Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method in which a water-containing liquid on an upper surface of a substrate is removed by a water absorber in a state where water repellency of the upper surface of the substrate is enhanced.SOLUTION: The substrate processing method includes a water repellent agent supplying step of supplying a water repellent agent-containing liquid for increasing a contact angle of water with respect to a horizontal smooth surface made of the same material as an end face s1 of a protrusion P1 to a value exceeding 90 degrees to an upper surface of a substrate W, a water supplying step of supplying a water-containing liquid to the upper surface of the substrate W after supplying the water repellent agent-containing liquid to the upper surface of the substrate W, and a water absorbing step of removing the water-containing liquid from the upper surface of the substrate W by bringing a water absorbing body 41 for absorbing the water-containing liquid into contact with the water-containing liquid on the upper surface of the substrate W.SELECTED DRAWING: Figure 8A-E

Description

[Technical Field]

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

[0002] Patent Document 1 discloses that a substrate is dried after a processing liquid is supplied to the substrate.

[0003] Patent Document 1 states that "the pattern PT is reinforced by contacting a contact member 3, which is hygroscopic with respect to the rinse liquid, with the pattern PT so as to cover the entire substrate surface Wf, and the rinse liquid adhering to the substrate surface Wf is absorbed and removed by the contact member 3 while the pattern PT is in this reinforced state."

[0004] Patent document 1 states that "various substrate processing technologies have been proposed, such as hydrophobic drying technology (e.g., Patent document 3)," and also states that "use of the technology described in Patent document 3 requires complex equipment and processing, and therefore the cost is a major obstacle to practical application." [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-149763 Summary of the Invention [Problem to be solved by the invention]

[0006] The method and apparatus described in Patent Document 1 causes the contact member 3 to absorb the rinse liquid without increasing the water repellency of the upper surface of the substrate, including the surface of the pattern. Patent Document 1 rather contains negative comments about the hydrophobic drying technique.

[0007] At least one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus in which a water-containing liquid on the upper surface of a substrate is removed by a water absorbing body in a state in which the water repellency of the upper surface of the substrate is increased. [Means for solving the problem]

[0008] One embodiment of the present invention provides a substrate processing method for processing a substrate having a pattern including convex portions and concave portions formed on an upper surface thereof, the substrate processing method including: a water-repellent supplying step of supplying a water-repellent-containing liquid to the upper surface of the substrate, the water-repellent-containing liquid increasing the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees; a water supplying step of supplying a water-containing liquid to the upper surface of the substrate after supplying the water-repellent-containing liquid to the upper surface of the substrate; and a water absorbing step of removing the water-containing liquid from the upper surface of the substrate by bringing a water-absorbing body that absorbs the water-containing liquid into contact with the water-containing liquid on the upper surface of the substrate.

[0009] In the above embodiment, at least one of the following features may be added to the substrate processing method.

[0010] The substrate processing method further includes a post-water-repellent hydrophobic liquid supplying step of supplying a hydrophobic liquid that is soluble in the water-repellent agent-containing liquid to the upper surface of the substrate, thereby replacing the water-repellent agent-containing liquid on the upper surface of the substrate with the hydrophobic liquid, and a post-water-repellent amphipathic liquid supplying step of supplying an amphipathic liquid that has a higher water solubility than the hydrophobic liquid and is soluble in the hydrophobic liquid to the upper surface of the substrate, thereby replacing the hydrophobic liquid on the upper surface of the substrate with the amphipathic liquid, and the water supplying step is a step of replacing the amphipathic liquid on the upper surface of the substrate with the water-containing liquid by supplying the water-containing liquid that has a higher surface tension than the amphipathic liquid and is soluble in the amphipathic liquid to the upper surface of the substrate.

[0011] The substrate processing method further includes a chemical solution supplying step of supplying, to the upper surface of the substrate, a chemical solution that oxidizes the upper surface of the substrate; a rinse liquid supplying step of supplying, to the upper surface of the substrate, the water-containing liquid as a rinse liquid, thereby replacing the chemical solution on the upper surface of the substrate with the water-containing liquid; a pre-water-repellent amphipathic liquid supplying step of supplying, to the upper surface of the substrate, an amphipathic liquid that is soluble in the water-containing liquid, thereby replacing the water-containing liquid on the upper surface of the substrate with the amphipathic liquid; and a pre-water-repellent hydrophobic liquid supplying step of supplying, to the upper surface of the substrate, a hydrophobic liquid that has a lower water solubility than the amphipathic liquid and is soluble in the amphipathic liquid, thereby replacing the amphipathic liquid on the upper surface of the substrate with the hydrophobic liquid, and the water-repellent agent supplying step is a step of supplying, to the upper surface of the substrate, the water-repellent agent-containing liquid, thereby replacing the hydrophobic liquid on the upper surface of the substrate with the water-repellent agent-containing liquid.

[0012] The water absorbing step includes a step of bringing the water absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining the water absorbing body separated from the upper surface of the substrate.

[0013] The water absorption step includes a step of bringing the water absorbent body into contact with the water-containing liquid on the upper surface of the substrate in a state in which at least a portion of the recess is filled with air and the water-containing liquid is supported by the air in the recess and the protrusion before the water absorbent body comes into contact with the water-containing liquid on the upper surface of the substrate.

[0014] The water absorbing step includes a step of bringing the water absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining a state in which the substrate and the water absorbing body do not move relatively in the horizontal direction.

[0015] In the substrate processing method, spin drying, which involves drying the substrate by rotating the substrate, is not performed after the water-containing liquid on the upper surface of the substrate is brought into contact with the water-absorbing body.

[0016] Another embodiment of the present invention provides a substrate processing apparatus including: a substrate holder that horizontally holds a substrate having a pattern including convex portions and concave portions formed on an upper surface thereof; at least one nozzle that individually ejects a plurality of processing liquids toward the upper surface of the substrate held by the substrate holder, the processing liquid including a water-containing liquid and a water-repellent-containing liquid that increases the contact angle of water with a horizontal smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees; a water-absorbing body that absorbs the water-containing liquid; and a water-absorbing actuator that moves at least one of the substrate and the water-absorbing body to bring the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate held by the substrate holder, thereby removing the water-containing liquid from the upper surface of the substrate.

[0017] In the above embodiment, at least one of the following features may be added to the substrate processing apparatus.

[0018] The at least one nozzle individually ejects a plurality of processing liquids, including the water-repellent-containing liquid, a hydrophobic liquid that is soluble in the water-repellent-containing liquid, an amphipathic liquid that has a higher water solubility than the hydrophobic liquid and is soluble in the hydrophobic liquid, and the water-containing liquid that has a higher surface tension than the amphipathic liquid and is soluble in the amphipathic liquid, onto the upper surface of the substrate held by the substrate holder, and the substrate processing apparatus further includes at least one valve that causes the at least one nozzle to individually eject the plurality of processing liquids, and a control device that controls the at least one valve and the water-absorbing actuator.

[0019] The control device performs a water-repellent supplying step of supplying the water-repellent-containing liquid to the upper surface of the substrate, a post-water-repellent hydrophobic liquid supplying step of supplying the hydrophobic liquid to the upper surface of the substrate, thereby replacing the water-repellent-containing liquid on the upper surface of the substrate with the hydrophobic liquid, a post-water-repellent amphipathic liquid supplying step of supplying the amphipathic liquid to the upper surface of the substrate, thereby replacing the hydrophobic liquid on the upper surface of the substrate with the amphipathic liquid, a water supplying step of supplying the water-containing liquid to the upper surface of the substrate, thereby replacing the amphipathic liquid on the upper surface of the substrate with the water-containing liquid, and a water absorbing step of contacting the water-containing liquid on the upper surface of the substrate with the water-absorbing body, thereby removing the water-containing liquid from the upper surface of the substrate.

[0020] The at least one nozzle individually ejects a plurality of processing liquids, including the water-repellent-containing liquid, the water-containing liquid, a chemical liquid that oxidizes the top surface of the substrate, an amphipathic liquid that is soluble in the water-containing liquid, and a hydrophobic liquid that has a lower water solubility than the amphipathic liquid and is soluble in the amphipathic liquid, onto the top surface of the substrate held by the substrate holder, and the substrate processing apparatus further includes at least one valve that individually ejects the plurality of processing liquids from the at least one nozzle, and a control device that controls the at least one valve and the water-absorbing actuator.

[0021] the control device includes a chemical solution supplying step of supplying the chemical solution to the upper surface of the substrate; a rinse liquid supplying step of supplying the water-containing liquid as a rinse liquid to the upper surface of the substrate, thereby replacing the chemical solution on the upper surface of the substrate with the water-containing liquid; a pre-water-repellent amphipathic liquid supplying step of supplying the amphipathic liquid to the upper surface of the substrate, thereby replacing the water-containing liquid on the upper surface of the substrate with the amphipathic liquid; and a pre-water-repellent amphipathic liquid supplying step of supplying the hydrophobic liquid to the upper surface of the substrate, thereby replacing the water-containing liquid on the upper surface of the substrate with the amphipathic liquid. The method includes a pre-water-repellent hydrophobic liquid supplying step of replacing the amphipathic liquid on the upper surface of the substrate with the hydrophobic liquid, a water-repellent agent supplying step of replacing the hydrophobic liquid on the upper surface of the substrate with the water-repellent agent-containing liquid by supplying the water-repellent agent-containing liquid to the upper surface of the substrate, a water supplying step of supplying the water-containing liquid to the upper surface of the substrate, and a water-absorbing step of removing the water-containing liquid from the upper surface of the substrate by bringing the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate.

[0022] The water-absorbing actuator brings the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining the water-absorbing body separated from the upper surface of the substrate.

[0023] The water-absorbing actuator brings the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate in a state in which at least a portion of the recess is filled with air and the water-containing liquid is supported by the air in the recess and the protrusion before the water-absorbing body comes into contact with the water-containing liquid on the upper surface of the substrate.

[0024] The water-absorbing actuator brings the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining a state in which the substrate and the water-absorbing body do not move relatively in the horizontal direction.

