Substrate processing method and substrate processing apparatus

Abstract

The present invention provides a substrate processing method that can shorten the time during which the surface tension of the processing solution is applied to the pattern on the surface of the substrate. [Solution] The substrate processing method involves moving the substrate W, which is in an inclined position with respect to a vertical plane, and the liquid surface LS, which is the surface of the processing liquid in the immersion tank 21, relative to each other in the vertical direction. This changes the substrate W from an immersed state, where the entire substrate W is positioned in the processing liquid in the immersion tank 21, to a non-immersed state, where the entire substrate W is positioned above the liquid surface LS.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. The substrate includes, for example, a semiconductor wafer, a substrate for FPD (Flat Panel Display) such as a liquid crystal display device or an organic EL (electroluminescence) display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and the like.

Background Art

[0002] Patent Document 1 discloses tilting a substrate held in a vertical posture by a lifter.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 does not disclose the posture of the substrate when the substrate held by the lifter intersects the surface of the processing liquid in the inner tank.

[0005] At least one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus capable of shortening the time during which the surface tension of the processing liquid acts on the pattern on the surface of the substrate.

Means for Solving the Problems

[0006] One embodiment of the present invention provides a method for processing a substrate having a pattern formed on its surface including convex and concave portions, the method comprising an immersion release step, in which the substrate is changed from an immersed state in which the entire substrate is positioned in the processing liquid in the immersion tank to an unimmersed state in which the entire substrate is positioned above the liquid surface, by moving the substrate, which is in an inclined position with respect to a vertical plane, and the liquid surface, which is the surface of the processing liquid in the immersion tank, in the vertical direction relative to each other.

[0007] In the above embodiment, at least one of the following features may be added to the substrate processing method.

[0008] The immersion release step is a step of changing the substrate from the immersed state to the non-immersed state by moving the substrate in the inclined position and the liquid surface relatively in the vertical direction while the water-containing liquid as the processing liquid is stored in the immersion tank.

[0009] The substrate processing method further includes a water-repellent supply step of immersing the substrate in a water-repellent solution contained in an immersion tank, while the solution contains a water-repellent solution that increases the water contact angle with a horizontal smooth surface made of the same material as the end face of the protrusion to a value greater than 90 degrees; and a water supply step of immersing the substrate in a water-containing solution contained in an immersion tank, after the substrate has been immersed in the water-repellent solution in the immersion tank, while the water-containing solution is contained in the immersion tank.

[0010] The immersion release step includes a step of moving the substrate in the inclined position and the liquid surface relatively in the vertical direction while 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.

[0011] The substrate processing method further includes a post-hydrophobic liquid supply step, in which the substrate is immersed in the water-repellent agent-containing liquid in the immersion tank, and then the substrate is immersed in the hydrophobic liquid in the immersion tank, while a hydrophobic liquid that dissolves with the water-repellent agent-containing liquid is stored in the immersion tank; and a post-amphiphilic liquid supply step, in which the substrate is immersed in the water-repellent agent-containing liquid in the immersion tank, and then the substrate is immersed in the amphiphilic liquid in the immersion tank, while an amphiphilic liquid that has a higher water solubility than the hydrophobic liquid and dissolves with the hydrophobic liquid is stored in the immersion tank, wherein the water supply step is a step in which the substrate is immersed in the amphiphilic liquid in the immersion tank, and then the substrate is immersed in the water-containing liquid in the immersion tank, while a water-containing liquid that has a higher surface tension than the amphiphilic liquid and dissolves with the amphiphilic liquid is stored in the immersion tank.

[0012] The substrate processing method includes a chemical solution supply step of immersing the substrate in the chemical solution in the immersion tank, while the chemical solution for oxidizing the surface of the substrate is stored in the immersion tank; a rinsing solution supply step of immersing the substrate in the water-containing liquid in the immersion tank, after the substrate has been immersed in the chemical solution in the immersion tank, while the water-containing liquid used as a rinse solution is stored in the immersion tank; and a step of immersing the substrate in the water-containing liquid in the water-containing liquid, after the substrate has been immersed in the water-containing liquid in the immersion tank, while the amphiphilic liquid that dissolves with the water-containing liquid is stored in the immersion tank. The water repellent supply step further includes a step of supplying an amphiphilic liquid before immersion, and a step of supplying a hydrophobic liquid before immersion, wherein after immersing the substrate in the amphiphilic liquid in the immersion tank, the substrate is immersed in the hydrophobic liquid in the immersion tank, where the hydrophobic liquid has a lower water solubility than the amphiphilic liquid and dissolves with the amphiphilic liquid, and the water repellent supply step is a step of immersing the substrate in the water repellent liquid in the immersion tank, where the water repellent liquid is stored in the immersion tank.

[0013] The aforementioned inclined position is a position in which, when the substrate is moving upward relative to the liquid surface while the substrate is in contact with the liquid surface, the receding contact angle, which is the angle between the surface of the substrate and the liquid surface, approaches or coincides with 90 degrees.

[0014] The immersion release step is a step of changing the substrate from the immersed state to the non-immersed state by moving the substrate and the liquid surface relative to each other in the vertical direction while fixing the substrate in the inclined position.

[0015] The substrate processing method further includes a fixing step of pressing two grippers, which move together with the two support frames, against the end face of the substrate in a vertical position supported by the two support frames by moving the two support frames due to the weight of the substrate through contact between the outer periphery of the substrate and the two support frames, and a posture changing step of changing the posture of the two support frames and the two grippers while the two support frames and the two grippers are in contact with the substrate, thereby changing the posture of the substrate from the vertical position to the inclined position.

[0016] The substrate processing method further includes a posture changing step of changing the substrate between a vertical position and an inclined position using a plurality of translation actuators, and a lifting step of moving the substrate in the vertical or inclined position in the vertical direction using the plurality of translation actuators.

[0017] Another embodiment of the present invention provides a substrate processing apparatus comprising: a lifter that holds a substrate having a pattern including convex and concave portions formed on its surface in an inclined position tilted with respect to a vertical plane; an immersion tank that stores a processing liquid into which the substrate held by the lifter is immersed; a translation actuator that moves the substrate held by the lifter in the vertical direction between an immersion position in which the substrate held by the lifter is positioned in the immersion tank and a non-immersion position in which the substrate held by the lifter is positioned above the immersion tank; a drain valve that discharges the processing liquid from the immersion tank; and a control device that changes the substrate from an immersed state in which the entire substrate is positioned in the processing liquid in the immersion tank to a non-immersed state in which the entire substrate is positioned above the liquid surface of the processing liquid in the immersion tank by causing the translation actuator to raise the substrate in the inclined position held by the lifter and causing the drain valve to discharge the processing liquid from the immersion tank. At least one of the features of the substrate processing method described above may be added to the substrate processing apparatus.

[0018] In the above embodiment, at least one of the following features may be added to the substrate processing apparatus.

[0019] The lifter includes two support frames that support the substrate by contacting the outer periphery of the substrate and move under the weight of the substrate, and two grippers that move together with the two support frames and are pressed against the end face of the substrate in a vertical position supported by the two support frames, and the substrate processing apparatus further includes a posture changing actuator that changes the position of the two support frames and the two grippers to change the substrate from the vertical position to the inclined position.

[0020] The parallel movement actuator includes a plurality of parallel movement actuators that move the substrate held by the lifter vertically in parallel between the immersion position and the non-immersion position, and change the substrate held by the lifter between a vertical posture and an inclined posture.

Brief Description of the Drawings

[0021] [Figure 1] It is a schematic diagram for explaining an example of substrate processing according to an embodiment. [Figure 2A] It is a schematic cross-sectional view showing an example of the structure of the substrate to be processed. [Figure 2B] It is a schematic cross-sectional view of the substrate to which the water repellent-containing liquid is supplied. [Figure 2C] It is a schematic cross-sectional view of the substrate to which DIW (pure water) is supplied. [Figure 3A] It is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in the Wenzel state. [Figure 3B] It is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in the Cassie-Baxter state. [Figure 4A] It is a schematic diagram showing a state where the substrate in the inclined posture intersects with the liquid surface. [Figure 4B] It is a schematic cross-sectional view for explaining the receding contact angle when the substrate is in the vertical posture. <00's0096> [Figure 4C] It is a schematic cross-sectional view for explaining the receding contact angle when the substrate is in the inclined posture. [Figure 5] It is a schematic cross-sectional view for explaining a state where one droplet is stationary while contacting a horizontal rough surface larger than the same droplet at a contact angle exceeding 90 degrees. <000'0101>It is a schematic plan view showing the layout of a batch-type substrate processing apparatus according to an embodiment. [Figure 7] It is a schematic diagram showing a cross-section of the liquid processing tank cut along a vertical plane. [Figure 8] It is a schematic side view of the lifter. [Figure 9] It is a schematic front view of the lifter. [Figure 10A] This is a front view of the lifter with the base plate omitted. [Figure 10B] This is a front view of the lifter with the base plate omitted. [Figure 11] Figure 10B is a schematic cross-sectional view showing a section along the line XI-XI. [Figure 12] This is a schematic cross-sectional view showing multiple substrates in an inclined position, moving from an immersion position to a non-immersion position. [Modes for carrying out the invention]

[0022] Hereinafter, embodiments of this invention will be described in detail with reference to the accompanying drawings.

[0023] Figure 1 is a schematic diagram illustrating an example of the processing of a substrate W according to one embodiment. Figure 2A is a schematic cross-sectional view showing an example of the structure of the substrate W to be processed. Figure 2B is a schematic cross-sectional view of the substrate W to which a water-repellent agent-containing liquid has been supplied. Figure 2C is a schematic cross-sectional view of the substrate W to which DIW (pure water) has been supplied.

