 132, a fitting for connecting two or more pipes, and a manifold for connecting three or more pipes.

[0161] The high-temperature chemical flow path 132x includes an internal space in which a flowing or stationary high-temperature chemical (sulfuric acid or SPM) is disposed, and a cylindrical inner surface 132y that surrounds the entire periphery of the internal space. The internal space of the high-temperature chemical flow path 132x is a sealed space that is open only at the goal position of the high-temperature chemical flow path 132x. In other words, the internal space of the high-temperature chemical flow path 132x is in contact with the space outside the high-temperature chemical flow path 132x only at the goal position of the high-temperature chemical flow path 132x.

[0162] The inner surface 132y of the high-temperature chemical liquid flow path 132x is made of a resin such as a fluororesin. The fluororesin may be PTFE (Polytetrafluoroethylene) or PFA (Perfluoroalkoxy alkane), or may be other than these. The entire inner surface 132y of the high-temperature chemical liquid flow path 132x may be made of the same material, or a part of the inner surface 132y of the high-temperature chemical liquid flow path 132x may be made of a material different from the remaining part of the inner surface 132y of the high-temperature chemical liquid flow path 132x.

[0163] 17, the inner surface 132y of the high-temperature chemical liquid flow path 132x includes an uneven surface 172 that comes into contact with the chemical liquid (sulfuric acid or SPM) in the high-temperature chemical liquid flow path 132x. The uneven surface 172 is a rough surface having a surface roughness greater than that of the mirror surface 71 (see FIG. 5B).

[0164] The entire inner surface 132y of the high-temperature chemical liquid flow path 132x may be the uneven surface 172, or only a part of the inner surface 132y of the high-temperature chemical liquid flow path 132x may be the uneven surface 172. Fig. 17 shows an example in which all or a part of the inner surfaces of the sulfuric acid tank 132t and the second chemical liquid nozzle 132 are the uneven surface 172.

[0165] The uneven surface 172 is a water-repellent surface that has been subjected to a water-repellent treatment similar to that of the above-mentioned chemical liquid flow path 31x, and as a result, the contact angle of sulfuric acid is large, and the contact area with sulfuric acid is accordingly small. The water-repellent treatment may be at least one of cutting, laser processing, plastic processing, extrusion molding, blasting, and etching, or may be other than these.

[0166] As shown in Fig. 17, the uneven surface 172 is a solid surface provided with a plurality of recesses 172u and a plurality of protrusions 172h. The recesses 172u are recessed from the tips 172d of the protrusions 172h. The protrusions 172h protrude from the bottoms 172b of the recesses 172u. The bottoms 172b of the recesses 172u correspond to the bases of the protrusions 172h. The tips 172d of the protrusions 172h correspond to the opening ends of the recesses 172u. The tips 172d of two adjacent protrusions 172h form the entrances of the recesses 172u located between them.

[0167] The convex portion 172h may be linear with a depth longer than the width, or may be dot-like with a depth equal to or approximately equal to the width, or may be other than these. The same applies to the concave portion 172u. The cross section of the convex portion 172h may be any of a rectangle, a square, a triangle, an inverted triangle, a trapezoid, an inverted trapezoid, and a semicircle, or may be other than these. The same applies to the cross section of the concave portion 172u. FIG. 17 shows an example in which the cross sections of the convex portion 172h and the concave portion 172u are rectangular. The height of the convex portion 172h (length in the left-right direction in FIG. 17) may be uniform or may be non-uniform. The same applies to the depth of the concave portion 172u. The height of the convex portion 172h may be equal to or different from the width of the convex portion 172h (length in the up-down direction in FIG. 17). The depth of the concave portion 172u may be equal to or different from the width of the concave portion 172u.

[0168] The contact angle of water with the uneven surface 172 may be 119 degrees or more, and preferably 150 degrees or more.

[0169] The inner surface 132y of the high-temperature chemical liquid flow path 132x is a liquid-contacting part that comes into contact with the liquid. The liquid-contacting part is made of resin such as fluororesin. As described with reference to FIG. 9, fluororesin may contain impurities (small black circles in FIG. 9) different from fluororesin. One example of an impurity is a plasticizer. Such impurities may dissolve from the liquid-contacting part into the high-temperature chemical liquid. To prevent this, when the substrate processing apparatus 1 is started up, that is, when the substrate processing apparatus 1 is being prepared for use in a factory such as a semiconductor manufacturing factory, the liquid-contacting part is washed with a washing liquid. Such washing is also called flushing.