[0025] The substrate processing apparatus does not perform spin drying, which involves drying the substrate by rotating the substrate, after bringing the water-containing liquid on the upper surface of the substrate into contact with the water-absorbing body. [Brief explanation of the drawings]

[0026] [Figure 1A] 1 is a schematic plan view showing a layout of a substrate processing apparatus according to an embodiment; [Figure 1B] FIG. 2 is a schematic side view of the substrate processing apparatus. [Figure 2] FIG. 2 is a schematic diagram showing the interior of the processing unit as viewed horizontally. [Figure 3] FIG. 10 is a schematic view of the water absorber and the blocking plate viewed horizontally. [Figure 4] FIG. 10 is a schematic view of the water absorber and the blocking plate viewed horizontally. [Figure 5] FIG. 2 is a block diagram showing an electrical configuration of the substrate processing apparatus. [Figure 6] 1 is a schematic cross-sectional view showing an example of the structure of a substrate to be processed by a substrate processing apparatus. [Figure 7] 5A to 5C are process diagrams for explaining an example of substrate processing performed by the substrate processing apparatus. [Figure 8A-E] FIG. 10 is a schematic cross-sectional view for explaining a water absorption step. [Figure 9A] FIG. 1 is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in a Wenzel state. [Figure 9B] FIG. 1 is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in a Cassie-Baxter state. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0028] 1A is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment, and FIG.

[0029] 1A, the substrate processing apparatus 1 is a single-wafer processing apparatus that processes disk-shaped substrates W, such as semiconductor wafers, one by one. The substrate processing apparatus 1 includes a load port LP that holds carriers CA that accommodate multiple substrates W, such as FOUPs (Front-Opening Unified Pods), multiple processing units 2 that process the substrates W transferred from the carriers CA on the load port LP with processing fluids, such as processing liquids and processing gases, a transfer system TS that transfers the substrates W between the carriers CA on the load port LP and the multiple processing units 2, an outer wall 1a that forms an enclosed space that houses the multiple processing units 2 and the transfer system TS, and a control device 3 that controls the substrate processing apparatus 1.

[0030] The multiple processing units 2 form multiple towers TW. FIG. 1A shows an example in which four towers TW are formed. As shown in FIG. 1B, the multiple processing units 2 included in one tower TW are stacked one on top of the other. As shown in FIG. 1A, the multiple towers TW form two rows extending in the depth direction of the substrate processing apparatus 1 (left and right directions on the paper surface of FIG. 1A) in a plan view. In a plan view, the two rows face each other via a transport path TP.

[0031] The transport system TS includes an indexer robot IR that loads and unloads substrates W into and from carriers CA on the load port LP, and a center robot CR that loads and unloads substrates W into and from multiple processing units 2. The center robot CR is disposed on the transport path TP. The indexer robot IR is disposed between the load port LP and the center robot CR in a plan view. The indexer robot IR hands over substrates W to the center robot CR and receives substrates W from the center robot CR. The same is true for the center robot CR.

[0032] The indexer robot IR includes one or more hands Hi that support a substrate W horizontally. The hands Hi can move parallel in both the horizontal and vertical directions. The hands Hi can rotate about a vertical line. The hands Hi can load and unload a substrate W to and from a carrier CA on any of the load ports LP, and can transfer a substrate W to and from the center robot CR.

[0033] The center robot CR includes one or more hands Hc that support the substrate W horizontally. The hands Hc can move parallel in both the horizontal and vertical directions. The hands Hc can rotate about a vertical line. The hands Hc can transfer the substrate W to and from the indexer robot IR, and can transport the substrate W into and out of any of the processing units 2.

[0034] Next, the processing unit 2 will be described.

[0035] Fig. 2 is a horizontal schematic diagram of the interior of the processing unit 2. A water absorber 41 and a blocking plate 42, which will be described later, are omitted from Fig. 2. As shown in Fig. 2, the processing unit 2 includes a chamber 4 that accommodates a substrate W, and a spin chuck 10 that holds one substrate W horizontally within the chamber 4 and rotates the substrate W about a vertical rotation axis A1 that passes through the center of the substrate W.

[0036] The chamber 4 includes a box-shaped partition wall 5 having a passage opening 5b through which the substrate W passes, and a door 6 for opening and closing the passage opening 5b. The FFU 7 (fan filter unit 7) is disposed above an air outlet 5a disposed at the top of the partition wall 5. The FFU 7 constantly supplies clean air (air filtered by a filter) into the chamber 4 through the air outlet 5a. The gas within the chamber 4 is exhausted from the chamber 4 through an exhaust duct 8 connected to the bottom of a processing cup 21 (described later). 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.

[0037] The spin chuck 10 includes a disk-shaped spin base 11 that holds the substrate W horizontally, a spin shaft 12 that extends downward from the spin base 11 along a rotation axis A1, and a spin motor 13 that rotates the spin base 11 and the spin shaft 12 about the rotation axis A1. The spin base 11 is connected to a suction pipe 14 to which a suction valve 15 is attached.

[0038] When the suction valve 15 is opened while the substrate W is placed horizontally on the upper surface of the spin base 11, the suction force of a suction device such as a pump is transmitted to the spin base 11 via the suction piping 14. As a result, the lower surface of the substrate W is attracted to the upper surface of the spin base 11, and the substrate W is held by the spin chuck 10. The spin chuck 10 is not limited to a vacuum-type chuck, but may also be a clamp-type chuck in which multiple chuck pins contact the edge surface of the substrate W, or a chuck other than a vacuum-type or clamp-type chuck. When the spin chuck 10 is a clamp-type chuck, the multiple chuck pins correspond to the substrate holder. When the spin chuck 10 is a vacuum-type chuck, the spin base 11 corresponds to the substrate holder.

[0039] The processing unit 2 includes a cylindrical processing cup 21 that receives the processing liquid splashed from the substrate W. The processing cup 21 includes a plurality of guards 24 that receive the processing liquid discharged outward from the substrate W held on the spin chuck 10, a plurality of cups 23 that receive the processing liquid guided downward by the plurality of guards 24, and a cylindrical outer wall 22 that surrounds the plurality of guards 24 and the plurality of cups 23. Figure 2 shows an example in which four guards 24 and three cups 23 are provided, and the outermost cup 23 is integrated with the third guard 24 from the top.

[0040] The guard 24 includes a cylindrical portion 25 that surrounds the spin chuck 10 and an annular ceiling portion 26 that extends obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. The multiple ceiling portions 26 are stacked one on top of the other, and the multiple cylindrical portions 25 are arranged concentrically. The upper end of the annular ceiling portion 26 corresponds to the upper end of the guard 24 that surrounds the substrate W and the spin base 11 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.

[0041] The processing unit 2 includes an elevation actuator 27 that individually raises and lowers the multiple guards 24. The elevation actuator 27 stops the guards 24 at any position within a range from the upper position to the lower position. FIG. 2 shows a state in which two guards 24 are positioned at the upper position and the remaining two guards 24 are positioned at the lower position. The upper position is a position in which the upper ends of the guards 24 are positioned above the holding position in which the substrate W held by the spin chuck 10 is positioned. The lower position is a position in which the upper ends of the guards 24 are positioned below the holding position.

[0042] An actuator is a device that converts driving energy, such as electrical, fluid, magnetic, thermal, or chemical energy, into mechanical work, i.e., the movement of a tangible object. Actuators include electric motors (rotary motors), linear motors, air cylinders, and other devices. When the movement of the actuator differs from the movement of the object, a motion converter may be provided to convert the movement of the actuator into linear motion or rotation. For example, if the actuator is an electric motor that moves the object linearly, the rotation of the electric motor may be converted into linear motion by a motion converter such as a ball screw and ball nut.

[0043] Processing unit 2 includes a plurality of nozzles that discharge processing fluids such as processing liquid and processing gas toward substrate W held on spin chuck 10. The plurality of nozzles include first chemical liquid nozzle 31a, first rinsing liquid nozzle 31b, second chemical liquid nozzle 31c, second rinsing liquid nozzle 31d, water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g.

[0044] First chemical liquid nozzle 31a and second chemical liquid nozzle 31c are nozzles that eject chemical liquid toward the upper surface of substrate W. First rinsing liquid nozzle 31b and second rinsing liquid nozzle 31d are nozzles that eject rinsing liquid toward the upper surface of substrate W. Water repellent agent nozzle 31e is a nozzle that ejects a water repellent agent-containing liquid toward the upper surface of substrate W. Hydrophobic liquid nozzle 31f is a nozzle that ejects a hydrophobic liquid toward the upper surface of substrate W. Amphipathic liquid nozzle 31g is a nozzle that ejects an amphipathic liquid toward the upper surface of substrate W.

[0045] FIG. 2 shows an example in which the first chemical liquid is DFH (dilute hydrofluoric acid), the second chemical liquid is SC1 (a mixture of ammonia water, hydrogen peroxide, and water), and the rinse liquid is DIW (pure water). DFH is a chemical liquid that removes native silicon oxide films. SC1 is a chemical liquid that removes particles, organic matter, and the like from the substrate W. SC1 is an example of a chemical liquid that oxidizes the top surface of the substrate W.

[0046] First chemical liquid nozzle 31a may be a scan nozzle that moves the collision position of the chemical liquid on substrate W within the upper surface of substrate W, or may be a fixed nozzle that cannot move the collision position of the chemical liquid on substrate W. The same applies to the other nozzles. Figure 2 shows an example in which all the nozzles, that is, first chemical liquid nozzle 31a, first rinsing liquid nozzle 31b, second chemical liquid nozzle 31c, second rinsing liquid nozzle 31d, water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g, are scan nozzles.

[0047] First chemical liquid nozzle 31a and first rinse liquid nozzle 31b are connected to first nozzle actuator 35a, which moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b in at least one of the vertical and horizontal directions. First chemical liquid nozzle 31a and first rinse liquid nozzle 31b extend downward from first nozzle arm 34a, which extends horizontally within chamber 4. First nozzle actuator 35a moves first nozzle arm 34a, thereby moving first chemical liquid nozzle 31a and first rinse liquid nozzle 31b.

[0048] Second chemical liquid nozzle 31c and second rinse liquid nozzle 31d are connected to second nozzle actuator 35b, which moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d in at least one of the vertical and horizontal directions. Second chemical liquid nozzle 31c and second rinse liquid nozzle 31d extend downward from second nozzle arm 34b, which extends horizontally within chamber 4. Second nozzle actuator 35b moves second nozzle arm 34b, thereby moving second chemical liquid nozzle 31c and second rinse liquid nozzle 31d.

[0049] The water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g are connected to a third nozzle actuator 35c that moves the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in at least one of the vertical and horizontal directions. The water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g extend downward from a third nozzle arm 34c that extends horizontally within the chamber 4. The third nozzle actuator 35c moves the third nozzle arm 34c, thereby moving the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g.