[0024] The substrate W to be processed includes a front and back surface that are parallel to each other, and an annular end face that connects the outer edges of the front and back surfaces along the entire circumference of the front and back surfaces. Figure 2A shows the substrate W with its front surface facing upwards. The front surface of the substrate W corresponds to the top surface of the substrate W. The front surface of the substrate W is the device-forming surface on which devices are formed. The back surface of the substrate W is a non-device-forming surface on which no devices are formed. Both the front and back surfaces of the substrate W may be device-forming surfaces.

[0025] 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 perpendicular to the flat surface of the substrate W before the pattern PA is formed, and the plane direction of the substrate W is parallel to that surface. In Figure 2A, the vertical direction of the paper corresponds to the thickness direction of the substrate W, and the horizontal direction of the paper corresponds to the plane direction of the substrate W. The pattern PA may be formed before the substrate processing apparatus 1 (see Figure 6) processes the substrate W, or it may be formed while the substrate processing apparatus 1 is processing the substrate W.

[0026] Figure 2A shows an example of a cross-section of a substrate W cut with 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 extending in the thickness direction of the substrate W from the surface of the base layer s4 of the substrate W. The base layer s4 may be part of a disc-shaped substrate made of semiconductor material, or it may be 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 plane direction of the substrate W. Two protrusions P1 that are spaced apart and facing each other in the plane direction of the substrate W form a recess Q1 that is recessed in the thickness direction of the substrate W from the tips of the two protrusions P1.

[0027] Figure 2A shows an example where 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, prismatic, or plate-shaped, or it may have any other shape. The recess Q1 may be a hole or a groove. The protrusion P1 and recess Q1 may extend in the plane 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 to the tip of the protrusion P1, or it may vary. The width of the recess Q1 may be constant from the bottom to the entrance of the recess Q1, or it may vary.

[0028] The protrusion P1 may consist of only one layer, or it may consist of multiple layers stacked in the height direction of the protrusion P1. Figure 2A shows an example of the former. In the latter case, all layers included in a single protrusion P1 may be made of the same or different materials, or some of all the layers may be made of the same material but different from the rest of all the layers. The material of the protrusion P1 may be one or more of semiconductors, insulators, and metals, or it may be something other than these. The material of the end face s1 of the protrusion P1 may be a silicon-containing material such as silicon dioxide, or it may be something other than this.

[0029] The surface of pattern PA includes the surface of the protrusions P1 and the inner surface of the recesses Q1. The surface of the protrusions P1 includes an end face s1 corresponding to the tip of the protrusions P1 and a side surface s2 extending from the end face s1 to the base of the protrusions P1. The end face s1 of the protrusions P1 corresponds to the tip and top surfaces of the protrusions P1. Multiple end faces s1 of the protrusions P1 are arranged on a single plane. Multiple end faces s1 of the protrusions P1 correspond to part or all of the surface of the substrate W. The inner surface of the recesses Q1 includes a bottom surface s3 corresponding to the bottom of the recesses Q1 and a side surface extending from the bottom surface s3 to the entrance of the recesses Q1. The side surface of the recesses Q1 may also be the side surface s2 of the protrusions P1, or it may be different from the side surface s2. Figure 2A shows an example of the former. The side surface of the recesses Q1 forms the entrance of the recesses Q1.

[0030] When processing substrates W as shown in Figure 2A, one or more substrates W are held in a vertical position. The upper left of Figure 1 shows an example of multiple substrates W being held in a vertical position. After holding one or more substrates W in a vertical position, the substrates W are lowered into the immersion tank 21 that stores the processing liquid, thereby changing the state of the substrates W from non-immersed to immersed. The non-immersed state is when the entire substrate W is positioned above the liquid level LS, which is the surface of the processing liquid in the immersion tank 21. The immersed state is when the entire substrate W is placed in the processing liquid in the immersion tank 21. When one or more substrates W are changed to the immersed state, the entire surface, back surface, and edge surfaces of the substrates W come into contact with the processing liquid. As a result, the processing liquid is supplied to the one or more substrates W in the vertical position.

[0031] After supplying all the processing liquid to be supplied to one or more substrates W, the immersed substrates W are changed from a vertical position to an inclined position, as shown in the second position from the left in the lower row of Figure 1. An inclined position is a position in which the substrate W is tilted with respect to a vertical plane. More specifically, an inclined position is a position in which the substrate W is tilted at an angle of less than 90 degrees θi (see Figure 4A) around a horizontal line parallel to the surface of the substrate W with respect to a vertical plane, such that the surface of the substrate W faces upward or downward. The angle of inclination θi is the angle between the surface of the substrate W and the vertical plane. The angle of inclination θi may be 45 degrees or less. When multiple substrates W are held in an inclined position, all substrates W are parallel to each other while being separated from each other, and the centers of all substrates W are aligned along a single straight line. The distance between two horizontally adjacent substrates W may be constant or may vary.

[0032] After changing one or more immersed substrates W from a vertical position to an inclined position, the inclined substrates W are changed from an immersed state to a non-immersed state, as shown in the second, third, and fourth images from the left in the lower row of Figure 1. The change to a non-immersed state may be performed by raising the substrates W above the immersion tank 21, or by discharging the processing liquid from the immersion tank 21, or by both raising the substrates W and discharging the processing liquid. When the processing liquid is discharged from the immersion tank 21 while one or more substrates W are placed inside the immersion tank 21, the horizontal liquid level LS moves downward in parallel within the immersion tank 21. As a result, the liquid level LS in the immersion tank 21 drops from a position above the upper end of the substrates W to a position below the lower end of the substrates W, and the substrates W change from an immersed state to a non-immersed state. When changing the substrate W from an immersed state to an unimmersed state, the relative speed at which the surface of the substrate W and the liquid level LS in the immersion tank 21 move in the vertical direction may be constant or may change.

[0033] After changing one or more substrates W from an immersed state to a non-immersed state in an inclined position, the one or more substrates W are dried. The method of drying the substrates W may be reduced-pressure drying or another method. From the time the one or more substrates W are changed to a non-immersed state until drying, the one or more substrates W may be maintained in an inclined position or in a position other than an inclined position, such as a vertical position. In the latter case, after changing one or more substrates W from an inclined position to a non-immersed state, the one or more substrates W may be changed from an inclined position to a vertical position and maintained in a vertical position. After that, the one or more substrates W in a vertical position may be moved horizontally to a drying tank 2d (see Figure 6) for drying the substrates W.

[0034] The processing solution to be supplied to the substrate W may be at least one of the chemical solution and the rinsing solution, or it may contain a liquid other than the chemical solution and the rinsing solution in addition to or instead of at least one of the chemical solution and the rinsing solution. The chemical solution may contain at least one of the following: sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, hydrogen peroxide, organic acids (e.g., citric acid, oxalic acid, etc.), organic alkalis (e.g., TMAH (Tetramethylammonium hydroxide)), surfactants, and corrosion inhibitors, or it may be any other liquid. The rinsing solution may be any of the following: pure water (deionized water: DIW), carbonated water, electrolyzed ionized water, hydrogen water, ozonated water, hydrochloric acid water at a dilution concentration (e.g., about 1 to 100 ppm), and ammonia water at a dilution concentration (e.g., about 1 to 100 ppm), or it may be any other liquid. The rinsing solution is an example of a water-containing liquid. The water-containing liquid may be a liquid with a water content of 100% or substantially 100% (e.g., 99% or more), or it may be a liquid that also contains substances other than water.

[0035] The number of treatment solutions supplied to the substrate W until the substrate W is dried may be one or multiple. Figure 1 shows an example in which multiple treatment solutions are sequentially supplied to one or more substrates W. In this example, multiple treatment solutions are sequentially supplied to one or more substrates W in the order of DHF, DIW (pure water), SC1, DIW, IPA, toluene, water-repellent agent-containing solution, toluene, IPA, and DIW. When multiple treatment solutions are sequentially supplied to one or more substrates W, the substrate W may be changed from an immersed state to an unimmersed state while maintaining an inclined position, regardless of which treatment solution is in contact with one or more substrates W, or the substrate W may be changed from an immersed state to an unimmersed state while maintaining an inclined position only when a specific treatment solution is in contact with one or more substrates W.

[0036] When supplying multiple processing solutions sequentially to one or more substrates W, the processing solution in one immersion tank 21 may be replaced with another processing solution, or one or more substrates W may be moved from an immersion tank 21 containing one processing solution to an immersion tank 21 containing another processing solution. The former example will be described below. In the example shown in Figure 1, as shown in the second from the left in the upper row of Figure 1, one or more substrates W are immersed in DHF in the immersion tank 21. DHF (dilute hydrofluoric acid) is a chemical solution that removes the native oxide film of silicon. This removes the native oxide film from the substrates W.

[0037] After supplying DHF from the immersion tank 21 to one or more substrates W, the DHF is discharged from the immersion tank 21 and pure water is supplied to the immersion tank 21, thereby replacing the processing liquid (DHF) in the immersion tank 21 with another processing liquid (pure water). The supply of pure water to the immersion tank 21 may be started after the DHF has been removed from the immersion tank 21, or it may be started before the DHF has been removed from the immersion tank 21. In the latter case, the supply of pure water to the immersion tank 21 may be started before the liquid level LS of the DHF in the immersion tank 21 moves below the upper edge of one or more substrates W, or it may be started after the liquid level LS has moved below the upper edge of the substrates W. The contents of this paragraph also apply when performing replacements other than replacement from DHF to pure water.