[0170] However, even after cleaning, impurities such as plasticizers migrate from inside the fluororesin to the surface of the fluororesin. If the substrate processing apparatus 1 does not process substrates W for a long period of time (a period during which the liquid does not flow along the liquid contacting portion), many impurities accumulate in the liquid contacting portion and dissolve from the liquid contacting portion into the liquid when processing of the substrate W is resumed. Therefore, if the substrate processing apparatus 1 has not processed substrates W for a long period of time, cleaning must be performed before processing of the substrate W is resumed.

[0171] Cleaning requires not only cleaning fluid but also energy such as electricity. If the time required for cleaning is long, the amount of energy consumed and the amount of cleaning fluid used will increase. The same is true if cleaning is performed many times. In order to reduce cleaning costs and the burden on the environment, it is desirable to reduce the time required for cleaning and the number of times cleaning is performed.

[0172] On the other hand, even when the substrate processing apparatus 1 continues to process substrates W or when the period during which the substrate processing apparatus 1 does not process substrates W is short, contaminants such as impurities may leach into the liquid from the liquid contact part. For example, in an area where the liquid has low fluidity (an area where the liquid stagnates or accumulates), many impurities may accumulate in the liquid contact part and leach into the liquid from the liquid contact part at an unexpected time. It is also possible that foreign matter contained in the liquid may accumulate in an area where the liquid has low fluidity and flow downstream together with the liquid at an unexpected time.

[0173] The uneven surface 172 of the high-temperature chemical flow path 132x is a surface that contacts the tip 172d of the convex portion 172h when the high-temperature chemical liquid is away from the bottom 172b of the concave portion 172u. Therefore, the contact area between the high-temperature chemical liquid and the uneven surface 172 can be reduced compared to when the high-temperature chemical liquid contacts the bottom 172b of the concave portion 172u. Furthermore, since the high-temperature chemical liquid does not contact or is unlikely to contact the bottom 172b of the concave portion 172u, the area where the high-temperature chemical liquid contacts the uneven surface 172 can be limited. This narrows the range to be cleaned, and therefore the cleaning time can be shortened. Furthermore, when the contact area between the high-temperature chemical liquid and the high-temperature chemical flow path 132x is reduced, the amount of impurities eluted from the high-temperature chemical flow path 132x into the high-temperature chemical liquid per unit time is reduced, and therefore the concentration of impurities in the high-temperature chemical liquid can be reduced. The amount of foreign matter transferred from the high-temperature chemical liquid to the uneven surface 172 is also reduced, so that even if such foreign matter peels off from the uneven surface 172, the concentration of foreign matter in the high-temperature chemical liquid can be reduced.

[0174] FIG. 18 is a cross-sectional view showing an example of the cross-sectional structure of a sulfuric acid pipe 132p, which is an example of a high-temperature chemical liquid pipe. The inner peripheral surface of the sulfuric acid pipe 132p includes a striped surface 173 including a plurality of linear protrusions 173h and a plurality of linear grooves 173u that form a striped pattern extending in the axial direction of the sulfuric acid pipe 132p (the direction along the center line 132L of the sulfuric acid pipe 132p). The striped surface 173 is one of the forms of the uneven surface 172 (see FIG. 17). The linear protrusions 173h are one of the forms of the convex portions 172h (see FIG. 17), and the linear grooves 173u are one of the forms of the concave portions 172u (see FIG. 17). It is preferable that the inner surface of the sulfuric acid pipe 132p, preferably the entire section, or at least a portion of the section including the bent section, is made into such a striped surface 173.

[0175] The multiple linear protrusions 173h are arranged at intervals in the circumferential direction of the sulfuric acid pipe 132p (the direction around the center line 132L of the sulfuric acid pipe 132p). The multiple linear grooves 173u are similarly arranged. Each of the multiple linear grooves 173u is formed between two linear protrusions 173h that are closest in the circumferential direction of the sulfuric acid pipe 132p. FIG. 18 shows an example in which the striped surface 173 is endless and surrounds the center line 132L of the sulfuric acid pipe 132p. Only a portion of the inner circumferential surface of the sulfuric acid pipe 132p in the circumferential direction of the sulfuric acid pipe 132p may be the striped surface 173.

[0176] The linear grooves 173u and the linear protrusions 173h extend in a direction parallel to the center line 132L of the sulfuric acid pipe 132p. In a portion where the center line 132L of the sulfuric acid pipe 132p is linear, the linear grooves 173u and the linear protrusions 173h are also linear. In a portion where the center line 132L of the sulfuric acid pipe 132p is curved, the linear grooves 173u and the linear protrusions 173h are also curved. The width of the linear grooves 173u is shorter than the length of the linear grooves 173u. The width of the linear protrusions 173h is shorter than the length of the linear protrusions 173h. The width of the linear protrusions 173h may be equal to or different from the width of the linear grooves 173u.