[0050] First nozzle actuator 35a horizontally moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b between a processing position where the processing liquid discharged from first chemical liquid nozzle 31a or first rinse liquid nozzle 31b is supplied to the upper surface of substrate W and a standby position where first chemical liquid nozzle 31a and first rinse liquid nozzle 31b are positioned around processing cup 21 in a plan view. The same applies to second nozzle actuator 35b and rinse liquid actuator. Figure 2 shows a state where water repellent agent nozzle 31e, hydrophobic liquid nozzle 31f, and amphipathic liquid nozzle 31g are arranged at the processing positions.

[0051] First chemical liquid nozzle 31a is connected to first chemical liquid pipe 32a that guides the first chemical liquid. When first chemical liquid valve 33a attached to first chemical liquid pipe 32a is opened, the outlet of first chemical liquid nozzle 31a continuously discharges the first chemical liquid downward. Similarly, second chemical liquid nozzle 31c is connected to second chemical liquid pipe 32c that guides the second chemical liquid. When second chemical liquid valve 33c attached to second chemical liquid pipe 32c is opened, the outlet of second chemical liquid nozzle 31c continuously discharges the second chemical liquid downward.

[0052] The first chemical liquid may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, aqueous ammonia, hydrogen peroxide, organic acid (e.g., citric acid, oxalic acid, etc.), organic alkali (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and corrosion inhibitor, or may be a liquid other than these. The same applies to the second chemical liquid. The first chemical liquid may be a liquid having the same composition as the second chemical liquid but different from the second chemical liquid in at least one of concentration and temperature.

[0053] Although not shown, first chemical liquid valve 33a includes a valve body with an annular valve seat through which the chemical liquid passes, a valve element movable relative to the valve seat, and an actuator that moves the valve element between a closed position in which the valve element contacts the valve seat and an open position in which the valve element is separated from the valve seat. The same applies to the other valves. The actuator may be a pneumatic actuator, an electric actuator, or another type of actuator. Control device 3 controls the actuator to open and close first chemical liquid valve 33a, etc.

[0054] The first rinse liquid nozzle 31b is connected to a first rinse liquid pipe 32b that guides the first rinse liquid. When a first rinse liquid valve 33b attached to the first rinse liquid pipe 32b is opened, the outlet of the first rinse liquid nozzle 31b continuously discharges the first rinse liquid downward. Similarly, the second rinse liquid nozzle 31d is connected to a second rinse liquid pipe 32d that guides the second rinse liquid. When a second rinse liquid valve 33d attached to the second rinse liquid pipe 32d is opened, the outlet of the second rinse liquid nozzle 31d continuously discharges the second rinse liquid downward.

[0055] The first rinse liquid may be any of pure water (deionized water: DIW), carbonated water, electrolytic ionized water, hydrogen water, ozone water, diluted hydrochloric acid water (for example, about 1 to 100 ppm), and diluted ammonia water (for example, about 1 to 100 ppm), or may be a liquid other than these. The same applies to the second rinse liquid. The first rinse liquid may have the same composition as the second rinse liquid but differ from the second rinse liquid in at least one of the concentration and temperature. The rinse liquid is an example of a water-containing liquid. The water-containing liquid may be a liquid whose water content is 100% or substantially 100% (for example, 99% or more), or may be a liquid containing substances other than water.

[0056] The water repellent nozzle 31e is connected to a water repellent pipe 32e that guides a water repellent-containing liquid. When a water repellent valve 33e attached to the water repellent pipe 32e is opened, the outlet of the water repellent nozzle 31e continuously discharges the water repellent-containing liquid downward. Similarly, the hydrophobic liquid nozzle 31f is connected to a hydrophobic liquid pipe 32f that guides a hydrophobic liquid. When a hydrophobic liquid valve 33f attached to the hydrophobic liquid pipe 32f is opened, the outlet of the hydrophobic liquid nozzle 31f continuously discharges the hydrophobic liquid downward. The amphipathic liquid nozzle 31g is connected to an amphipathic liquid pipe 32g that guides an amphipathic liquid. When an amphipathic liquid valve 33g attached to the amphipathic liquid pipe 32g is opened, the outlet of the amphipathic liquid nozzle 31g continuously discharges the amphipathic liquid downward.

[0057] The hydrophobic liquid is a liquid that dissolves in the water-repellent-containing liquid. The amphipathic liquid is a liquid that dissolves in both the hydrophobic liquid and the water-containing liquid. The amphipathic liquid may also be a liquid that dissolves in the water-repellent-containing liquid. If the solubility of water in the hydrophobic liquid is lower than the solubility of water in the amphipathic liquid, the hydrophobic liquid may also be a liquid that dissolves in the water-containing liquid. The solubility of water in the amphipathic liquid is lower than the solubility of water in the water-containing liquid. The surface tension of the amphipathic liquid is lower than the surface tension of the water-containing liquid. The surface tension of the amphipathic liquid may be equal to, higher than, or lower than the surface tension of the hydrophobic liquid. The surface tension of the hydrophobic liquid may be equal to, higher than, or lower than the surface tension of the water-containing liquid.

[0058] The hydrophobic liquid and the amphipathic liquid may be organic solvents. In this case, the hydrophobic liquid may be at least one of alcohols such as IPA (isopropyl alcohol), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. The same is true for amphiphilic liquids.

[0059] The water-repellent agent-containing liquid is a liquid that modifies the upper surface of the substrate W. The water-repellent agent-containing liquid is a liquid that makes the upper surface of the substrate W hydrophobic. After the water-repellent agent-containing liquid is supplied, the upper surface of the substrate W is a water-repellent surface. As will be described later, the upper surface of the substrate W is a rough surface on which a pattern PA (see FIG. 6) including convex portions P1 and concave portions Q1 is formed. The water-repellent agent-containing liquid is a liquid that increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end surface s1 of the convex portion P1 to a value greater than 90 degrees.

[0060] The water-repellent-containing liquid may be a liquid containing 100% or substantially 100% water-repellent, or may be a liquid containing substances other than the water-repellent. In the latter case, the water-repellent-containing liquid may be a solution containing the water-repellent as a solute and a solvent that dissolves in the water-repellent. In this case, the solvent of the water-repellent-containing liquid may be at least one of the specific examples of organic solvents mentioned above, such as IPA. The solvent contained in the water-repellent-containing liquid may be a liquid having the same composition as the hydrophobic liquid.

[0061] The water repellent agent may be at least one of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDTS), 3-aminopropyltriethoxysilane (APTES), benzyltrichlorosilane (Bn-TS), 11-cyanoundecyltrichlorosilane, 11-iodoundecyltrichlorosilane, 11-bromoundecyltrichlorosilane, 11-chloroundecyltrichlorosilane, and undecyltrichlorosilane (H-UTS). That is, the water repellent agent may be a silylating agent.

[0062] In the following, an example will be described in which the water repellent-containing liquid is a solution containing FDTS as a solute and toluene as a solvent, the hydrophobic liquid is toluene, and the amphipathic liquid is IPA.

[0063] Next, the water absorbent body 41 will be described.

[0064] 3 and 4 are schematic diagrams showing the water absorbent body 41 and the blocking plate 42 viewed horizontally. Fig. 3 shows the water absorbent body 41 and the blocking plate 42 in the upper position, and Fig. 4 shows the water absorbent body 41 and the blocking plate 42 in the lower position. Fig. 3 shows a vertical cross section of the water absorbent body 41 and the blocking plate 42, and Fig. 4 shows the appearance of the water absorbent body 41 and the blocking plate 42.

[0065] The processing unit 2 includes a water absorber 41 that comes into contact with water on the substrate W held on the spin chuck 10, thereby removing water from the upper surface of the substrate W. The water absorber 41 is disposed in the chamber 4. The water absorber 41 is disposed above the substrate W held on the spin chuck 10.

[0066] 3 and 4 show an example in which the water absorbent body 41 is in the form of a horizontal sheet or plate. The water absorbent body 41 may be in a shape other than a sheet or plate, and may be held in a position other than horizontal. When viewed in the vertical direction, the area of ​​the water absorbent body 41 may be equal to or approximately equal to the area of ​​the substrate W, or may be larger or smaller than the area of ​​the substrate W. In the example shown in FIGS. 3 and 4, the water absorbent body 41 is in the form of a horizontal disk whose diameter is equal to or larger than the diameter of the substrate W.

[0067] 3 and 4 show an example in which the water absorbent body 41 is attached to a blocking plate 42. The blocking plate 42 corresponds to a water absorbent body holder that holds the water absorbent body 41. The blocking plate 42 is a horizontal, circular plate with a diameter equal to or greater than the diameter of the substrate W. The blocking plate 42 is a plate that has lower water absorption properties than the water absorbent body 41. The blocking plate 42 is disposed above the water absorbent body 41. The lower surface of the blocking plate 42 is in contact with the water absorbent body 41. The lower surface of the blocking plate 42 is concentric with the lower surface 41L of the water absorbent body 41. The center of the lower surface of the blocking plate 42 is disposed on the rotation axis A1 of the substrate W. The diameter of the lower surface of the blocking plate 42 may be equal to the diameter of the lower surface 41L of the water absorbent body 41, or may be larger or smaller than that diameter.

[0068] The water absorbent body 41 is a member that absorbs and retains water. The water absorbed by the water absorbent body 41 is not limited to a liquid with a water content of 100% or substantially 100%, but may also contain liquids other than water. The water absorbent body 41 may be solid or semi-solid, or may contain a solid portion and a semi-solid portion (a gel-like or jelly-like portion). The water absorbent body 41 may contain a liquid contained in the solid or semi-solid portion. When at least a portion of the water absorbent body 41 is solid, the entire water absorbent body 41 or the solid portion may be flexible.

[0069] The water absorbent body 41 may be solid or porous, or may include both solid and porous portions. When at least a portion of the water absorbent body 41 is porous and absorbs water by capillary action, the entire water absorbent body 41 or a porous portion thereof may be elastically deformable like a sponge, or may have a strength that does not or hardly deforms elastically. When at least a portion of the water absorbent body 41 is porous as described above, the diameter of the pores opened on the surface of the water absorbent body 41 may be equal to the distance between two adjacent protrusions P1 (see FIG. 6), or may be larger or smaller than that distance, as long as the water absorbent body 41 can remove water from the substrate W.