[0038] As shown in the third image from the left in the upper row of Figure 1, after replacing the DHF in the immersion tank 21 with pure water, the treatment solution in the immersion tank 21 is replaced with another treatment solution in the following order: SC1, DIW, IPA, toluene, water-repellent agent-containing solution, toluene, IPA, DIW. For example, when replacing the pure water in the immersion tank 21 with SC1, the pure water is drained from the immersion tank 21 and SC1 is supplied to the immersion tank 21, as described above. As a result, as shown in the fourth image from the left in the upper row of Figure 1, SC1 in the immersion tank 21 is supplied to one or more substrates W. SC1 (a mixture of ammonia water, hydrogen peroxide, and water) is a chemical solution that removes particles, organic matter, etc. from the substrate W. SC1 is an example of a chemical solution that oxidizes the surface of the substrate W.

[0039] Toluene is an example of a hydrophobic liquid. IPA (isopropyl alcohol) is an example of an amphiphilic liquid. A hydrophobic liquid is a liquid that dissolves in a water-repellent solution. An amphiphilic liquid is a liquid that dissolves in both hydrophobic liquids and water-containing solutions. An amphiphilic liquid may also dissolve in a water-repellent solution. A hydrophobic liquid may also dissolve in a water-containing solution if the solubility of water in a hydrophobic liquid is less than the solubility of water in an amphiphilic liquid. The solubility of water in an amphiphilic liquid is less than the solubility of water in a water-containing solution. The surface tension of an amphiphilic liquid is lower than the surface tension of a water-containing solution. The surface tension of an amphiphilic liquid may be equal to the surface tension of a hydrophobic liquid, or it may be higher or lower than that surface tension. The surface tension of a hydrophobic liquid may be equal to the surface tension of a water-containing solution, or it may be higher or lower than that surface tension.

[0040] The hydrophobic liquid and amphiphilic liquid may be an organic solvent. In this case, the hydrophobic liquid may be at least one of the following: 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 applies to amphiphilic liquids.

[0041] The water-repellent agent-containing liquid is a liquid that modifies the surface of the substrate W. The water-repellent agent-containing liquid is a liquid that makes the surface of the substrate W hydrophobic. After the water-repellent agent-containing liquid is supplied, the surface of the substrate W is a water-repellent surface. The surface of the substrate W is a rough surface on which a pattern PA (see Figure 2A) is formed, which includes convex portions P1 and concave portions Q1. The water-repellent agent-containing liquid is a liquid that increases the contact angle of water with respect to the end face s1 of the convex portion P1 and a horizontal smooth surface made of the same material to a value greater than 90 degrees.

[0042] The water-repellent agent-containing liquid may be a liquid containing 100% or substantially 100% water-repellent agent, or it may be a liquid containing substances other than water-repellent agents. In the latter case, the water-repellent agent-containing liquid may be a solution containing a water-repellent agent as a solute and a solvent that dissolves with the water-repellent agent. In this case, the solvent of the water-repellent agent-containing liquid may be at least one of the aforementioned specific examples of organic solvents such as IPA. The solvent contained in the water-repellent agent-containing liquid may be a liquid with the same composition as the hydrophobic liquid.

[0043] The water repellent may be at least one of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDTS), 3-aminopropyltriethoxysilane (APTES), benzyltrichlorosilane (Bn-TS), 11-cyanoundecyltrichlorosilane, 11-iodonundecyltrichlorosilane, 11-bromoundecyltrichlorosilane, 11-chloroundecyltrichlorosilane, or undecyltrichlorosilane (H-UTS). In other words, the water repellent may also be a silylating agent.

[0044] When one or more substrates W are immersed in a hydrophobic liquid such as toluene and then immersed in a water-repellent agent-containing solution, the water-repellent agent-containing solution mixes with the hydrophobic liquid in the recesses Q1 and enters the recesses Q1. As a result, the hydrophobic liquid in contact with the substrate W is replaced by the water-repellent agent-containing solution. The water-repellent agent-containing solution comes into contact not only with the end faces s1 and side surfaces s2 of the protrusions P1, but also with the bottom surface s3 of the recesses Q1. As shown in Figure 2B, the water-repellent agent contained in the water-repellent agent-containing solution adheres to the surface of the substrate W, such as the end faces s1 of the protrusions P1, and forms a water-repellent film R1 on at least a portion of the surface of the substrate W. If the water-repellent agent is a silylation agent, the hydrogen atoms of the hydroxyl groups exposed on the surface of the substrate W are replaced with silyl groups containing silicon atoms and multiple methyl groups, and the multiple silyl groups form the water-repellent film R1. This increases the water repellency of the surface of the substrate W. Note that Figures 2B and 2C depict a boundary between the water-repellent agent-containing liquid and the water-repellent film R1, but in reality, no such boundary exists.

[0045] The water-repellent agent contained in the water-repellent agent-containing liquid is a substance that increases the water contact angle with respect to a horizontal smooth surface made of the same material as the end face s1 of the protrusion P1 to a value greater than 90 degrees. Assuming that the surface of the substrate W is a smooth surface, when the water-repellent agent-containing liquid is supplied to the surface of the substrate W, the water contact angle with respect to the surface of the substrate W will exceed 90 degrees. According to Wenzel's formula, when comparing the water contact angles with smooth and rough surfaces made of the same material, when the water contact angle with respect to the smooth surface exceeds 90 degrees, the water contact angle with respect to the rough surface is greater than the water contact angle with respect to the smooth surface. The surface of the substrate W is a rough surface on which a fine pattern PA is formed. Therefore, the water contact angle with respect to the surface of the substrate W is greater than when the surface of the substrate W is a smooth surface.

[0046] After supplying the water-repellent agent-containing liquid, a hydrophobic liquid (toluene), an amphiphilic liquid (IPA), and pure water are supplied in that order. The hydrophobic liquid enters the recess Q1 while mixing with the water-repellent agent-containing liquid in the recess Q1. The same applies to the amphiphilic liquid and pure water. Therefore, when one or more substrates W are immersed in pure water, the pure water enters the recess Q1 while mixing with the amphiphilic liquid in the recess Q1. Figure 2C shows a state where the recess Q1 is filled with pure water, and the entire surface, back surface, and edge faces of the substrate W are in contact with the pure water.

[0047] Figure 3A is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in the Wenzel state. Figure 3B is a schematic cross-sectional view showing an example of a droplet in contact with a rough surface in the Cassie-Baxter state. As shown in Figure 3A, 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 to the recess Q1 located between them.

[0048] As shown in Figure 3A, 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 the recess Q1. As shown in Figure 3B, 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 tip of the convex part P1. In the CB state, the water droplet is supported by the air in the recess Q1 and the tip of the convex part P1. In other words, when a water droplet is placed on a horizontal rough surface under normal temperature and pressure conditions (room temperature and 1 atmosphere), the bottom of the recess Q1 is separated from the water droplet, while the tip of the convex part P1 is in contact with the water droplet. Room temperature is, for example, a constant or nearly constant temperature within the range of 10 to 30°C.

[0049] Whether a water droplet on a rough surface adopts the W state or the 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 (higher water repellency of the rough surface), the more likely the water droplet on the rough surface is to enter the CB state.

[0050] Pure water is a liquid with high surface tension. The water repellent contained in the water repellent 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 face s1 of the protrusion P1 to a value greater than 90 degrees, and the surface of the substrate W is rough. Therefore, the surface free energy of the surface of the substrate W is low (the surface of the substrate W is highly water-repellent). For this reason, when the amphiphilic liquid in contact with the surface of the substrate W is replaced with pure water, the pure water can come into contact with the surface of the substrate W in a CB state. In other words, in the process of replacing the amphiphilic liquid in contact with the surface of the substrate W with pure water, at least one of the amphiphilic liquid and the pure water can be discharged from the recess Q1, and at least a part of the recess Q1 can be filled with air.

[0051] After replacing the water-repellent agent-containing liquid in contact with the surface of the substrate W with pure water, which is an example of a water-containing liquid, via a hydrophobic liquid and an amphiphilic liquid, the pure water in contact with the surface of the substrate W may be in the W state or the CB state. When changing one or more substrates W in an inclined position from an immersed state to an unimmersed state, the pure water in the immersion tank 21 may change from the W state to the CB state at the point where the surface of the substrate W and the liquid surface LS in the immersion tank 21 intersect. Figures 4B and 4C show examples where the pure water is in the CB state and in contact with the surface of the substrate W at the point where the substrate W and the liquid surface LS intersect. When water is in the CB state and in contact with the surface of a horizontal substrate W, the contact angle of the water with respect to the surface of the substrate W may be 100 degrees or more, preferably 140 degrees or more.

[0052] Figure 4A is a schematic diagram showing the state in which the inclined substrate W and the liquid surface LS intersect. Figure 4B is a schematic cross-sectional view illustrating the receding contact angle θr when the substrate W is in a vertical position. Figure 4C is a schematic cross-sectional view illustrating the receding contact angle θr when the substrate W is in an inclined position. Figure 5 is a schematic cross-sectional view illustrating the state in which a single liquid droplet is stationary while in contact with a horizontal rough surface larger than the droplet at a contact angle of more than 90 degrees.

[0053] As shown in Figure 4A, when the substrate W is changed from an immersed state to an unimmersed state, the liquid level LS in the immersion tank 21 intersects with the front, back, and end faces of the substrate W. As a result, a boundary line BL between the substrate W and the liquid level LS is formed on the front, back, and end faces of the substrate W by the processing liquid in the immersion tank 21. On the right side of Figure 4A, the boundary line BL is shown as a thick line. The boundary line BL is a horizontal or nearly horizontal closed curve that encircles the entire circumference of the substrate W. The boundary line BL corresponds to the interface between air (gas), processing liquid (liquid), and substrate W (solid). Since the substrate W and the processing liquid attract each other at their interface, when the substrate W and the liquid level LS move relatively in the vertical direction, the boundary line BL is positioned slightly above the liquid level LS.