[0177] Next, the effects of this embodiment in the case where the processing unit 2 described with reference to FIG. 15 and the like is provided will be described.

[0178] The effects on the water flow path and the solvent flow path are as described above.

[0179] Additionally, in this embodiment, the high temperature chemical (sulfuric acid and SPM) is guided by the high temperature chemical flow path 132x toward the substrate W. The high temperature chemical flow path 132x includes an uneven surface 172 that comes into contact with the high temperature chemical.

[0180] The uneven surface 172 of the high-temperature chemical liquid flow path 132x includes a recess 172u at least partially filled with air, and a protrusion 172h in contact with the high-temperature chemical liquid that is in contact with the air in the recess 172u. Since at least a portion of the recess 172u is filled with air, the contact area between the high-temperature chemical liquid and the uneven surface 172 is reduced compared to when the entire recess 172u is filled with the high-temperature chemical liquid. Furthermore, since the high-temperature chemical liquid does not or is unlikely to come into contact with the inner surface of the recess 172u, the area in which the high-temperature chemical liquid comes into contact with the uneven surface 172 can be limited. This narrows the area to be cleaned with the cleaning liquid, thereby shortening the cleaning time.

[0181] In this embodiment, all or a part of the uneven surface 172 is made of fluororesin. Fluororesin is a highly water-repellent material. Whether a droplet on a rough surface adopts the Wenzel state or the Cassie-Baxter state depends on factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface properties of the rough surface. By making the uneven surface 172 from a highly water-repellent material, it is possible to maintain a state in which at least a part of the recesses 172u is filled with air. This makes it possible to reduce the contact area between the high-temperature chemical liquid and the uneven surface 172 while limiting the area in which the high-temperature chemical liquid comes into contact with the uneven surface 172.

[0182] In this embodiment, the high-temperature chemical liquid (high-temperature sulfuric acid) is guided from the sulfuric acid tank 132t to the sulfuric acid pipe 132p (high-temperature chemical liquid pipe). The uneven surface 172 is provided on the inner surface of the sulfuric acid tank 132t. The time that the high-temperature sulfuric acid contacts the sulfuric acid tank 132t is longer than the time that the high-temperature sulfuric acid contacts the sulfuric acid pipe 132p. Therefore, by reducing the contact area between the high-temperature sulfuric acid and the sulfuric acid tank 132t, the contaminants transferred from the sulfuric acid tank 132t to the high-temperature sulfuric acid can be effectively reduced. In particular, when the sulfuric acid tank 132t made of fluororesin is used, the elution of the plasticizer and the formation of impurities can be suppressed. If the sulfuric acid tank 132t is made of quartz, this problem does not occur, but the cost is high. Therefore, by making the sulfuric acid tank 132t of fluororesin, the cost can be reduced while the problem of elution of impurities (plasticizer) can be overcome, thereby improving the substrate processing quality and improving the yield.

[0183] In this embodiment, SPM, which is a high-temperature chemical liquid, is generated, and the inner surface of second chemical liquid nozzle 132 through which the SPM flows and is discharged from outlet 132d is provided with uneven surface 172. When the discharge of SPM from second chemical liquid nozzle 132 is stopped, the SPM stays inside second chemical liquid nozzle 132. Impurities (typically plasticizer) are eluted from second chemical liquid nozzle 132 made of fluororesin into the stagnant SPM. If the SPM is then discharged from second chemical liquid nozzle 132 together with the eluted impurities and supplied to substrate W, this may cause processing defects and reduce product yield. Therefore, by reducing the contact area between the SPM and second chemical liquid nozzle 132, it is possible to effectively reduce contaminants transferred from second chemical liquid nozzle 132 to the SPM, thereby reducing processing defects.

[0184] In this embodiment, an uneven surface 172 is provided on the inner surface (at least the inner surface of the bent portion) of the sulfuric acid pipe 132p constituting the high-temperature chemical liquid flow path 132x. In the bent portion, an area where the fluidity of the liquid is low (an area where the liquid stagnates or accumulates) may occur. In such a case, it is considered that contaminants such as impurities (typically plasticizers) eluted from the resin material (fluororesin such as PTFE and PFA) constituting the sulfuric acid pipe 132p accumulate in the bent portion and flow together with the high-temperature chemical liquid at an unexpected timing. If the uneven surface 172 is provided on the inner surface of the bent portion, the resistance applied to the high-temperature chemical liquid from the inner surface of the bent portion is reduced, so that the decrease in the speed of the high-temperature chemical liquid at the bent portion can be reduced, and the area where the high-temperature chemical liquid stagnates or accumulates can be reduced. Therefore, the impurities and foreign matter accumulated in such an area can be reduced, and the contaminants that move from the inner surface of the bent portion to the high-temperature chemical liquid flowing in the bent portion can be reduced.