[0070] The water absorbent body 41 may be made of a water-absorbent resin or a hydrophilic material, or may include a portion made of a water-absorbent resin and a portion made of a hydrophilic material. The water absorbent body 41 may include a portion made of a material other than a water-absorbent resin or a hydrophilic material in addition to or instead of at least one of the portion made of a water-absorbent resin and the portion made of a hydrophilic material. Only the surface of the water absorbent body 41 may be made of a material that retains water, such as a water-absorbent resin or a hydrophilic material.

[0071] The water-absorbing resin may be a water-absorbing polymer or other materials. When the water-absorbing resin is a water-absorbing polymer, the water-absorbing resin may contain at least one of a polyacrylate-based polymer, a starch-acrylate graft polymer, a vinyl acetate copolymer, a maleic anhydride copolymer, a polyvinyl alcohol-based polymer, and a CMC (carboxymethyl cellulose)-based polymer, or may contain other materials.

[0072] The hydrophilic material may be an inorganic material such as glass and silicon dioxide, or may be a non-inorganic material.

[0073] In the examples shown in FIGS. 3 and 4 , the lower surface 41L of the water absorber 41 is parallel to the upper surface of the substrate W held by the spin chuck 10. When observed on the order of micrometers, the lower surface 41L of the water absorber 41 may be a horizontal plane with no or almost no unevenness, or may be an uneven surface including at least one of a plurality of convex portions protruding downward and a plurality of concave portions recessed upward. The lower surface 41L of the water absorber 41 may include both a flat surface and an uneven surface. When the lower surface 41L of the water absorber 41 includes an uneven surface, the uneven surface may be part of a porous body. In this case, the plurality of concave portions of the uneven surface correspond to a plurality of pores of the porous body that are open on the surface of the porous body.

[0074] The processing unit 2 includes a vertical actuator 44v that translates the water absorbent body 41 up and down to position the water absorbent body 41 at any position within a range between an upper position and a lower position. The vertical actuator 44v is an example of a water absorbent actuator. FIGS. 3 and 4 show an example in which the vertical actuator 44v translates the shielding plate 42 up and down to translate the water absorbent body 41 up and down. The upper position is a position in which the water absorbent body 41 is spaced upward from the water on the substrate W held by the spin chuck 10. The lower position is a position in which the water absorbent body 41 is in contact with the water on the substrate W held by the spin chuck 10. The lower position may be a position in which the water absorbent body 41 is in contact with the upper surface of the substrate W, or a position spaced upward from the upper surface of the substrate W.

[0075] Regardless of the size of the water absorbent body 41, the processing unit 2 may include at least one horizontal actuator that moves the water absorbent body 41 horizontally relative to the substrate W. The spin motor 13 is an example of a horizontal actuator. The at least one horizontal actuator may include a rotational actuator that rotates the water absorbent body 41 about a vertical line, or may include a translational actuator that translates the water absorbent body 41 horizontally. The rotational actuator may rotate the water absorbent body 41 about a rotational axis A1 that passes through the water absorbent body 41, or may rotate the water absorbent body 41 about a vertical line that does not pass through the water absorbent body 41.

[0076] The shielding plate 42 is supported on a support arm 44 via a support shaft 43 extending upward from the shielding plate 42. The shielding plate 42 and the support shaft 43 may be fixed to the support arm 44, or may be rotatable relative to the support arm 44 about a rotation axis A1. In the latter case, the processing unit 2 may include a rotation actuator 44r that rotates the shielding plate 42 and the support shaft 43 about the rotation axis A1 relative to the support arm 44. If the processing unit 2 includes a heater 45 (see FIG. 3 ), which will be described later, the heater 45 may be connected to a power source via a slip ring that includes a rotatable ring and a brush that rubs against the rotating ring to supply power to the ring.

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

[0078] 5 is a block diagram showing the electrical configuration of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control device 3 that controls the electrical and electronic devices provided in the substrate processing apparatus 1. The control device 3 includes at least one computer that can communicate with each other. The computer includes a computer main body 3a and a peripheral device 3d connected to the computer main body 3a.

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

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

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

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

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

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

[0085] FIG. 6 is a schematic cross-sectional view showing an example of the structure of a substrate W processed by the substrate processing apparatus 1. The substrate W includes a front surface and a back surface that are parallel to each other, and an annular end surface that connects the outer edges of the front surface and the back surface along the entire periphery of the front surface and the back surface. FIG. 6 shows the state in which the front surface of the substrate W faces upward. The front surface of the substrate W corresponds to the upper surface of the substrate W. The front surface of the substrate W is a device formation surface on which devices are formed. The back surface of the substrate W is a non-device formation surface on which devices are not formed. Both the front surface and the back surface of the substrate W may be device formation surfaces.

[0086] The front and back surfaces of the substrate W are flat surfaces parallel to each other. When the pattern PA is formed on the surface of the substrate W, the surface of the substrate W is, strictly speaking, an uneven surface. The thickness direction of the substrate W is a direction perpendicular to the flat surface of the substrate W before the pattern PA is formed, and the surface direction of the substrate W is a direction parallel to the flat surface. In Figure 6, the up-down direction on the paper surface corresponds to the thickness direction of the substrate W, and the left-right direction on the paper surface corresponds to the surface direction of the substrate W. If the pattern PA is on the top surface of the substrate W when the water repellent agent-containing liquid is supplied to the top surface of the substrate W, the pattern PA may be formed before the substrate processing apparatus 1 processes the substrate W, or may be formed while the substrate processing apparatus 1 is processing the substrate W.

[0087] FIG. 6 shows an example of a cross section of a substrate W cut along a plane perpendicular to the flat surface of the substrate W before the pattern PA is formed. In this example, a plurality of protrusions P1 are formed on the surface of a base layer s4 of the substrate W, extending in the thickness direction of the substrate W. The base layer s4 may be part of a disk-shaped semiconductor substrate, or a thin film formed on the substrate. The pattern PA includes a plurality of protrusions P1 and a plurality of recesses Q1. The plurality of protrusions P1 are spaced apart from each other in the surface direction of the substrate W. Two protrusions P1 face each other in the surface direction of the substrate W with a gap between them, forming recesses Q1 recessed in the thickness direction of the substrate W from the tips of the two protrusions P1.

[0088] FIG. 6 shows an example in which the cross section of the protrusion P1 is rectangular and extends in the thickness direction of the substrate W. The protrusion P1 may be cylindrical, prism-shaped, or plate-shaped, or may have other shapes. The recess Q1 may be a hole or a groove. The protrusion P1 may extend in the surface direction of the substrate W rather than in the thickness direction of the substrate W. The width of the protrusion P1 may be constant from the base of the protrusion P1 to the tip of the protrusion P1, or may vary. The width of the recess Q1 may be constant from the bottom of the recess Q1 to the entrance of the recess Q1, or may vary.

[0089] The protrusion P1 may be composed of only one layer, or may be composed of multiple layers stacked in the height direction of the protrusion P1. FIG. 6 shows an example of the former. In the latter case, all layers included in one protrusion P1 may be made of the same or different materials, or some of the layers may be made of the same material different from the rest of the layers. The material of the protrusion P1 may be one or more of a semiconductor, an insulator, and a metal, or may be other materials. The material of the end surface s1 of the protrusion P1 may be a silicon-containing material such as silicon dioxide, or may be other materials.

[0090] The surface of the pattern PA includes the surfaces of the convex portions P1 and the inner surfaces of the concave portions Q1. The surface of the convex portions P1 includes end faces s1 corresponding to the tips of the convex portions P1 and side faces s2 extending from the end faces s1 to the bases of the convex portions P1. The end faces s1 of the convex portions P1 correspond to the tip and top surfaces of the convex portions P1. The end faces s1 of the multiple convex portions P1 are arranged on a single plane. The end faces s1 of the multiple convex portions P1 correspond to part or all of the upper surface of the substrate W. The inner surfaces of the concave portions Q1 include bottom faces s3 corresponding to the bottom of the concave portions Q1 and side faces extending from the bottom faces s3 to the entrances of the concave portions Q1. The side faces of the concave portions Q1 may also serve as the side faces s2 of the convex portions P1, or may be different from the side faces s2. Figure 6 shows an example of the former. The side faces of the concave portions Q1 form the entrances of the concave portions Q1.

[0091] Next, an example of processing of the substrate W performed by the substrate processing apparatus 1 will be described.

[0092] Fig. 7 is a process diagram for explaining an example of processing of a substrate W performed by the substrate processing apparatus 1. In the following, Fig. 2 will be referred to. Fig. 7 will be referred to as appropriate.

[0093] When the substrate W is processed by the substrate processing apparatus 1, a loading step (step S1 in FIG. 7) of loading the substrate W into the chamber 4 is performed.

[0094] Specifically, with the shielding plate 42 in the upper position, all guards 24 in the lower position, and all scan nozzles in the standby position, the center robot CR (see FIG. 1A) places the substrate W on the hand Hc onto the spin base 11 with the surface of the substrate W facing upward, and then retracts the hand Hc from the inside of the chamber 4. Once the substrate W is placed on the spin base 11, the lower surface of the substrate W is attracted to the upper surface of the spin base 11, and the substrate W is held by the spin chuck 10. Then, the spin motor 13 is driven, and the substrate W begins to rotate (step S2 in FIG. 7).

[0095] Next, a first chemical liquid supplying step (step S3 in FIG. 7) of supplying DHF, which is an example of a first chemical liquid, onto the upper surface of the substrate W is performed.

[0096] Specifically, with blocking plate 42 in the upper position and at least one guard 24 in the upper position, first nozzle actuator 35a moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b from the standby position to the processing position. Then, first chemical liquid valve 33a is opened, and first chemical liquid nozzle 31a begins to discharge DHF. After a predetermined time has elapsed since first chemical liquid valve 33a was opened, first chemical liquid valve 33a is closed, and the discharge of DHF is stopped.

[0097] The DHF discharged from first chemical liquid nozzle 31a collides with the upper surface of substrate W, which is rotating at the first chemical liquid supply speed, and then flows outward along the upper surface of substrate W. As a result, DHF is supplied to the entire upper surface of substrate W, and a liquid film of DHF is formed covering the entire upper surface of substrate W. While first chemical liquid nozzle 31a is discharging DHF, first nozzle actuator 35a may move first nozzle arm 34a to move the collision position of DHF with the upper surface of substrate W between the center and the outer periphery, or may keep the collision position stationary at the center. Whether or not the collision position is moved applies similarly to the processing liquid supplied to the upper surface of substrate W after DHF.