[0054] When the substrate W and the liquid level LS in the immersion tank 21 move relatively vertically while the liquid level LS intersects with the substrate W, the surface tension of the processing liquid in the immersion tank 21 is applied to the surface of the substrate W through the boundary line BL. If the relative speeds at which the substrate W and the liquid level LS move vertically are the same, changing the substrate W from an immersed state to an unimmersed state in an inclined position shortens the time that the substrate W and the liquid level LS intersect compared to changing the substrate W from an immersed state to an unimmersed state in a vertical position. This shortens the time that the surface tension of the processing liquid in the immersion tank 21 is applied to the pattern PA on the surface of the substrate W. Furthermore, when the substrate W in contact with the processing liquid in the immersion tank 21 is raised, resistance is applied from the processing liquid in the immersion tank 21 to the substrate W. In other words, a portion of the force that raises the substrate W is converted into resistance from the processing liquid to the substrate W. The pattern PA is subjected to this resistance. By changing the substrate W from an immersed state to an unimmersed state while it is tilted, the time during which such resistance is applied to the pattern PA can also be shortened.

[0055] When the substrate W and the liquid level LS in the immersion tank 21 move relative to each other in the vertical direction while the liquid level LS in the immersion tank 21 intersects with the substrate W, the processing liquid in the immersion tank 21 moves downward relative to the substrate W. In other words, the direction parallel to the surface of the substrate W and toward the lower end of the substrate W corresponds to the direction of travel of the processing liquid relative to the substrate W. The thick black arrows in Figures 4B and 4C indicate the direction of travel of the processing liquid flowing along the surface of the substrate W. When the substrate W is moving upward relative to the liquid level LS while the liquid level LS in the immersion tank 21 intersects with the substrate W, the angle between the substrate W and the liquid level LS corresponds to the receding contact angle θr. Figure 4B shows the receding contact angle θr when the substrate W is in a vertical position. Figure 4C shows the receding contact angle θr when the substrate W is in an inclined position. As can be seen by comparing Figures 4B and 4C, the receding contact angle θr increases when the substrate W is inclined with respect to the vertical plane. When the substrate W is in an inclined position, the retraction contact angle θr may be 90 degrees, or it may be greater than or less than 90 degrees.

[0056] We consider a state in which a single liquid droplet is at rest, in contact with a horizontal smooth surface larger than the droplet at a contact angle greater than 90 degrees. The component of the surface tension applied from the surface of the droplet to the smooth surface perpendicular to the smooth surface (Fs) can be defined as (Equation 1) Fs = 2πrγsinθ. Here, r is the radius of the circular interface between the droplet and the smooth surface, γ is the surface tension of the liquid constituting the droplet, and θ is the angle (contact angle) that the surface of the droplet and the smooth surface make at their intersection (see Figure 5). As shown in Figure 5, if the smooth surface in the same state is replaced with a rough surface, that is, the surface of a horizontal substrate W (more precisely, the end faces s1 of the multiple protrusions P1), the component of the surface tension applied from the surface of the droplet to the surface of the substrate W perpendicular to the surface of the substrate W (Fr) can be defined as (Equation 2) Fr = 2πrγsinθ × w / p. Here, w is the width of the convex P1, and p is the pitch (the distance between the centers of two adjacent convex P1s). Everything else is the same as in Equation 1.

[0057] In equation (2), Fr = 2πrγsinθ × w / p, Fr is maximized when θ = 90. In other words, in equation 2, when θ = 90, the component of the surface tension applied from the surface of the droplet to the surface of the substrate W (the perpendicular component of surface tension) is maximized, and the component of the same surface tension parallel to the surface of the substrate W (the parallel component of surface tension) is zero. Therefore, by bringing θ, that is, the angle between the surface of the droplet and the surface of the substrate W at their intersection, closer to 90 degrees, the parallel component of surface tension can be reduced, and by setting this angle to 90 degrees, the parallel component of surface tension can theoretically be made zero.

[0058] As described above, when the substrate W is moving upward relative to the liquid level LS in the immersion tank 21, the liquid level LS in the immersion tank 21 is in contact with the surface of the substrate W at a receding contact angle θr. The tilted position of the substrate W is a position in which the substrate W is tilted at an angle of less than 90 degrees θi around a horizontal line parallel to the surface of the substrate W with respect to a vertical plane, so that the surface of the substrate W faces upward or downward. When the substrate W is tilted, regardless of whether the surface of the substrate W is facing upward or downward, the receding contact angle θr increases. The receding contact angle θr increases by the amount by which the tilt angle θi of the substrate W increases.

[0059] When transitioning one or more inclined substrates W from an immersion state to an unimmersion state, the inclination angle θi of the substrates W may be set such that the receding contact angle θr approaches or matches 90 degrees. In this way, the component of the surface tension applied to the surface of the substrates W from the liquid level LS in the immersion tank 21 in a direction parallel to the surface of the substrates W (the parallel component of surface tension) can be eliminated or reduced. The parallel component of surface tension is the force in the width direction of the protrusions P1. By eliminating or reducing this component, the collapse rate of the pattern PA can be reduced.

[0060] Next, we will describe the substrate processing apparatus 1 that performs the aforementioned processing on the substrate W.

[0061] Figure 6 is a schematic plan view showing the layout of a batch-type substrate processing apparatus 1 according to one embodiment.

[0062] The substrate processing apparatus 1 is a batch-type apparatus that processes multiple substrates W at once. The substrate processing apparatus 1 includes a load port LP that holds carriers CA that accommodate disc-shaped substrates W such as semiconductor wafers, a processing unit 2 that processes the substrates W transported from the load port LP with processing liquids such as chemical solutions and rinsing solutions, a transport system 8 that transports the substrates W between the load port LP and the processing unit 2, and a control device 3 that controls the substrate processing apparatus 1.

[0063] The processing unit 2 includes multiple liquid processing tanks 2L for storing processing liquid into which multiple substrates W are immersed, and a drying processing tank 2d for drying the multiple substrates W by a drying method such as vacuum drying. Vacuum drying is a drying method that evaporates the liquid adhering to the substrates W by reducing the atmospheric pressure. The multiple pairs of liquid processing tanks 2L are arranged in a straight line in the depth direction of the substrate processing apparatus 1 (left-right direction in Figure 6) in a plan view. The drying processing tank 2d is located between the transport system 8 and the multiple liquid processing tanks 2L in the depth direction of the substrate processing apparatus 1 in a plan view.

[0064] Each liquid treatment tank 2L may be a dedicated liquid treatment tank that supplies only one type of treatment liquid to multiple substrates W, or it may be a general-purpose liquid treatment tank that sequentially supplies multiple treatment liquids to multiple substrates W. Both dedicated and general-purpose liquid treatment tanks may be included in multiple liquid treatment tanks 2L. Figure 6 shows an example where all liquid treatment tanks 2L are general-purpose liquid treatment tanks.

[0065] The transport system 8 includes a carrier transport device 9 that transports carriers CA between the load port LP and the processing unit 2 and accommodates multiple carriers CA, and a posture change robot 10 that loads and unloads multiple substrates W to and from the carriers CA held by the carrier transport device 9 and changes the posture of the substrates W between a horizontal and a vertical position. The posture change robot 10 performs a batch assembly operation to form one batch with multiple substrates W taken out from multiple carriers CA, and a batch release operation to accommodate the multiple substrates W included in one batch into multiple carriers CA.

[0066] The transport system 8 further includes a main transport robot 11 that transports multiple substrates W between the attitude changing robot 10 and the processing unit 2, and multiple sub-transport robots 12 that transport multiple substrates W between the main transport robot 11 and the processing unit 2. Figure 6 shows an example in which two sub-transport robots 12 and two pairs of liquid processing tanks 2L are provided. The sub-transport robots 12 load and unload multiple substrates W into and from each of the two paired liquid processing tanks 2L, and transport multiple substrates W between the two paired liquid processing tanks 2L.

[0067] The main transport robot 11 receives a batch of substrates W, consisting of multiple substrates (for example, 50) from the attitude changing robot 10, and passes the received batch of substrates W to one of the multiple sub-transport robots 12. In the multiple substrates W that make up the batch, the orientation of the surfaces of all substrates W may be the same, or the orientation of the surface of one or more substrates W may be different from the orientation of the surfaces of the other substrates W. The sub-transport robot 12 immerses the batch of substrates W received from the main transport robot 11 in the processing liquid in at least one liquid processing tank 2L. After that, the main transport robot 11 receives the batch of substrates W from the sub-transport robot 12 and carries the received batch of substrates W into the drying processing tank 2d.

[0068] The control device 3 controls the electrical and electronic equipment provided in the substrate processing device 1. The control device 3 includes at least one computer that can communicate with each other. The computer includes a memory 3b for storing information such as programs, and a CPU 3a (central processing unit) that controls the substrate processing device 1 according to the programs stored in the memory 3b. By controlling the substrate processing device 1, the control device 3 performs transport and processing of the substrate W. In other words, the control device 3 is programmed to transport and process the substrate W.

[0069] The control device 3 may store multiple recipes. That is, the data 3c stored in the control device 3 may contain multiple recipes. In addition to or instead of multiple recipes, the data 3c may include a setting value for the inclination angle θi (see Figure 4A), which will be described later. The setting value for the inclination angle θi may be part of a recipe or may be different from a recipe. A recipe is information that defines the processing content, processing conditions, and processing procedure for the substrate W. Multiple recipes differ from each other in at least one of the processing content, processing conditions, and processing procedure for the substrate W. The control device 3 controls the substrate processing apparatus 1 so that the substrate W is processed according to the recipe specified by the host computer. The control device 3 is programmed to transport and process the substrate W, etc.