[0185] It should be noted that there are other chemicals besides sulfuric acid and SPM that are supplied to the substrate at temperatures higher than room temperature. For example, phosphoric acid is another example of a chemical used at high temperatures.

[0186] Any two or more of the above mentioned features may be combined. Any two or more of the above mentioned steps may be combined.

[0187] 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]

[0188] 1: substrate processing apparatus 1, 10: spin chuck, 11: chuck pin, 12: spin base, 31: chemical nozzle, 31F: chemical filter, 31L: center line of chemical piping, 31P: chemical pump, 31d: outlet of chemical nozzle, 31p: chemical piping, 31t: chemical tank, 31v: chemical valve, 31x: chemical flow path, 31y: inner surface of chemical flow path, 32: rinse liquid nozzle, 32d: outlet of rinse liquid nozzle, 32p: rinse liquid piping, 32v: rinse liquid valve, 33: solvent nozzle 33d: outlet of solvent nozzle, 33F: solvent filter, 33P: solvent pump, 33p: solvent pipe, 33t: solvent tank, 33v: solvent valve, 33x: solvent flow path, 33y: inner surface of solvent flow path, 71: mirror surface, 72: uneven surface, 72b: bottom of recess, 72d: tip of protrusion, 72h: protrusion, 72u: recess, 73: striped surface, 73h: linear protrusion, 73u: linear groove, 74: bent portion, 74c: corner portion, 74d: downstream portion, 74u: upstream portion, 75: mold, 75c: core, 7 5r: ring, 75s: space, 81: lifter, 82: inner tank, 83: outer tank, 84: circulation piping, 85: pump, 86: filter, 87: nozzle, W: substrate, 131: first chemical nozzle, 131d: outlet, 131p: first chemical piping, 131v: first chemical valve, 131x: chemical flow path, 132: second chemical nozzle, 132F: sulfuric acid filter, 132P: sulfuric acid pump, 132d: outlet, 132h: heater, 132p: sulfuric acid piping, 132t: sulfuric acid tank, 132 x: high temperature chemical flow path, 133: third chemical nozzle, 133d: discharge port, 133p: third chemical pipe, 133x: chemical flow path, 134: rinse liquid nozzle, 134d: discharge port, 134p: rinse liquid pipe, 134x: rinse liquid flow path, 135F: filter, 135P: pump, 135p: hydrogen peroxide pipe, 135t: hydrogen peroxide tank, 135x: chemical flow path, 172: uneven surface, 172h: convex portion, 172u: concave portion, 173: striped surface, 173h: linear protrusion, 173u: linear groove

Claims

1. A substrate holder for holding a substrate; a water flow path for directing water toward the substrate held by the substrate holder; a solvent flow path that guides an organic solvent, which is a liquid having a surface tension lower than that of water, toward the substrate held by the substrate holder; The water flow path includes an uneven surface including a recess at least partially filled with air and a protrusion in contact with the water in contact with the air in the recess, The solvent flow path includes a mirror surface in contact with the organic solvent.

2. The substrate processing apparatus according to claim 1 , wherein the uneven surface is made of a fluororesin.

3. The water flow path includes a water tank that stores the water, and a water pipe that guides the water supplied from the water tank, The substrate processing apparatus according to claim 1 , wherein the uneven surface is provided on an inner surface of the water tank.

4. the solvent flow path includes a solvent tank that stores the organic solvent, and a solvent pipe that guides the organic solvent supplied from the solvent tank, The substrate processing apparatus according to claim 1 , wherein the mirror surface is provided on an inner surface of the solvent tank.

5. The substrate processing apparatus according to claim 1 , wherein the uneven surface is provided at a bent portion of the water flow path.

6. a high-temperature chemical flow path for guiding a high-temperature chemical that is higher than room temperature toward the substrate held by the substrate holder; 3 . The substrate processing apparatus according to claim 1 , wherein the high-temperature chemical flow path includes an uneven surface including a recess at least partially filled with air and a protrusion in contact with the high-temperature chemical liquid which is in contact with the air in the recess.

7. The substrate processing apparatus according to claim 6 , wherein the uneven surface of the high-temperature chemical liquid is made of a fluororesin.