[0098] Next, a first rinsing liquid supplying step (step S4 in FIG. 7) is performed in which pure water, which is an example of a first rinsing liquid, is supplied to the upper surface of the substrate W.

[0099] Specifically, with shielding plate 42 in the upper position, at least one guard 24 in the upper position, and first chemical liquid nozzle 31a and first rinse liquid nozzle 31b in the processing position, first rinse liquid valve 33b is opened, and first rinse liquid nozzle 31b begins to discharge deionized water. The deionized water discharged from first rinse liquid nozzle 31b collides with the upper surface of substrate W, which is rotating at the first rinse liquid supply speed, and then flows outward along the upper surface of substrate W. As a result, DHF on substrate W is replaced with deionized water, and a liquid film of deionized water is formed covering the entire upper surface of substrate W. When a predetermined time has elapsed since first rinse liquid valve 33b was opened, first rinse liquid valve 33b is closed. Then, first nozzle actuator 35a moves first chemical liquid nozzle 31a and first rinse liquid nozzle 31b to the standby position.

[0100] Next, a second chemical liquid supplying step (step S5 in FIG. 7) of supplying SC1, which is an example of a second chemical liquid, to the upper surface of the substrate W is performed.

[0101] Specifically, with shielding plate 42 in the upper position and at least one guard 24 in the upper position, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d from the standby position to the processing position. Then, second chemical liquid valve 33c is opened, and second chemical liquid nozzle 31c begins to discharge SC1. SC1 discharged from second chemical liquid nozzle 31c collides with the upper surface of substrate W, which is rotating at the second chemical liquid supply speed, and then flows outward along the upper surface of substrate W. This replaces the deionized water on substrate W with SC1, forming a liquid film of SC1 that covers the entire upper surface of substrate W. When a predetermined time has elapsed since second chemical liquid valve 33c was opened, second chemical liquid valve 33c is closed.

[0102] Next, a second rinsing liquid supplying step (step S6 in FIG. 7) is performed in which pure water, which is an example of a second rinsing liquid, is supplied to the upper surface of the substrate W.

[0103] Specifically, with shield plate 42 in the upper position, at least one guard 24 in the upper position, and second chemical liquid nozzle 31c and second rinse liquid nozzle 31d in the processing position, second rinse liquid valve 33d is opened, and second rinse liquid nozzle 31d begins to discharge deionized water. The deionized water discharged from second rinse liquid nozzle 31d collides with the upper surface of substrate W, which is rotating at the second rinse liquid supply speed, and then flows outward along the upper surface of substrate W. As a result, DHF on substrate W is replaced with deionized water, and a liquid film of deionized water is formed covering the entire upper surface of substrate W. When a predetermined time has elapsed since second rinse liquid valve 33d was opened, second rinse liquid valve 33d is closed. Then, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d to the standby position.

[0104] Next, a pre-water-repellent amphipathic liquid supplying step (step S7 in FIG. 7) is performed in which IPA, which is an example of an amphipathic liquid, is supplied onto the upper surface of the substrate W.

[0105] Specifically, with the blocking plate 42 in the upper position and at least one guard 24 in the upper position, the third nozzle actuator 35c moves the water-repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g from the standby position to the processing position. The amphipathic liquid valve 33g is then opened, and the amphipathic liquid nozzle 31g begins to discharge IPA. The IPA discharged from the amphipathic liquid nozzle 31g collides with the upper surface of the substrate W, which is rotating at the first pre-water-repellent supply speed, and then flows outward along the upper surface of the substrate W. This replaces the deionized water on the substrate W with IPA, forming a liquid film of IPA that covers the entire upper surface of the substrate W. After a predetermined time has elapsed since the amphipathic liquid valve 33g was opened, the amphipathic liquid valve 33g is closed.

[0106] Next, a pre-water-repellent hydrophobic liquid supplying step (step S8 in FIG. 7) is performed in which toluene, which is an example of a hydrophobic liquid, is supplied onto the upper surface of the substrate W.

[0107] Specifically, with the blocking plate 42 in the upper position, at least one guard 24 in the upper position, and the water-repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the hydrophobic liquid valve 33f is opened, and the hydrophobic liquid nozzle 31f begins to discharge toluene. The toluene discharged from the hydrophobic liquid nozzle 31f collides with the upper surface of the substrate W, which is rotating at the second pre-water-repellent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the IPA on the substrate W is replaced with toluene, and a liquid film of toluene is formed that covers the entire upper surface of the substrate W. When a predetermined time has elapsed since the hydrophobic liquid valve 33f was opened, the hydrophobic liquid valve 33f is closed.

[0108] Next, a water repellent agent supplying step (step S9 in FIG. 7) of supplying a water repellent agent-containing liquid onto the upper surface of the substrate W is performed.

[0109] Specifically, with the blocking plate 42 in the upper position, at least one guard 24 in the upper position, and the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the water repellent agent valve 33e is opened, and the water repellent agent nozzle 31e begins to discharge the water repellent agent-containing liquid. The water repellent agent-containing liquid discharged from the water repellent agent nozzle 31e collides with the upper surface of the substrate W, which is rotating at the water repellent agent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the toluene on the substrate W is replaced with the water repellent agent-containing liquid, and a liquid film of the water repellent agent-containing liquid is formed to cover the entire upper surface of the substrate W. When a predetermined time has elapsed since the water repellent agent valve 33e was opened, the water repellent agent valve 33e is closed.

[0110] Next, a post-water-repellent hydrophobic liquid supplying step (step S10 in FIG. 7) is performed in which toluene, which is an example of a hydrophobic liquid, is supplied onto the upper surface of the substrate W.

[0111] Specifically, with the blocking plate 42 in the upper position, at least one guard 24 in the upper position, and the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the hydrophobic liquid valve 33f is opened, and the hydrophobic liquid nozzle 31f begins to discharge toluene. The toluene discharged from the hydrophobic liquid nozzle 31f collides with the upper surface of the substrate W, which is rotating at the first post-water-repellent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the water repellent agent-containing liquid on the substrate W is replaced with toluene, and a toluene liquid film is formed that covers the entire upper surface of the substrate W. When a predetermined time has elapsed since the hydrophobic liquid valve 33f was opened, the hydrophobic liquid valve 33f is closed.

[0112] Next, a post-water-repellent amphipathic liquid supplying step (step S11 in FIG. 7) is performed in which IPA, which is an example of an amphipathic liquid, is supplied onto the upper surface of the substrate W.

[0113] Specifically, with the blocking plate 42 in the upper position, at least one guard 24 in the upper position, and the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g in the processing position, the amphipathic liquid valve 33g is opened, and the amphipathic liquid nozzle 31g begins to discharge IPA. The IPA discharged from the amphipathic liquid nozzle 31g collides with the upper surface of the substrate W, which is rotating at the second post-water-repellent supply speed, and then flows outward along the upper surface of the substrate W. As a result, the toluene on the substrate W is replaced with IPA, and a liquid film of IPA is formed that covers the entire upper surface of the substrate W. After a predetermined time has elapsed since the amphipathic liquid valve 33g was opened, the amphipathic liquid valve 33g is closed. Then, the third nozzle actuator 35c moves the water repellent agent nozzle 31e, the hydrophobic liquid nozzle 31f, and the amphipathic liquid nozzle 31g to their standby positions.

[0114] Next, a water supplying step (step S12 in FIG. 7) is performed in which pure water, which is an example of a water-containing liquid, is supplied to the upper surface of the substrate W.

[0115] Specifically, with shielding plate 42 in the upper position and at least one guard 24 in the upper position, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d from the standby position to the processing position. Then, second rinse liquid valve 33d is opened, and second rinse liquid nozzle 31d begins to discharge deionized water. The deionized water discharged from second rinse liquid nozzle 31d collides with the upper surface of substrate W, which is rotating at the water supply speed, and then flows outward along the upper surface of substrate W. As a result, IPA on substrate W is replaced with deionized water, and a liquid film of deionized water is formed that covers the entire upper surface of substrate W. After a predetermined time has elapsed since second rinse liquid valve 33d was opened, second rinse liquid valve 33d is closed. Then, second nozzle actuator 35b moves second chemical liquid nozzle 31c and second rinse liquid nozzle 31d to the standby position.

[0116] Next, a water absorbing step (step S14 in FIG. 7) is performed in which the water absorber 41 (see FIG. 3) is brought into contact with the pure water on the upper surface of the substrate W.

[0117] Specifically, the vertical actuator 44v moves the shielding plate 42 from the upper position to the lower position. This causes the water absorber 41 attached to the shielding plate 42 to descend and come into contact with the pure water on the upper surface of the substrate W held by the spin chuck 10. As will be described later, while the water absorber 41 is absorbing the pure water, at least one of the substrate W and the water absorber 41 may or may not rotate. FIG. 7 shows an example in which the rotation of the substrate W is stopped before the water absorber 41 absorbs the pure water (step S13 in FIG. 7). When the water absorber 41 comes into contact with the pure water, the pure water is absorbed by the water absorber 41, and the amount of pure water on the upper surface of the substrate W decreases. As a result, all or almost all of the pure water is removed from the upper surface of the substrate W. When a predetermined time has elapsed since the water absorber 41 came into contact with the pure water on the upper surface of the substrate W held by the spin chuck 10, the vertical actuator 44v moves the shielding plate 42 to the upper position.

[0118] Next, an unloading step (step S15 in FIG. 7) of unloading the substrate W from the chamber 4 is performed.

[0119] Specifically, if at least one of the substrate W and the water absorber 41 is rotating, the rotation of at least one of the substrate W and the water absorber 41 is stopped. If at least one guard 24 is positioned in the upper position, all of the guards 24 are lowered to the lower position. With the suction of the substrate W released, the center robot CR supports the substrate W supported on the spin base 11 with the hand Hc, and retracts the hand Hc together with the substrate W from inside the chamber 4. As a result, the processed substrate W is carried out of the chamber 4.

[0120] Next, the water absorption process will be described.

[0121] 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views for explaining the water absorption step (step S14 in FIG. 7). FIG. 9A is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in the Wenzel state. FIG. 9B is a schematic cross-sectional view showing an example of a droplet contacting a rough surface in the Cassie-Baxter state. In the following description, unless otherwise specified, the upper surface of the substrate W includes the surface of the pattern PA.