[0070] Next, we will explain the 2L liquid treatment tank.

[0071] Figure 7 is a schematic diagram showing a cross-section of the liquid treatment tank 2L cut in a vertical plane. The liquid treatment tank 2L includes an immersion tank 21 for storing the treatment liquid. The immersion tank 21 includes a cylindrical peripheral wall 21p extending vertically and a bottom wall 21b that closes the bottom of the peripheral wall 21p. The peripheral wall 21p forms an opening 21o through which the substrate W to be treated passes vertically, and a storage space 21s for storing the treatment liquid to be supplied to the substrate W that has passed below the opening 21o. The storage space 21s extends downward from the opening 21o. Multiple substrates W are placed in the immersion tank 21 and immersed in the treatment liquid in the immersion tank 21. The liquid treatment tank 2L may or may not include an overflow tank 22 for storing the treatment liquid that overflows from the immersion tank 21. Figure 7 shows an example of the former.

[0072] The substrate processing apparatus 1 includes two processing liquid nozzles 23 that discharge processing liquid within the immersion tank 21, two individual pipes 24i that guide the processing liquid to the two processing liquid nozzles 23, and a common pipe 24c that guides the processing liquid to the two individual pipes 24i. The processing liquid flowing through the common pipe 24c is supplied to the two processing liquid nozzles 23 through the two individual pipes 24i. Each processing liquid nozzle 23 supplies processing liquid into the immersion tank 21 by discharging processing liquid from a discharge port 23p located within the immersion tank 21, and at the same time forms an upflow of processing liquid in the processing liquid within the immersion tank 21.

[0073] The substrate processing apparatus 1 includes one or more processing liquid pipes that guide the processing liquid toward two processing liquid nozzles 23. Figure 7 shows an example in which one or more processing liquid pipes are a first chemical pipe 26a, a second chemical pipe 26b, a rinse liquid pipe 26c, a water-repellent pipe 26d, a hydrophobic liquid pipe 26e, and an amphiphilic liquid pipe 26f. The first chemical pipe 26a guides DHF, an example of a first chemical, toward the two processing liquid nozzles 23. The second chemical pipe 26b guides SC1, an example of a second chemical, toward the two processing liquid nozzles 23. The rinse liquid pipe 26c guides pure water, an example of a rinse liquid, toward the two processing liquid nozzles 23. The water-repellent pipe 26d guides a water-repellent containing liquid toward the two processing liquid nozzles 23. The hydrophobic liquid pipe 26e guides toluene, an example of a hydrophobic liquid, toward the two processing liquid nozzles 23. The amphiphilic liquid piping 26f guides IPA, an example of an amphiphilic liquid, to two processing nozzles 23. These pipes are connected to the two processing nozzles 23 via a common pipe 24c and two individual pipes 24i.

[0074] The substrate processing apparatus 1 includes one or more processing liquid valves that switch between an open state, allowing processing liquid to flow downstream through one or more processing liquid pipes, and a closed state, stopping the processing liquid. Figure 7 shows an example where one or more processing liquid valves are a first chemical valve 25a, a second chemical valve 25b, a rinse liquid valve 25c, a water-repellent valve 25d, a hydrophobic liquid valve 25e, and an amphiphilic liquid valve 25f. When the first chemical valve 25a is opened, that is, when the first chemical valve 25a is switched from the closed state to the open state, two processing liquid nozzles 23 discharge DHF. Similarly, when the second chemical valve 25b is opened, two processing liquid nozzles 23 discharge SC1. When the rinse liquid valve 25c is opened, two processing liquid nozzles 23 discharge pure water. When the water-repellent valve 25d is opened, two processing liquid nozzles 23 discharge a water-repellent containing liquid. When the hydrophobic liquid valve 25e is opened, the two processing liquid nozzles 23 discharge toluene. When the amphiphilic liquid valve 25f is opened, the two processing liquid nozzles 23 discharge IPA.

[0075] Although not shown in the figures, the first chemical solution valve 25a includes a valve body provided with an annular valve seat through which the chemical solution passes, a valve element movable relative to the valve seat, and an actuator that moves the valve element between a closed position where the valve element is in contact with the valve seat and an open position where the valve element is away from the valve seat. The same applies to the other valves. The actuator may be a pneumatic actuator or an electric actuator, or any other type of actuator. The control device 3 opens and closes the first chemical solution valve 25a by controlling the actuator. The contents of this paragraph also apply to valves other than the first chemical solution valve 25a.

[0076] The substrate processing apparatus 1 includes a discharge pipe 27p for guiding the processing liquid discharged from the immersion tank 21, and a drain valve 27v that switches between an open state in which the processing liquid is discharged from the immersion tank 21 to the discharge pipe 27p and a closed state in which the discharge of the processing liquid from the immersion tank 21 to the discharge pipe 27p is stopped. The discharge pipe 27p is connected to an outlet that opens at the bottom of the inner surface of the immersion tank 21. If the liquid processing tank 2L includes an overflow tank 22, the substrate processing apparatus 1 further includes a discharge pipe 28p for guiding the processing liquid discharged from the overflow tank 22, and a drain valve 28v that switches between an open state in which the processing liquid is discharged from the overflow tank 22 to the discharge pipe 28p and a closed state in which the discharge of the processing liquid from the overflow tank 22 to the discharge pipe 28p is stopped.

[0077] When the drain valve 27v is opened, that is, when the drain valve 27v is switched from the closed state to the open state, the treatment liquid in the immersion tank 21 is discharged to the discharge pipe 27p through the outlet that opens at the bottom of the inner surface of the immersion tank 21. As a result, the liquid level LS in the immersion tank 21 moves downward in parallel. When replacing the treatment liquid in the immersion tank 21 with another treatment liquid, the control device 3 opens one of the first chemical valve 25a, the second chemical valve 25b, the rinse liquid valve 25c, the water repellent valve 25d, the hydrophobic liquid valve 25e, and the amphiphilic liquid valve 25f at the same time as or before opening the drain valve 27v. For example, when replacing the DHF in the immersion tank 21 with pure water, the control device 3 opens the rinse liquid valve 25c at the same time as or before opening the drain valve 27v. As a result, the DHF is discharged from the immersion tank 21 and pure water is supplied to the immersion tank 21.

[0078] Next, we will explain the lifter 13.

[0079] Figure 8 is a schematic side view of the lifter 13. Figure 9 is a schematic front view of the lifter 13. Figures 10A and 10B are front views of the lifter 13 with the base plate 14 omitted. Figure 11 is a schematic cross-sectional view showing a cross section along the line XI-XI shown in Figure 10B. Figure 12 is a schematic cross-sectional view showing multiple substrates W in an inclined position moving from an immersion position to an unimmersion position. Figure 10A shows the support frame 16 and gripper 17 in the open position. Figure 10B shows the support frame 16 and gripper 17 in the closed position. Figures 10A and 10B show the substrates W in a vertical position.

[0080] In the following description, the vertical direction is the direction perpendicular to the substrate W held by the lifter 13, and the horizontal direction is the horizontal direction perpendicular to the vertical direction. The lifter 13 changes between a vertical position, where the substrate W fixed to the lifter 13 is in a vertical position, and an inclined position, where the substrate W fixed to the lifter 13 is in an inclined position. In the following, unless otherwise specified, the lifter 13 in the vertical position will be described. When the lifter 13 is in the vertical position, the vertical direction is horizontal. When the lifter 13 is in an inclined position, the vertical direction is inclined with respect to the horizontal plane. The horizontal direction is horizontal regardless of the position of the lifter 13. Multiple substrates W are fixed to the lifter 13 in a state where they are arranged in the vertical direction. The vertical direction corresponds to the thickness direction of the substrate W. The horizontal direction may be the depth direction of the substrate processing apparatus 1, or it may be a direction different from the depth direction.

[0081] The auxiliary transport robot 12 includes a lifter 13 that holds one or more substrates W, and two translation actuators 19 that move the lifter 13 vertically in parallel. The two translation actuators 19 keep the lifter 13 stationary at any position within the range from the upper position (shown by the solid line in Figure 7) to the lower position (shown by the dashed line in Figure 7). The upper position is a non-immersion position where the entirety of the one or more substrates W held by the lifter 13 is positioned above the opening 21o of the immersion tank 21. The lower position is an immersion position where the entirety of the one or more substrates W held by the lifter 13 is positioned inside the immersion tank 21, that is, in the storage space 21s.

[0082] The lifter 13 is an example of a substrate holder that holds one or more substrates W. The lifter 13 can hold multiple substrates W that are the same shape and size. The number of substrates W held by the lifter 13 may be 50, or more or less than 50. The multiple substrates W are fixed to the lifter 13, preventing them from moving relative to the lifter 13. When the multiple substrates W are fixed to the lifter 13, all the substrates W are parallel to each other while being spaced apart, and the centers of all the substrates W are aligned along a single straight line extending vertically.

[0083] As shown in Figures 8 and 9, the lifter 13 includes two base plates 14, two support shafts 15, two support frames 16, and two grippers 17. The two base plates 14 are positioned on either side of one or more substrates W, facing each other vertically in a vertical orientation. The two support shafts 15 are supported by the two base plates 14 in a orientation that extends vertically from one of the two base plates 14 to the other of the two base plates 14. The two support frames 16 are supported by the two base plates 14 via the two support shafts 15 so that they can rotate relative to the two base plates 14. The two grippers 17 are pressed against the end faces of one or more substrates W supported by the two support frames 16 when the two support frames 16 rotate relative to the two base plates 14. One or more substrates W are secured by the two grippers 17 while being supported by the two support frames 16 between the two base plates 14.