8. the high-temperature chemical flow path includes a high-temperature chemical tank that stores the high-temperature chemical, and a high-temperature chemical pipe that guides the high-temperature chemical supplied from the high-temperature chemical tank; The substrate processing apparatus according to claim 6 , wherein the uneven surface of the high-temperature chemical flow path is provided on an inner surface of the high-temperature chemical tank.

9. The substrate processing apparatus according to claim 8 , wherein the uneven surface is provided at a bent portion of the high-temperature chemical flow path.

10. The high-temperature chemical flow path includes a high-temperature chemical pipe that guides the high-temperature chemical, and a high-temperature chemical nozzle that discharges the high-temperature chemical guided by the high-temperature chemical pipe, The substrate processing apparatus according to claim 6 , wherein the uneven surface of the high-temperature chemical flow path is provided on an inner surface of the high-temperature chemical nozzle.

11. The substrate processing apparatus according to claim 10 , wherein the uneven surface is provided at a bent portion of the high-temperature chemical flow path.

12. a water supplying step of guiding the water toward a substrate held by a substrate holder through a water flow path including the uneven surface, in a state in which at least a portion of the concave portions of the uneven surface is filled with air and the convex portions of the uneven surface are in contact with water that is in contact with the air in the concave portions; a solvent supplying step of guiding the organic solvent, which is a liquid having a lower surface tension than the water, to the substrate held by the substrate holder through a solvent flow path including the mirror surface, before or after the water supplying step, while the mirror surface is in contact with the organic solvent, which is a liquid having a lower surface tension than the water.

13. The method further includes a high-temperature chemical supply step of guiding a high-temperature chemical, the high-temperature chemical being higher than room temperature, toward the substrate held by the substrate holder; 13. The substrate processing method of claim 12, wherein the high-temperature chemical liquid supplying step includes a step of circulating the high-temperature chemical liquid through a high-temperature chemical liquid flow path including the uneven surface in a state in which at least a portion of the concave portions of the uneven surface are filled with air and the convex portions of the uneven surface are in contact with the high-temperature chemical liquid that is in contact with the air in the concave portions.

14. A substrate holder for holding a substrate; a high-temperature chemical flow path that guides a high-temperature chemical that is higher than room temperature toward the substrate held by the substrate holder; The high-temperature chemical liquid flow path includes an uneven surface including a recess at least partially filled with air, and a protrusion in contact with the high-temperature chemical liquid which is in contact with the air in the recess.

15. a solvent flow path that guides an organic solvent, which is a liquid having a surface tension lower than that of the high-temperature chemical liquid, toward the substrate held by the substrate holder; The substrate processing apparatus according to claim 14 , wherein the solvent flow path includes a mirror surface in contact with the organic solvent.

16. The substrate processing apparatus according to claim 14 , wherein the uneven surface is made of a fluororesin.

17. the high-temperature chemical flow path includes a high-temperature chemical tank that stores the high-temperature chemical, and a high-temperature chemical pipe that guides the high-temperature chemical supplied from the high-temperature chemical tank; The substrate processing apparatus according to claim 14 , wherein the uneven surface is provided on an inner surface of the high-temperature chemical tank.

18. The high-temperature chemical flow path includes a high-temperature chemical pipe that guides the high-temperature chemical, and a high-temperature chemical nozzle that discharges the high-temperature chemical guided by the high-temperature chemical pipe, The substrate processing apparatus according to claim 14 , wherein the uneven surface is provided on an inner surface of the high-temperature chemical nozzle.

19. The substrate processing apparatus according to claim 17 or 18, wherein the uneven surface is provided at a bent portion of the high-temperature chemical flow path.

20. A high-temperature chemical supply step includes guiding a high-temperature chemical, the high-temperature chemical being higher than room temperature, toward a substrate held by a substrate holder; The substrate processing method includes a step of circulating the high-temperature chemical liquid through a high-temperature chemical liquid flow path including the uneven surface in a state in which at least a portion of the concave portions of the uneven surface are filled with air and the convex portions of the uneven surface are in contact with the high-temperature chemical liquid that is in contact with the air in the concave portions.

21. The substrate processing method of claim 20, further comprising a solvent supplying step of guiding the organic solvent, which is a liquid having a lower surface tension than the high-temperature chemical liquid, toward the substrate held by the substrate holder through a solvent flow path including the mirror surface, before or after the high-temperature chemical liquid supplying step, while the mirror surface is in contact with the organic solvent, which is a liquid having a lower surface tension than the high-temperature chemical liquid.

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