[0122] In one example of the processing of the substrate W described above, a water-repellent agent-containing liquid is supplied after the hydrophobic liquid is supplied (step S9 in FIG. 7). When the water-repellent agent-containing liquid is supplied to the upper surface of the substrate W, the water-repellent agent-containing liquid mixes with the hydrophobic liquid on the substrate W and forms a liquid film that covers the entire upper surface of the substrate W. As shown in FIG. 8A, the water-repellent agent-containing liquid on the substrate W mixes with the hydrophobic liquid in the recess Q1 and enters the recess Q1. As a result, the hydrophobic liquid on the substrate W is replaced with the water-repellent agent-containing liquid.

[0123] The water-repellent-agent-containing liquid on the substrate W contacts not only the end faces s1 and side faces s2 of the convex portions P1 but also the bottom faces s3 of the concave portions Q1. As shown in FIG. 8A, the water-repellent agent contained in the water-repellent-agent-containing liquid adheres to the upper surface of the substrate W, such as the end faces s1 of the convex portions P1, and forms a water-repellent film R1 on at least a portion of the upper surface of the substrate W. If the water-repellent agent is a silylation agent, the hydrogen atoms of the hydroxyl groups exposed on the upper surface of the substrate W are substituted with silyl groups containing a silicon atom and multiple methyl groups, and the multiple silyl groups form the water-repellent film R1. This enhances the water-repellent properties of the upper surface of the substrate W. Note that FIG. 8A depicts a boundary between the water-repellent-agent-containing liquid and the water-repellent film R1, but in reality, no such boundary exists.

[0124] The water-repellent agent contained in the water-repellent-containing liquid is a substance that increases the contact angle of water with a horizontal, smooth surface made of the same material as the end surface s1 of the convex portion P1 to a value greater than 90 degrees. Assuming that the top surface of the substrate W is smooth, when the water-repellent-containing liquid is supplied to the top surface of the substrate W, the contact angle of water with the top surface of the substrate W exceeds 90 degrees. According to Wenzel's equation, when comparing the contact angles of water with smooth and rough surfaces made of the same material, if the contact angle of water with the smooth surface exceeds 90 degrees, the contact angle of water with the rough surface is greater than the contact angle of water with the smooth surface. The top surface of the substrate W is a rough surface on which a fine pattern PA is formed. Therefore, the contact angle of water with the top surface of the substrate W is greater than if the top surface of the substrate W were a smooth surface.

[0125] After the water-repellent-agent-containing liquid has been supplied, the hydrophobic liquid, the amphipathic liquid, and pure water are supplied in this order. The hydrophobic liquid mixes with the water-repellent-agent-containing liquid on the substrate W to form a liquid film that covers the entire upper surface of the substrate W, and mixes with the water-repellent-agent-containing liquid in the recess Q1 to enter the recess Q1. The same applies to the amphipathic liquid and pure water. Therefore, when pure water is being supplied, as shown in FIG. 8B, the pure water mixes with the amphipathic liquid on the substrate W to form a liquid film that covers the entire upper surface of the substrate W, and mixes with the amphipathic liquid in the recess Q1 to enter the recess Q1.

[0126] After supplying pure water, which is an example of a water-containing liquid, the water absorbent 41 is brought into contact with the pure water on the substrate W. Fig. 8C shows a state before the water absorbent 41 comes into contact with the pure water on the substrate W. Fig. 8D shows a state in which the water absorbent 41 is in contact with the pure water on the substrate W. The thick black arrows in Fig. 8D represent pure water moving from below the water absorbent 41 into the water absorbent 41.

[0127] 8D , when the water absorber 41 comes into contact with the pure water on the substrate W, the pure water is absorbed by the water absorber 41. When the water absorber 41 is absorbing the pure water on the substrate W, the water absorber 41 may be in contact with the upper surface of the substrate W or may be spaced apart from the upper surface of the substrate W. When the water absorber 41 is absorbing the pure water on the substrate W, the substrate W and the water absorber 41 may be moved relatively in at least one of the vertical and horizontal directions. The pure water on the substrate W may be absorbed by the water absorber 41 without moving the substrate W and the water absorber 41 relatively in the horizontal direction.

[0128] Before the water absorbent body 41 comes into contact with the pure water on the substrate W, the pure water on the substrate W may be in the Wenzel state or the Cassie-Baxter state. Fig. 8C shows an example in which the pure water on the substrate W is in the Cassie-Baxter state before the water absorbent body 41 comes into contact with the pure water on the substrate W. When the pure water on the substrate W is in the Cassie-Baxter state, the contact angle of water with respect to the upper surface of the substrate W to which the water repellent-containing liquid has been supplied may be 100 degrees or more, preferably 140 degrees or more.

[0129] As shown in FIG. 9A, the rough surface is a solid surface provided with a plurality of recesses Q1 and a plurality of protrusions P1. The recesses Q1 are recessed from the tips of the protrusions P1. The protrusions P1 protrude from the bottom of the recesses Q1. The bottom of the recesses Q1 corresponds to the base of the protrusions P1. The tips of two adjacent protrusions P1 form the entrance of the recess Q1 located between them.

[0130] As shown in FIG. 9A, the Wenzel state (hereinafter also referred to as the W state) is a state in which a water droplet on a horizontal rough surface penetrates into a recess Q1. As shown in FIG. 9B, the Cassie-Baxter state (hereinafter also referred to as the CB state) is a state in which the recess Q1 is filled with air and the water droplet is supported by the tips of the protrusions P1. In the CB state, the water droplet is supported by the air in the recess Q1 and the tips of the protrusions P1. In other words, when a water droplet is placed on a horizontal rough surface under normal temperature and pressure (room temperature and 1 atmosphere), the tips of the protrusions P1 come into contact with the water droplet while the bottom of the recess Q1 is separated from the water droplet. Room temperature is, for example, a constant or approximately constant temperature within the range of 10 to 30°C.

[0131] 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 thought that the higher the surface tension of the liquid and the lower the surface free energy of the rough surface (the more water-repellent the rough surface is), the more likely the water droplet on the rough surface will adopt the CB state.

[0132] Pure water is a liquid with high surface tension. The water-repellent agent contained in the water-repellent-containing liquid is a substance that increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end surface s1 of the convex portion P1 to a value exceeding 90 degrees, and the upper surface of the substrate W is rough. Therefore, the surface free energy of the upper surface of the substrate W is low (the upper surface of the substrate W has high water repellency). Therefore, when the amphipathic liquid on the substrate W is replaced with pure water, the pure water can contact the upper surface of the substrate W in a CB state. In other words, during the process of replacing the amphipathic liquid on the substrate W with pure water, at least one of the amphipathic liquid and the pure water can be discharged from the concave portion Q1, and at least a portion of the concave portion Q1 can be filled with air.

[0133] Because the water absorber 41 absorbs the pure water on the substrate W, whether the pure water is in the CB state or the W state and is in contact with the upper surface of the substrate W, a force pulling the pure water on the substrate W upward toward the water absorber 41 is applied to the pure water. When the pure water is in contact with the upper surface of the substrate W in the CB state, all or almost all of the pure water outside the recess Q1 is absorbed by the water absorber 41. Because there is no or almost no pure water in the recess Q1, all or almost all of the pure water is thereby removed from the upper surface of the substrate W.

[0134] When the pure water is in contact with the upper surface of the substrate W in the W state, the pure water in the recessed portion Q1 moves out of the recessed portion Q1 during the process in which the pure water outside the recessed portion Q1 is absorbed by the water absorbent 41. This is because the pure water is in a state in which it can come into contact with the upper surface of the substrate W in the CB state, and the water absorbent 41 pulls the pure water in the recessed portion Q1 upward. After the pure water in the recessed portion Q1 moves out of the recessed portion Q1, all or almost all of the pure water outside the recessed portion Q1 is absorbed by the water absorbent 41. As a result, all or almost all of the pure water is removed from the upper surface of the substrate W.

[0135] After a predetermined time has elapsed since the water absorber 41 began to come into contact with the pure water on the substrate W, the water absorber 41 is moved upward, thereby increasing the vertical distance between the substrate W and the water absorber 41. The thick black arrow in FIG. 8E indicates the upward movement of the water absorber 41. As shown in FIG. 8E, when the distance between the substrate W and the water absorber 41 increases, the pure water held in the water absorber 41 moves away from the end surface s1 of the protrusion P1. As a result, all or almost all of the pure water is removed from the upper surface of the substrate W.

[0136] After the gap between the substrate W and the water absorber 41 is increased, the center robot CR (see FIG. 1A) removes the substrate W from the spin chuck 10. If at least one of the substrate W and the water absorber 41 is rotated, the rotation of at least one of the substrate W and the water absorber 41 is stopped before the center robot CR supports the substrate W. After the gap between the substrate W and the water absorber 41 is increased, no visible pure water remains on the top surface of the substrate W. After the water absorber 41 has absorbed the pure water on the substrate W and before the center robot CR supports the substrate W, spin drying may be performed by rotating the substrate W on the spin chuck 10 (see FIG. 2) to dry the substrate W. Even if pure water remains in the recess Q1 before spin drying, the amount is small. Therefore, spin drying can be performed while preventing collapse of the pattern PA (collapse of the protrusion P1).

[0137] After the substrate W is unloaded from the spin chuck 10, the water absorber 41 is dried. The water absorber 41 may be dried by at least one of rotating the water absorber 41, heating the water absorber 41, supplying gas to the water absorber 41, increasing the temperature in the chamber 4, decreasing the air pressure in the chamber 4, and decreasing the humidity in the chamber 4, or by a method other than these. When heating the water absorber 41, the water absorber 41 may be heated by a heater 45 (see FIG. 3) built into the shielding plate 42.

[0138] In addition to or instead of drying the water absorbent body 41, the water absorbent body 41 may be replaced. The water absorbent body 41 may be replaced every time one or more substrates W are processed in one processing unit 2, or may be replaced every time a certain period of time has elapsed, or at any time. In addition to or instead of at least one of drying and replacing the water absorbent body 41, the water absorbent body 41 may be cleaned. For example, the water absorbent body 41 may be cleaned by bringing the water absorbent body 41 into contact with the liquid on the upper surface of a dummy substrate (a disc dedicated to cleaning and having the same shape as the substrate W) while the dummy substrate is held and rotated on the spin chuck 10.