[0084] As shown in Figures 10A and 10B, the two support shafts 15 are positioned horizontally spaced apart in a vertically extending orientation. The two support shafts 15 are parallel to each other and positioned at equal heights. The two support shafts 15 are positioned between two base plates 14. Each support shaft 15 is supported by each base plate 14. One support shaft 15 is rotatable around the centerline of the other support shaft 15 relative to the two base plates 14. The same applies to the other support shaft 15. If the support frame 16 is rotatable relative to the support shafts 15, each support shaft 15 may be fixed to each base plate 14.

[0085] The two support frames 16 are supported by two support shafts 15. The support frames 16 include a lower frame 16L positioned below the support shafts 15 and an upper frame 16u positioned above the support shafts 15. A gripper 17 is fixed to the upper frame 16u. The gripper 17 is positioned above the support shafts 15. The upper frame 16u and the gripper 17 are positioned to the side of the substrate W. The lower frame 16L is positioned below the substrate W. The substrate W is supported by the two lower frames 16L. When the two lower frames 16L support multiple substrates W, the outer periphery of each substrate W is inserted one by one into a plurality of retaining grooves 16a (see Figure 10B) provided in the lower frames 16L. The retaining grooves 16a are arc-shaped and extend circumferentially along the outer periphery of the substrate W. The outer periphery of the substrate W is inserted into the retaining groove 16a, thereby restricting the movement of the substrate W relative to the support frame 16.

[0086] One support frame 16 is rotatable around one pivot 15 with respect to the two base plates 14, along with one pivot 15 and one gripper 17. Similarly, the other support frame 16 is rotatable around the other pivot 15 with respect to the two base plates 14, along with the other pivot 15 and the other gripper 17. Each support frame 16 is movable between an open position (shown in Figure 10A) and a closed position (shown in Figure 10B) with respect to the two base plates 14. The open position is the position where the substrate W can pass up and down between the two grippers 17. The closed position is the position where the two grippers 17 are pressed against the end faces of one or more substrates W supported by the two support frames 16. The support frames 16 are held in the closed position. The support frames 16 may return to the closed position by the weight of the support frames 16 and the grippers 17, or by the restoring force of an elastic body such as a spring that holds the support frames 16 in the closed position.

[0087] As shown in Figure 10A, the main transport robot 11 includes a pair of support bars 11b that support multiple substrates W in a vertical position by contacting the substrates W, an opening / closing actuator (not shown) that increases or decreases the distance between the pair of support bars 11b, and a transmission arm 11a that transmits power from the opening / closing actuator to the pair of support bars 11b. The pair of support bars 11b extend vertically and face each other laterally with a gap between them. The pair of support bars 11b are parallel to each other. The pair of support bars 11b support multiple substrates W in a vertical position by contacting the outer periphery of all substrates W at a position below the center of all substrates W.

[0088] When the pair of support bars 11b of the main transport robot 11 place one or more substrates W on the two support frames 16, the outer edges of the one or more substrates W are inserted into one or more retaining grooves 16a of one support frame 16 and one or more retaining grooves 16a of the other support frame 16, and the weight of the one or more substrates W causes the two support frames 16 to rotate from the open position to the closed position. When the two support frames 16 reach the closed position, with the one or more substrates W supported by each support frame 16, the two grippers 17 are pressed against the end faces of the one or more substrates W. As a result, the one or more substrates W are fixed to the lifter 13.

[0089] The pair of support bars 11b of the main transport robot 11 can hold the substrate W with two grippers 17 pressed against the end face of the substrate W. When the pair of support bars 11b attempt to lift one or more substrates W fixed to the lifter 13, the two support frames 16 rotate from the closed position to the open position, and the two grippers 17 move away from the end face of one or more substrates W. Subsequently, one or more substrates W are lifted by the pair of support bars 11b of the main transport robot 11, and one or more substrates W move upward away from the two support frames 16.

[0090] As shown in Figure 11, the gripper 17 includes a pressing surface 17a that contacts the end face of the substrate W. The pressing surface 17a may have a vertical arc or cylindrical cross-section, or it may have a horizontal V-shaped cross-section. Figure 11 shows an example of the latter. In this example, the pressing surface 17a forms a V-shaped pressing groove. The inner surface of the pressing groove corresponds to the pressing surface 17a having a horizontal V-shaped cross-section that opens towards the substrate W.

[0091] The substrate W is supported by the support frame 16 with a portion of its outer periphery positioned within the retaining groove 16a of the support frame 16. When the gripper 17 is away from the substrate W, the substrate W is movable relative to the support frame 16 within the gap between the substrate W and the retaining groove 16a. If the substrate W is tilted, as the support frame 16 approaches the closed position, the end face of the substrate W moves along the pressing surface 17a of the gripper 17 while in contact with it. This changes the substrate W to a vertical position, in which state it is fixed to the lifter 13.

[0092] As described above, the sub-transport robot 12 includes two translation actuators 19 that translate the lifter 13 vertically. The two translation actuators 19 also function as attitude change actuators that change the orientation of the substrate W between a vertical and an inclined orientation by changing the orientation of the lifter 13. The two translation actuators 19 are connected to two base plates 14 via two couplings 18, such as bearings. Figure 9 shows an example in which the couplings 18 include a laterally extending central axis and bearings surrounding the central axis. The bearings are attached to the translation actuators 19, and the central axis is attached to the base plates 14. One base plate 14 is rotatable around a laterally extending axis of rotation relative to one translation actuator 19. The other base plate 14 is rotatable around a laterally extending axis of rotation relative to the other translation actuator 19.

[0093] Figures 8, 9, and 12 show an example where the translation actuator 19 is an extendable electric cylinder. An actuator is a device that converts driving energy, which can be expressed as electrical, fluid, magnetic, thermal, or chemical energy, into mechanical work. Actuators include electric motors (rotary motors), linear motors, air cylinders, and other devices. If the motion of the actuator differs from the motion of the object, a motion converter may be provided to convert the motion of the actuator into linear motion or rotation. If the actuator is an electric motor and the object is moving in a linear motion, a motion converter such as a ball screw and ball nut may be used to convert the rotation of the electric motor into linear motion.

[0094] The two translation actuators 19 independently raise and lower the two base plates 14. When the two translation actuators 19 move the two base plates 14 in the same direction at the same speed and by the same amount, the lifter 13 moves in a parallel direction upward or downward. As a result, one or more substrates W fixed to the lifter 13 move in a parallel direction upward or downward while the orientation of the substrates W is kept constant. As shown in Figure 12, when the two translation actuators 19 move the two base plates 14 relatively in the vertical direction, one or more substrates W fixed to the lifter 13 change between a vertical orientation and an inclined orientation. The inclination angle θi of the substrate W (see Figure 4A) increases as the relative amount of movement of the two base plates 14 in the vertical direction increases, and decreases as the amount of movement decreases.

[0095] As shown in Figure 12, with one or more substrates W fixed to the lifter 13, the control device 3 moves two base plates 14 relatively in the vertical direction using two translation actuators 19. This changes the position of one or more substrates W fixed to the lifter 13 from a vertical to an inclined position. The control device 3 controls the relative movement of the two base plates 14 in the vertical direction to incline the substrates W with respect to the vertical plane at any inclination angle θi (see Figure 4A) within a range of less than 90 degrees. The control device 3 inclines the lifter 13 with the two translation actuators 19 so that the inclination angle θi of the substrates W matches a set value stored in the control device 3. When processing the substrates W as described above, the inclination angle θi of the substrates W is set so that the retraction contact angle θr (see Figure 4C) approaches or matches 90 degrees.

[0096] When the substrate processing device 1 processes the substrates W, the control device 3 causes the main transport robot 11 to place one batch of substrates W onto the lifter 13. This fixes one batch of substrates W to the lifter 13 in a vertical position. Subsequently, the control device 3 causes two base plates 14 to move downward by the same amount at the same speed using two parallel movement actuators 19. This causes one batch of substrates W fixed to the lifter 13 in a vertical position to move downward in parallel, passing the liquid level LS in the immersion tank 21 downwards. In other words, one batch of substrates W fixed to the lifter 13 in a vertical position changes from a non-immersed state to an immersed state, and the processing liquid in the immersion tank 21 is supplied to each substrate W.

[0097] In the aforementioned processing of substrate W, multiple processing solutions are sequentially supplied to one or more substrates W in the following order: DHF, DIW (pure water), SC1, DIW, IPA, toluene, water-repellent agent-containing solution, toluene, IPA, and DIW. In this case, the control device 3 positions one batch of substrates W in a vertical position, fixed to the lifter 13, within the immersion tank 21, while replacing the processing solution (DHF) in the immersion tank 21 with another processing solution (pure water). Subsequently, the control device 3 continues to replace the processing solution in the immersion tank 21 with another processing solution, while positioning one batch of substrates W in a vertical position, fixed to the lifter 13, within the immersion tank 21, until the IPA in the immersion tank 21 is replaced with pure water.

[0098] After supplying all the processing liquid to be supplied to one or more substrates W, the control device 3 changes the substrates W from a vertical to an inclined position by moving two base plates 14 relatively vertically using two parallel-movement actuators 19, as shown in Figure 12. In this state, the control device 3 moves the two base plates 14 upward by the same amount at the same speed using the two parallel-movement actuators 19. As a result, the inclined substrates W of the batch, fixed to the lifter 13, move upward in parallel, changing from an immersed state to an unimmersed state. In other words, the substrates W of the batch pass upward above the liquid level LS in the immersion tank 21 while remaining in an inclined position. This shortens the time that the substrates W and the liquid level LS intersect compared to when the substrates W are changed from an immersed state to an unimmersed state in a vertical position.