[0139] When drying the water absorbent body 41, the control device 3 (see FIG. 1A) may detect the dry state of the water absorbent body 41 based on the detection value of a water absorbent body sensor 46 (see FIG. 3) that measures at least one of the temperature and moisture content of the water absorbent body 41. The water absorbent body sensor 46 may be either a thermometer that measures the temperature of the water absorbent body 41 or a moisture meter that measures the moisture content of the water absorbent body 41, or it may include both of these. The thermometer may be of a contact type or a non-contact type, or may be of a different type. If the thermometer is of a non-contact type, it may be of an optical type. The moisture meter may be of a microwave type or an electrical resistance type, or may be of a different type.

[0140] When drying the water absorbent body 41, the control device 3 may increase or decrease the humidity in the chamber 4 using a humidity adjusting device 47 (see FIG. 3 ), thereby improving the uniformity of drying of the water absorbent body 41. The humidity adjusting device 47 may be either a humidifier or a dehumidifier, or may include both. The humidifier may be of an ultrasonic type, a heating type, or other types. The control device 3 may control the humidity in the chamber 4 by controlling the humidity adjusting device 47 based on the value detected by a hygrometer 48 (see FIG. 3 ) that detects the humidity in the chamber 4.

[0141] Next, the effects of this embodiment will be described.

[0142] In this embodiment, a water-repellent agent-containing liquid is supplied to the upper surface of the substrate W. A pattern PA including convex portions P1 and concave portions Q1 is formed on the upper surface of the substrate W. Therefore, the upper surface of the substrate W is not smooth but rough. When the water-repellent agent-containing liquid is supplied to a horizontal, smooth surface made of the same material as the end surfaces s1 of the convex portions P1, the contact angle of water with the smooth surface increases to a value greater than 90 degrees. According to Wenzel's equation, when the contact angle of water with a smooth surface exceeds 90 degrees, the contact angle of water with a rough surface made of the same material as the smooth surface exceeds the contact angle of water with the smooth surface. Therefore, when the water-repellent agent-containing liquid is supplied to the upper surface of the substrate W, the contact angle of water with the upper surface of the substrate W increases to a value well greater than 90 degrees.

[0143] After the water-repellent agent-containing liquid is supplied to the upper surface of the substrate W, a water-containing liquid is supplied to the upper surface of the substrate W. Thereafter, the water-absorbing body 41 is brought into contact with the water-containing liquid on the upper surface of the substrate W. Not only is the upper surface of the substrate W, including the surface of the pattern PA, highly water-repellent, but the surface tension of the liquid (water-containing liquid) in contact with the upper surface of the substrate W is also high, so the force with which the upper surface of the substrate W repels the water-containing liquid promotes the movement of the water-containing liquid to the water-absorbing body 41. As a result, all or almost all of the water-containing liquid can be removed from the upper surface of the substrate W by the water-absorbing body 41, and the upper surface of the substrate W can be dried. Since the surface tension of the water-containing liquid is high, the water-containing liquid on the substrate W tends to move toward the water-containing liquid adhering to the water-absorbing body 41. Therefore, the liquid is less likely to remain on the upper surface of the substrate W than when a liquid with a lower surface tension than the water-containing liquid is absorbed by the water-absorbing body 41.

[0144] In this embodiment, the water-repellent-agent-containing liquid on the upper surface of the substrate W is replaced with a hydrophobic liquid, and the hydrophobic liquid on the upper surface of the substrate W is replaced with an amphipathic liquid. When the water-repellent agent contained in the water-repellent-agent-containing liquid comes into contact with water, unwanted substances may be generated in the water-repellent-agent-containing liquid. By replacing the water-repellent-agent-containing liquid with a hydrophobic liquid in which the solubility of water is lower than that of the amphipathic liquid, the generation of such unwanted substances can be prevented or the amount of such substances generated can be reduced. In addition, the amount of water-repellent-agent-containing liquid remaining in the water-containing liquid can be reduced compared to when the water-repellent-agent-containing liquid on the upper surface of the substrate W is replaced with an amphipathic liquid.

[0145] In this embodiment, the upper surface of the substrate W is oxidized by supplying a chemical solution to the upper surface of the substrate W. As a result, at least a portion of the upper surface of the substrate W is terminated with hydroxy groups (OH groups). When the upper surface of the substrate W is oxidized with a chemical solution, the number of hydroxy groups exposed on the upper surface of the substrate W increases. If the water repellent agent is a silylating agent, the hydrogen atoms of the hydroxy groups are substituted with silyl groups of the water repellent agent. Therefore, by supplying a chemical solution to the upper surface of the substrate W, the water repellency of the upper surface of the substrate W can be efficiently increased.

[0146] Furthermore, the chemical liquid on the upper surface of the substrate W is replaced with a water-containing liquid as a rinse liquid, rather than with a water-repellent-containing liquid. Thereafter, the water-containing liquid on the upper surface of the substrate W is replaced with an amphipathic liquid, and the amphipathic liquid on the upper surface of the substrate W is replaced with a hydrophobic liquid. Even if any water-containing liquid remains after replacing the water-containing liquid with the amphipathic liquid, this water-containing liquid diffuses into the amphipathic liquid on the upper surface of the substrate W. Then, the amphipathic liquid is replaced with a hydrophobic liquid. The hydrophobic liquid is a liquid in which water dissolves less than in the amphipathic liquid. Therefore, the water remaining on the upper surface of the substrate W can be eliminated or reduced.

[0147] When the water-repellent agent contained in the water-repellent-containing liquid comes into contact with water, unwanted substances may be generated in the water-repellent-containing liquid. Since the water-containing liquid used as a rinse liquid is gradually replaced with the amphipathic liquid and the hydrophobic liquid, the water-repellent-containing liquid can be supplied to the top surface of the substrate W with no water remaining on the substrate W or with only a very small amount of water remaining. Therefore, the water repellency of the top surface of the substrate W can be increased while preventing or reducing the generation of unwanted substances.

[0148] In this embodiment, the water absorbent body 41 maintains a state where it is separated from the upper surface of the substrate W for all or part of the period during which it absorbs the water-containing liquid on the upper surface of the substrate W. When the water absorbent body 41 is moved between the upper position and the lower position, the water absorbent body 41 maintains a state where it is separated from the upper surface of the substrate W for all or part of the period during which it is located at the lower position. Because the water absorbent body 41 is separated from the upper surface of the substrate W, it is possible to eliminate or shorten the period during which the convex portions P1 are pressed downward by the water absorbent body 41. In addition, it is possible to eliminate or reduce foreign matter that adheres to the convex portions P1 when the water absorbent body 41 comes into contact with the convex portions P1.

[0149] In this embodiment, before the water absorbent body 41 comes into contact with the water-containing liquid on the upper surface of the substrate W, the water-containing liquid is supported by the air in the recessed portion Q1 and the protruding portion P1. In other words, since the upper surface of the substrate W has high water repellency and the surface tension of the water-containing liquid is high, the water-containing liquid changes from the Wenzel state to the Cassie-Baxter state before the water absorbent body 41 absorbs the water-containing liquid on the upper surface of the substrate W. In this state, the water absorbent body 41 is brought into contact with the water-containing liquid on the upper surface of the substrate W.

[0150] When the water-containing liquid remains in the recessed portion Q1, the surface of the water-containing liquid (the interface between the water-containing liquid and air) is formed between the two protruding portions P1, and the surface tension of the water-containing liquid is applied to the two protruding portions P1. If the force applied to the protruding portions P1 is strong or if the strength of the protruding portions P1 is low, the protruding portions P1 collapse. If at least a portion of the recessed portion Q1 is filled with air before the water-absorbing portion 41 comes into contact with the water-containing liquid on the upper surface of the substrate W, the water-containing liquid in the recessed portion Q1 does not generate a collapsing force that collapses the protruding portions P1, or the time for which the collapsing force is generated is short. Furthermore, the water-containing liquid on the protruding portions P1 moves upward toward the water-absorbing portion 41 without moving horizontally or almost without moving horizontally relative to the protruding portions P1. If the water-containing liquid moves horizontally relative to the tips of the protruding portions P1 and moves away from the tips of the protruding portions P1, the pattern PA may collapse. Therefore, collapse of the pattern PA can be eliminated or reduced.

[0151] In this embodiment, the substrate W and the water absorbent body 41 are maintained in a state where they do not move relative to each other in the horizontal direction during all or part of the period during which the water absorbent body 41 absorbs the water-containing liquid on the upper surface of the substrate W. When the substrate W and the water absorbent body 41 move relative to each other in the horizontal direction, a phenomenon may occur in which the water-containing liquid moves horizontally relative to the tips of the convex portions P1 and moves away from the tips of the convex portions P1. When such a phenomenon occurs, a force is applied from the water-containing liquid to the tips of the convex portions P1, which moves the tips of the convex portions P1 horizontally relative to the bases of the convex portions P1. If this force is large or if the strength of the convex portions P1 is low, the pattern PA may collapse. By maintaining a state in which the substrate W and the water absorbent body 41 do not move relative to each other in the horizontal direction, such a phenomenon can be prevented, or the time during which the phenomenon occurs can be shortened.

[0152] In this embodiment, spin drying, which involves rotating the substrate W to dry the substrate W, is not performed after the water-containing liquid on the upper surface of the substrate W is brought into contact with the water-absorbing body 41. This reduces the time required to process the substrate W compared to when spin drying is performed. If spin drying is performed with droplets present on the upper surface of the substrate W, a phenomenon occurs in which the droplets move horizontally relative to the tips of the protrusions P1 and separate from the tips of the protrusions P1. At this time, a force is applied from the droplets to the tips of the protrusions P1, moving the tips of the protrusions P1 horizontally relative to the base of the protrusions P1. If this force is large or if the strength of the protrusions P1 is low, the pattern PA may collapse during spin drying. If spin drying is not performed, this phenomenon can be prevented.

[0153] Next, another embodiment will be described.

[0154] Instead of ejecting the chemical liquid, rinse liquid, water repellent agent-containing liquid, hydrophobic liquid, and amphipathic liquid from separate nozzles, two or more of these may be ejected from a single nozzle.

[0155] The water-containing liquid supplied to the upper surface of the substrate W in the water supplying step (step S12 in FIG. 7) may not be pure water, but may be a foamable water-containing liquid that foams under normal temperature and pressure conditions, such as carbonated water. In this case, the transition of the foamable water-containing liquid from the Wenzel state to the Cassie-Baxter state can be promoted by the gas generated from the foamable water-containing liquid.