[0099] The control device 3 changes the inclined position of one batch of substrates W fixed to the lifter 13 to a non-immersed state, and then changes the inclined position of one batch of substrates W fixed to the lifter 13 from an inclined position to a vertical position by moving two base plates 14 relatively in the vertical direction using two parallel movement actuators 19. Subsequently, the control device 3 causes the main transport robot 11 to lift the batch of substrates W from the lifter 13. This releases the fixation of the batch of substrates W to the lifter 13, and the batch of substrates W moves upward away from the lifter 13. After that, the control device 3 causes the main transport robot 11 to carry the batch of substrates W into the drying tank 2d, and dries the batch of substrates W in the drying tank 2d.

[0100] Next, the effects of this embodiment will be described.

[0101] In this embodiment, the substrate W, in an inclined position relative to the vertical plane, and the liquid surface LS, which is the surface of the processing liquid in the immersion tank 21, are moved relative to each other in the vertical direction. As a result, the inclined substrate W passes over the liquid surface LS in an upward direction, changing from an immersed state to an unimmersed state. Changing the substrate W from an immersed state to an unimmersed state while it is in an inclined position shortens the time that the substrate W and the liquid surface LS intersect compared to changing the substrate W from an immersed state to an unimmersed state while it is in a vertical position. This shortens the time that the surface tension of the processing liquid in the immersion tank 21 is applied to the pattern PA on the surface of the substrate W.

[0102] In this embodiment, with a water-containing liquid such as pure water stored in the immersion tank 21, the inclined substrate W and the liquid surface LS are moved relative to each other in the vertical direction. This shortens the time that the surface tension of the water-containing liquid in the immersion tank 21 is applied to the pattern PA compared to when the substrate W is changed from a non-immersed state to an immersed state in a vertical position. Excluding liquid metals such as mercury, water has the highest surface tension of all liquids. Therefore, the time that a large surface tension is applied to the pattern PA can be shortened.

[0103] In this embodiment, the substrate W is immersed in a water-repellent agent-containing liquid in the immersion tank 21. Assuming that the surface of the substrate W is smooth, when the water-repellent agent-containing liquid is supplied to the surface of the substrate W, the contact angle of water with respect to the surface of the substrate W will exceed 90 degrees. According to Wenzel's formula, when comparing the contact angles of water with smooth and rough surfaces made of the same material, when the contact angle of water with respect to the smooth surface exceeds 90 degrees, the contact angle of water with respect to the rough surface is greater than the contact angle of water with respect to the smooth surface. The surface of the substrate W is a rough surface with a fine pattern PA formed thereon. Therefore, the contact angle of water with respect to the surface of the substrate W to which the water-repellent agent-containing liquid is supplied will be well above 90 degrees. In other words, when a water droplet is on the horizontal surface of the substrate W, the contact angle of water with respect to the surface of the substrate W (static contact angle) will be well above 90 degrees.

[0104] After immersing the substrate W in the water-repellent agent-containing liquid in the immersion tank 21, the substrate W, in an inclined position, is changed from an immersed state to an unimmersed state by moving the water-containing liquid, such as pure water, relative to the liquid surface LS in the vertical direction while the water-containing liquid is stored in the immersion tank 21. As the supply of the water-repellent agent-containing liquid and the inclination of the substrate W cause the receding contact angle θr to approach or equal 90 degrees, the component of the surface tension applied to the surface of the substrate W from the water-containing liquid in a direction parallel to the surface of the substrate W (the parallel component of surface tension) can be eliminated or reduced. The parallel component of surface tension is the force in the width direction of the protrusion P1. By eliminating or reducing this component, the collapse rate of the pattern PA can be reduced.

[0105] In this embodiment, at least a portion of the recess Q1 is filled with air, and a water-containing liquid such as pure water is supported by the air in the recess Q1 and the protrusion P1, while the inclined substrate W and the liquid surface LS are moved relative to each other in the vertical direction. In other words, because the surface of the substrate W has high water repellency and the surface tension of water is high, the water-containing liquid contacts the surface of the substrate W in the CB state. When the water-containing liquid in contact with the surface of the substrate W changes from the W state to the CB state, the contact angle of the water-containing liquid with respect to the surface of the substrate W increases. As a result, the receding contact angle θr approaches or equals 90 degrees, so the parallel component of the surface tension can be eliminated or reduced.

[0106] In this embodiment, the water-repellent agent-containing liquid on the surface of the substrate W is replaced with a hydrophobic liquid such as toluene, and then the hydrophobic liquid on the surface of the substrate W is replaced with an amphiphilic liquid such as IPA. Subsequently, the amphiphilic liquid on the surface of the substrate W is replaced with a water-containing liquid such as pure water. 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. Since the water-repellent agent-containing liquid is replaced with a hydrophobic liquid whose solubility in water is lower than that of the amphiphilic liquid, the generation of such unwanted substances can be prevented or the amount of such substances generated can be reduced. In addition, compared to the case where the water-repellent agent-containing liquid on the surface of the substrate W is replaced with an amphiphilic liquid, the amount of water-repellent agent-containing liquid remaining in the water-containing liquid can be reduced.

[0107] In this embodiment, the surface of the substrate W is oxidized by supplying a chemical solution to the substrate W. As a result, at least a portion of the surface of the substrate W is terminated with hydroxyl groups (OH groups). When the surface of the substrate W is oxidized with a chemical solution, the number of hydroxyl groups exposed on the surface of the substrate W increases. If the water repellent is a silylating agent, the hydrogen atoms of the hydroxyl groups are replaced by silyl groups of the water repellent. Therefore, by supplying a chemical solution to the surface of the substrate W, the water repellency of the substrate W surface can be efficiently increased.

[0108] Furthermore, instead of replacing the chemical solution on the surface of the substrate W with a water-repellent solution, it is replaced with a water-containing solution used as a rinse. Subsequently, the water-containing solution on the surface of the substrate W is replaced with an amphiphilic liquid, and then the amphiphilic liquid on the surface of the substrate W is replaced with a hydrophobic liquid. Even if some water-containing solution remains after being replaced with the amphiphilic liquid, this water-containing solution diffuses into the amphiphilic liquid on the surface of the substrate W. Subsequently, the amphiphilic liquid is replaced with a hydrophobic liquid. A hydrophobic liquid is a liquid with lower water solubility than an amphiphilic liquid. Therefore, the water remaining on the surface of the substrate W can be eliminated or reduced.

[0109] 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 gradually replacing the water-containing liquid used as a rinse solution with an amphiphilic liquid and a hydrophobic liquid, the water-repellent agent-containing liquid can be supplied to the surface of the substrate W in a state where no water remains on the substrate W or the amount of water remaining is extremely small. Therefore, the water repellency of the surface of the substrate W can be improved while preventing the generation of such unwanted substances or reducing the amount of such substances generated.

[0110] In this embodiment, the inclination angle θi of the substrate W with respect to the vertical plane is set so that the receding contact angle θr approaches or matches 90 degrees. The receding contact angle θr is the angle between the surface of the substrate W and the liquid surface LS when the substrate W is moving upward relative to the liquid surface LS while the substrate W is intersecting the liquid surface LS. In this way, the component of the surface tension applied to the surface of the substrate W from the processing liquid in the immersion tank 21 that is parallel to the surface of the substrate W (the parallel component of surface tension) can be eliminated or reduced, and the collapse rate of the pattern PA can be reduced.

[0111] In this embodiment, the substrate W is fixed in an inclined position, and the inclined substrate W and the liquid surface LS are moved relatively in the vertical direction. When the substrate W and the liquid surface LS are moved relatively in the vertical direction while they are in contact, forces such as resistance are applied from the processing liquid to the substrate W. Since the substrate W is fixed in an inclined position, it is possible to prevent the position of the substrate W from changing due to such forces, and thus reduce fluctuations in the surface tension applied to the pattern PA from the processing liquid in the immersion tank 21.

[0112] In this embodiment, the substrate W is placed on two support frames 16. When the outer periphery of the substrate W comes into contact with the two support frames 16, the weight of the substrate W is applied to the two support frames 16, causing them to move. Consequently, the two grippers 17 move and are pressed against the end face of the substrate W, which is supported by the two support frames 16 in a vertical position. This fixes the position of the substrate W relative to the two support frames 16 and the two grippers 17 (hereinafter also referred to as the two support frames 16, etc.). In this state, the position of the two support frames 16, etc. is changed. When the position of the two support frames 16, etc. changes, the position of the substrate W also changes. As a result, the substrate W changes from a vertical position to an inclined position and is fixed in the inclined position. Therefore, while fixing the substrate W in an inclined position, the inclined substrate W and the liquid surface LS can be moved relatively in the vertical direction.

[0113] In this embodiment, the power of multiple translation actuators 19 is transmitted to the substrate W, thereby changing the substrate W between a vertical and an inclined position. Furthermore, the power of the multiple translation actuators 19 is transmitted to the substrate W, causing the substrate W in either a vertical or inclined position to be moved vertically in parallel. In other words, the multiple translation actuators 19 also function as attitude change actuators for changing the orientation of the substrate W. Therefore, it is not necessary to provide a dedicated attitude change actuator.

[0114] Next, other embodiments will be described.

[0115] When supplying the processing solution to the substrate W is started, instead of lowering one or more substrates W in a vertical position towards the immersion tank 21, one or more substrates W in an inclined position may be lowered towards the immersion tank 21. In other words, one or more substrates W may be changed from a vertical position to an inclined position before being changed to an immersed state. By doing so, the time during which the surface tension of the processing solution in the immersion tank 21 is applied to the pattern PA can be shortened compared to when the substrate W is changed from a non-immersed state to an immersed state in a vertical position.