[0156] Instead of supplying a hydrophobic liquid such as toluene and then supplying the water-repellent agent-containing liquid, the water-repellent agent-containing liquid may be supplied onto the upper surface of the substrate W that is covered with an amphipathic liquid such as IPA. In other words, the supply of the hydrophobic liquid between the supply of the amphipathic liquid and the supply of the water-repellent agent-containing liquid may be omitted.

[0157] Instead of supplying the hydrophobic liquid after supplying the water-repellent agent-containing liquid, the amphipathic liquid may be supplied onto the upper surface of the substrate W covered with the water-repellent agent-containing liquid. In other words, the supply of the hydrophobic liquid between the supply of the water-repellent agent-containing liquid and the supply of the amphipathic liquid may be omitted.

[0158] The substrate W may be raised when the pure water on the substrate W is brought into contact with the water absorbent body 41. Alternatively, the substrate W may be raised and the water absorbent body 41 may be lowered at the same time.

[0159] The substrate processing apparatus 1 is not limited to an apparatus for processing a disk-shaped substrate W, but may be an apparatus for processing a polygonal substrate W.

[0160] Any two or more of the above-described configurations may be combined. Any two or more of the above-described steps may be combined.

[0161] 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]

[0162] 1: substrate processing apparatus, 3: control device, 10: spin chuck, 11: spin base, 31a: first chemical liquid nozzle, 31b: first rinse liquid nozzle, 31c: second chemical liquid nozzle, 31d: second rinse liquid nozzle, 31e: water repellent agent nozzle, 31f: hydrophobic liquid nozzle, 31g: amphipathic liquid nozzle, 33a: first chemical liquid valve, 33b: first rinse liquid valve, 33c: second chemical liquid valve, 33d: second rinse liquid valve, 33e: water repellent agent valve lube, 33f: hydrophobic liquid valve, 33g: amphiphilic liquid valve, 41: water absorber, 41L: bottom surface, 42: blocking plate, 43: support shaft, 44: support arm, 44r: rotational actuator, 44v: vertical actuator, 45: heater, 46: water absorber sensor, 47: humidity control device, 48: hygrometer, P1: convex portion, PA: pattern, Q1: concave portion, R1: water-repellent film, W: substrate, s1: end face, s2: side face, s3: bottom face, s4: base layer

Claims

1. A substrate processing method for processing a substrate having a pattern including convex portions and concave portions formed on an upper surface thereof, comprising: a water-repellent supplying step of supplying a water-repellent-containing liquid onto the upper surface of the substrate, the water-repellent-containing liquid increasing the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees; a water supplying step of supplying a water-containing liquid to the upper surface of the substrate after supplying the water-repellent agent-containing liquid to the upper surface of the substrate; a water absorbing step of removing the water-containing liquid from the upper surface of the substrate by bringing a water absorbent that absorbs the water-containing liquid into contact with the water-containing liquid on the upper surface of the substrate.

2. The substrate processing method includes: a post-water-repellent hydrophobic liquid supplying step of supplying a hydrophobic liquid that is soluble in the water-repellent agent-containing liquid onto the upper surface of the substrate, thereby replacing the water-repellent agent-containing liquid on the upper surface of the substrate with the hydrophobic liquid; a post-water-repellent amphipathic liquid supplying step of supplying an amphipathic liquid, which has a higher solubility in water than the hydrophobic liquid and is soluble in the hydrophobic liquid, onto the upper surface of the substrate, thereby replacing the hydrophobic liquid on the upper surface of the substrate with the amphipathic liquid, 2. The substrate processing method according to claim 1, wherein the water supplying step is a step of replacing the amphipathic liquid on the upper surface of the substrate with the water-containing liquid by supplying the water-containing liquid, which has a surface tension greater than that of the amphipathic liquid and is soluble in the amphipathic liquid, to the upper surface of the substrate.

3. The substrate processing method includes: a chemical solution supplying step of supplying a chemical solution to the upper surface of the substrate to oxidize the upper surface of the substrate; a rinse liquid supplying step of supplying the water-containing liquid as a rinse liquid onto the upper surface of the substrate, thereby replacing the chemical liquid on the upper surface of the substrate with the water-containing liquid; a pre-water-repellent amphipathic liquid supplying step of supplying an amphipathic liquid that is soluble in the water-containing liquid onto the upper surface of the substrate, thereby replacing the water-containing liquid on the upper surface of the substrate with the amphipathic liquid; a pre-water-repellent hydrophobic liquid supplying step of supplying a hydrophobic liquid, which has a lower solubility in water than the amphipathic liquid and is soluble in the amphipathic liquid, onto the upper surface of the substrate, thereby replacing the amphipathic liquid on the upper surface of the substrate with the hydrophobic liquid, 3. The substrate processing method according to claim 1, wherein the water-repellent supplying step is a step of replacing the hydrophobic liquid on the upper surface of the substrate with the water-repellent-containing liquid by supplying the water-repellent-containing liquid to the upper surface of the substrate.

4. 3. The substrate processing method according to claim 1, wherein the water absorbing step includes a step of bringing the water absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining the water absorbing body separated from the upper surface of the substrate.

5. 3. The substrate processing method according to claim 1, wherein the water absorbing step includes a step of bringing the water absorbing body into contact with the water-containing liquid on the upper surface of the substrate in a state in which at least a part of the recess is filled with air and the water-containing liquid is supported by the air in the recess and the protrusion before the water absorbing body comes into contact with the water-containing liquid on the upper surface of the substrate.

6. 3. The substrate processing method according to claim 1, wherein the water absorption step includes a step of bringing the water absorbent body into contact with the water-containing liquid on the upper surface of the substrate while maintaining a state in which the substrate and the water absorbent body do not move relatively in a horizontal direction.

7. 3. The substrate processing method according to claim 1, wherein spin drying, which dries the substrate by rotating the substrate, is not performed after the water-containing liquid on the upper surface of the substrate is brought into contact with the water-absorbing body.

8. a substrate holder that horizontally holds a substrate having a pattern including protrusions and recesses formed on an upper surface thereof; at least one nozzle that individually ejects a plurality of treatment liquids, including a water-repellent-containing liquid that increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end faces of the convex portions to a value exceeding 90 degrees, and a water-containing liquid, toward the upper surface of the substrate held by the substrate holder; a water absorbent body that absorbs the water-containing liquid; a water-absorbing actuator that moves at least one of the substrate and the water-absorbing body to bring the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate held by the substrate holder, thereby removing the water-containing liquid from the upper surface of the substrate.

9. the at least one nozzle individually ejects a plurality of processing liquids, including the water-repellent-agent-containing liquid, a hydrophobic liquid that dissolves in the water-repellent-agent-containing liquid, an amphipathic liquid that has a higher solubility for water than the hydrophobic liquid and dissolves in the hydrophobic liquid, and the water-containing liquid that has a higher surface tension than the amphipathic liquid and dissolves in the amphipathic liquid, toward the top surface of the substrate held by the substrate holder; the substrate processing apparatus further includes at least one valve that causes the at least one nozzle to individually discharge the plurality of processing liquids; and a control device that controls the at least one valve and the water suction actuator; The control device a water repellent supplying step of supplying the water repellent-containing liquid onto the upper surface of the substrate; a post-water-repellent hydrophobic liquid supplying step of supplying the hydrophobic liquid to the upper surface of the substrate, thereby replacing the water-repellent agent-containing liquid on the upper surface of the substrate with the hydrophobic liquid; a post-water-repellent amphipathic liquid supplying step of supplying the amphipathic liquid to the upper surface of the substrate, thereby replacing the hydrophobic liquid on the upper surface of the substrate with the amphipathic liquid; a water supplying step of supplying the water-containing liquid onto the upper surface of the substrate to replace the amphipathic liquid on the upper surface of the substrate with the water-containing liquid; a water absorbing step of removing the water-containing liquid from the upper surface of the substrate by bringing the water absorbent body into contact with the water-containing liquid on the upper surface of the substrate.

10. the at least one nozzle individually ejects a plurality of processing liquids, including the water-repellent-containing liquid, the water-containing liquid, a chemical liquid for oxidizing the upper surface of the substrate, an amphipathic liquid that dissolves in the water-containing liquid, and a hydrophobic liquid that has a lower solubility of water than the amphipathic liquid and dissolves in the amphipathic liquid, toward the upper surface of the substrate held by the substrate holder; the substrate processing apparatus further includes at least one valve that causes the at least one nozzle to individually discharge the plurality of processing liquids; and a control device that controls the at least one valve and the water suction actuator; The control device a chemical solution supplying step of supplying the chemical solution to the upper surface of the substrate; a rinse liquid supplying step of supplying the water-containing liquid as a rinse liquid onto the upper surface of the substrate, thereby replacing the chemical liquid on the upper surface of the substrate with the water-containing liquid; a pre-water-repellent amphipathic liquid supplying step of supplying the amphipathic liquid to the upper surface of the substrate to replace the water-containing liquid on the upper surface of the substrate with the amphipathic liquid; a pre-water-repellent hydrophobic liquid supplying step of supplying the hydrophobic liquid to the upper surface of the substrate, thereby replacing the amphipathic liquid on the upper surface of the substrate with the hydrophobic liquid; a water-repellent supplying step of supplying the water-repellent-containing liquid onto the upper surface of the substrate to replace the hydrophobic liquid on the upper surface of the substrate with the water-repellent-containing liquid; a water supplying step of supplying the water-containing liquid to the upper surface of the substrate; a water absorbing step of removing the water-containing liquid from the upper surface of the substrate by bringing the water absorbent body into contact with the water-containing liquid on the upper surface of the substrate.

11. 10. The substrate processing apparatus according to claim 8, wherein the water absorbing actuator brings the water absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining the water absorbing body separated from the upper surface of the substrate.

12. 10. The substrate processing apparatus according to claim 8, wherein the water-absorbing actuator brings the water-absorbing body into contact with the water-containing liquid on the upper surface of the substrate in a state in which at least a portion of the recess is filled with air before the water-absorbing body comes into contact with the water-containing liquid on the upper surface of the substrate, and the water-containing liquid is supported by the air in the recess and the protrusion.

13. 10. The substrate processing apparatus according to claim 8, wherein the water absorbing actuator brings the water absorbing body into contact with the water-containing liquid on the upper surface of the substrate while maintaining a state in which the substrate and the water absorbing body do not move relatively in a horizontal direction.

14. 10. The substrate processing apparatus according to claim 8, wherein spin drying, which dries the substrate by rotating the substrate, is not performed after the water-containing liquid on the upper surface of the substrate is brought into contact with the water-absorbing body.

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