[0116] When supplying multiple processing solutions to one or more substrates W, one or more substrates W may be changed from a vertical position to an inclined position while one or more substrates W are in contact with the last processing solution, or one or more substrates W may be changed from a vertical position to an inclined position while one or more substrates W are in contact with processing solutions other than the last processing solution.

[0117] The processing liquid supplied to the substrate W at the end may be a water-containing liquid other than pure water, or a liquid other than a water-containing liquid. In other words, when the substrate W and the liquid surface LS intersect, the liquid surface LS may be the surface of a water-containing liquid other than pure water, or the surface of a liquid other than a water-containing liquid.

[0118] If it is acceptable for the orientation of the substrate W to change when the substrate W intersects with the liquid level LS, then it is not necessary to fix the substrate W in an inclined position.

[0119] Instead of multiple translation actuators 19 also serving as attitude change actuators, a dedicated attitude change actuator independent of the translation actuators 19 may be provided.

[0120] The water-containing liquid supplied to the substrate W may not be pure water, but rather an effervescent water-containing liquid such as carbonated water that fizzes under normal temperature and pressure conditions. In this case, the transition of the effervescent water-containing liquid from the Wenzel state to the Cassie-Baxter state can be accelerated by the gas generated from the effervescent water-containing liquid.

[0121] Instead of supplying a hydrophobic liquid such as toluene before supplying the water-repellent agent-containing liquid, the water-repellent agent-containing liquid may be supplied to the substrate W in contact with an amphiphilic liquid such as IPA. In other words, the supply of the hydrophobic liquid between the supply of the amphiphilic liquid and the supply of the water-repellent agent-containing liquid may be omitted.

[0122] Instead of supplying a hydrophobic liquid after supplying a water-repellent agent-containing liquid, an amphiphilic liquid may be supplied to the substrate W in contact 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 amphiphilic liquid may be omitted.

[0123] The processing solution to be supplied to the substrate W does not necessarily have to contain a water-repellent agent. For example, a chemical solution other than the water-repellent agent may be supplied to the substrate W, and then the chemical solution may be washed away with a rinsing solution.

[0124] The substrate processing apparatus 1 is not limited to an apparatus for processing a disc-shaped substrate W, but may also be an apparatus for processing a polygonal substrate W.

[0125] You may combine two or more of the above-mentioned configurations. You may also combine two or more of the above-mentioned processes.

[0126] Although embodiments of the present invention have been described in detail, these are merely specific examples used to clarify the technical content of the present invention, and the present invention should not be construed as being limited to these specific examples. The spirit and scope of the present invention are limited only by the appended claims. [Explanation of Symbols]

[0127] 1: Substrate processing device, 3: Control device, 13: Lifter, 16: Support frame, 17: Gripper, 18: Fitting, 19: Parallel movement actuator, 21: Immersion tank, 27v: Drain valve, BL: Boundary line, LS: Liquid level, PA: Pattern, P1: Convex part, Q1: Recess, s1: End face of convex part, W: Substrate, θr: Recessed contact angle

Claims

1. A method for processing a substrate on which a pattern including convex and concave portions is formed on the surface, A substrate processing method including an immersion release step, which involves moving the substrate, which is in an inclined position with respect to a vertical plane, and the liquid surface, which is the surface of the processing liquid in the immersion tank, relatively in the vertical direction, thereby changing the substrate from an immersed state, in which the entire substrate is positioned in the processing liquid in the immersion tank, to a non-immersed state, in which the entire substrate is positioned above the liquid surface.

2. The substrate processing method according to claim 1, wherein the immersion release step is a step of changing the substrate from the immersed state to the non-immersed state by moving the substrate in the inclined position and the liquid surface relatively in the vertical direction while the water-containing liquid as the processing liquid is stored in the immersion tank.

3. A water-repellent supply step involves immersing the substrate in the water-repellent liquid contained in the immersion tank, while the water-repellent liquid containing the water-repellent liquid, which increases the water contact angle with a horizontal smooth surface made of the same material as the end face of the protrusion to a value greater than 90 degrees, is stored in the immersion tank. The substrate processing method according to claim 2, further comprising: a water supply step of immersing the substrate in the water-repellent agent-containing liquid in the immersion tank, and then immersing the substrate in the water-containing liquid in the immersion tank while the water-containing liquid is stored in the immersion tank.

4. The substrate processing method according to claim 3, wherein the immersion release step includes a step of moving the substrate in the inclined position and the liquid surface relatively in the vertical direction while 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.

5. The substrate processing method is After immersing the substrate in the water-repellent agent-containing liquid in the immersion tank, a post-water-repellent hydrophobic liquid supply step is performed, in which the substrate is immersed in the hydrophobic liquid in the immersion tank while a hydrophobic liquid that dissolves with the water-repellent agent-containing liquid is stored in the immersion tank, The process further includes a step of supplying an amphiphilic liquid after immersing the substrate in the hydrophobic liquid in the immersion tank, wherein an amphiphilic liquid, which has a higher water solubility than the hydrophobic liquid and dissolves with the hydrophobic liquid, is stored in the immersion tank, and the substrate is then immersed in the amphiphilic liquid in the immersion tank. The substrate processing method according to claim 3 or 4, wherein the water supply step is a step of immersing the substrate in the amphiphilic liquid in the immersion tank, and then immersing the substrate in the water-containing liquid in the immersion tank while the water-containing liquid, which has a higher surface tension than the amphiphilic liquid and dissolves with the amphiphilic liquid, is stored in the immersion tank.

6. The substrate processing method is A chemical solution supply step involves immersing the substrate in the chemical solution in the immersion tank, while the chemical solution for oxidizing the surface of the substrate is stored in the immersion tank. After immersing the substrate in the chemical solution in the immersion tank, a rinsing liquid supply step is performed in which the substrate is immersed in the water-containing liquid in the immersion tank while the water-containing liquid, which serves as the rinsing liquid, is stored in the immersion tank. A pre-water-repellent amphiphilic liquid supply step is performed, in which the substrate is immersed in the water-containing liquid in the immersion tank, and then the substrate is immersed in the amphiphilic liquid in the immersion tank, while an amphiphilic liquid that dissolves with the water-containing liquid is stored in the immersion tank. The process further includes a step of supplying a pre-hydrophobic liquid, in which, after immersing the substrate in the amphiphilic liquid in the immersion tank, the substrate is immersed in the hydrophobic liquid in the immersion tank, while a hydrophobic liquid having a lower water solubility than the amphiphilic liquid and dissolving with the amphiphilic liquid is stored in the immersion tank, The substrate processing method according to claim 3 or 4, wherein the water-repellent supply step is a step of immersing the substrate in the hydrophobic liquid in the immersion tank, and then immersing the substrate in the water-repellent liquid in the immersion tank while the water-repellent liquid is stored in the immersion tank.

7. The substrate processing method according to any one of claims 1 to 4, wherein the inclined posture is a posture in which the receding contact angle, which is the angle between the surface of the substrate and the liquid surface, approaches or coincides with 90 degrees when the substrate is moving upward relative to the liquid surface while the substrate and the liquid surface are in contact.

8. The substrate processing method according to any one of claims 1 to 4, wherein the immersion release step is a step of changing the substrate from the immersed state to the non-immersed state by moving the substrate in the inclined position and the liquid surface relative to each other in the vertical direction while fixing the substrate in the inclined position.

9. A fixing step in which the two grippers, which move together with the two support frames, are pressed against the end face of the vertically positioned substrate supported by the two support frames by the weight of the substrate moving the two support frames due to the contact between the outer periphery of the substrate and the two support frames, The substrate processing method according to claim 8, further comprising a posture changing step of changing the posture of the two support frames and the two grippers while the two support frames and the two grippers are in contact with the substrate, thereby changing the substrate from the vertical posture to the inclined posture.

10. A posture changing step in which the substrate is changed between a vertical position and a tilted position using multiple parallel movement actuators, A substrate processing method according to any one of claims 1 to 4, further comprising a lifting step of moving the substrate in a vertical or inclined position in a parallel vertical direction using the plurality of parallel movement actuators.

11. A lifter that holds a substrate in an inclined position with respect to a vertical plane, the substrate having a pattern formed on its surface including convex and concave portions, An immersion tank for storing a processing liquid into which the substrate held by the lifter is immersed, A translation actuator that moves the substrate held by the lifter in the vertical direction between an immersion position in which the substrate held by the lifter is positioned inside the immersion tank and a non-immersion position in which the substrate held by the lifter is positioned above the immersion tank, A drain valve for discharging the processing liquid from the immersion tank, A substrate processing apparatus comprising: a control device that changes the substrate from an immersed state in which the entire substrate is positioned in the processing liquid in the immersion tank to an unimmersed state in which the entire substrate is positioned above the liquid surface, which is the surface of the processing liquid in the immersion tank, by causing the parallel movement actuator to raise the substrate in the tilted position held by the lifter, and causing the drain valve to discharge the processing liquid in the immersion tank, thereby changing the substrate.

12. The aforementioned lifter is Two support frames support the substrate by contacting its outer periphery and move under the weight of the substrate, It includes two grippers that move together with the two support frames and are pressed against the end face of the vertically positioned substrate supported by the two support frames, The substrate processing apparatus according to claim 11, further comprising a posture changing actuator that changes the orientation of the substrate from the vertical orientation to the inclined orientation by changing the orientation of the two support frames and the two grippers.

13. The substrate processing apparatus according to claim 11 or 12, wherein the translation actuators include a plurality of translation actuators that translate the substrate held by the lifter in the vertical direction between the immersed position and the non-immersed position, and change the substrate held by the lifter between a vertical position and an inclined position.

Images