Substrate processing method and substrate processing apparatus

Abstract

In the substrate processing method, a substrate in an inclined posture in which the substrate is inclined with respect to a vertical plane and a liquid level, which is the surface of a processing liquid in an immersion tank, are moved relative to each other in the vertical direction. As a result, the substrate is changed from an immersed state in which the entire substrate is disposed in the treatment liquid in the immersion tank to a non-immersed state in which the entire substrate is disposed above the liquid level.

Description

Technical Field

[0001] This invention relates to a substrate processing method and a substrate processing apparatus. Substrates include, for example, substrates for FPD (Flat Panel Display) devices such as semiconductor wafers, liquid crystal display devices, and organic EL (electroluminescence) display devices; substrates for optical discs; substrates for magnetic disks; substrates for optical discs; substrates for photomasks; ceramic substrates; and substrates for solar cells. Background Technology

[0002] Patent document 1 discloses a substrate that tilts to maintain a vertical posture by an elevator.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2012-209285 Summary of the Invention

[0006] Patent document 1 does not disclose the posture of the substrate when it is held by the elevator and intersects with the surface of the processing liquid in the inner tank.

[0007] At least one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus capable of shortening the time required for the surface tension of a processing liquid to be applied to the pattern on the surface of a substrate.

[0008] One embodiment of the present invention provides a substrate processing method for processing a substrate having a pattern including protrusions and recesses formed on its surface. The method includes a de-immersion step in which the substrate, which is in an inclined position relative to a vertical plane, and the surface of the processing liquid in the immersion tank, i.e., the liquid surface, are moved relative to each other in the vertical direction, thereby changing the substrate from an immersed state in the processing liquid in the immersion tank to a non-immersion state in which the substrate is entirely disposed above the liquid surface.

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

[0010] The unimmersion process is a process in which the substrate in the tilted position and the liquid surface are moved relative to each other in the vertical direction while the substrate is in the immersion tank with an aqueous liquid as the treatment liquid, thereby changing the substrate from the immersion state to the non-immersion state.

[0011] The substrate processing method further includes: a water-repellent supply step of immersing the substrate in the water-repellent liquid in the immersion tank while the immersion tank contains a water-repellent liquid, wherein the water-repellent liquid increases the contact angle of water with respect to 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 the water-repellent liquid in the immersion tank while the immersion tank contains an aqueous liquid, after immersing the substrate in the water-repellent liquid in the immersion tank.

[0012] The process of removing the impregnation includes a process of moving the substrate in an inclined position and the liquid surface relative to each other in the vertical direction, with at least a portion of the recess filled with air and the aqueous liquid supported by the air in the recess and the protrusion.

[0013] The substrate processing method further includes: after immersing the substrate in the water-repellent liquid in the immersion tank, and with a hydrophobic liquid that is fused with the water-repellent liquid stored in the immersion tank, immersing the substrate in the hydrophobic liquid in the immersion tank and then supplying the hydrophobic liquid after water removal; and after immersing the substrate in the hydrophobic liquid in the immersion tank, and with an amphiphilic liquid in the immersion tank having a higher solubility for water than the hydrophobic liquid and fused with the hydrophobic liquid stored in the immersion tank, immersing the substrate in the amphiphilic liquid in the immersion tank and then supplying the amphiphilic liquid after water removal, wherein the water supply step is, after immersing the substrate in the amphiphilic liquid in the immersion tank, and with an aqueous liquid in the immersion tank having a higher surface tension than the amphiphilic liquid and fused with the amphiphilic liquid stored in the immersion tank, immersing the substrate in the aqueous liquid in the immersion tank.

[0014] The substrate processing method further includes: a solution supply step of immersing the substrate in the solution stored in the immersion tank to oxidize the surface of the substrate; a rinsing solution supply step of immersing the substrate in the aqueous liquid stored in the immersion tank after immersing the substrate in the solution; and a rinsing solution supply step of immersing the substrate in the aqueous liquid stored in the immersion tank after immersing the substrate in the aqueous liquid stored in the immersion tank. The process of supplying the amphiphilic liquid before water repellency in the amphiphilic liquid; and the process of supplying the hydrophobic liquid before water repellency in the hydrophobic liquid in the immersion tank after immersing the substrate in the amphiphilic liquid in the immersion tank, wherein the immersion tank contains a hydrophobic liquid with a water solubility lower than that of the amphiphilic liquid and which is compatible with the amphiphilic liquid, wherein the water repellency supply process is the process of immersing the substrate in the water repellency liquid in the immersion tank after immersing the substrate in the hydrophobic liquid in the immersion tank, wherein the immersion tank contains the water repellency liquid in the immersion tank.

[0015] The tilting posture is a posture in which, when the substrate moves upward relative to the liquid surface while the substrate is intersecting the liquid surface, the angle formed between the surface of the substrate and the liquid surface, i.e., the retreating contact angle, is close to 90 degrees or consistent with that angle.

[0016] The process of removing the immersion is a process in which the substrate is fixed in the tilted position while the substrate and the liquid surface in the tilted position are moved relative to each other in the vertical direction, thereby changing the substrate from the immersion state to the non-immersion state.

[0017] The substrate processing method further includes: a fixing step in which the two support frames are moved by the weight of the substrate through contact between the outer periphery of the substrate and the two support frames, thereby pressing two clamps that move together with the two support frames against the end face of the substrate in a vertical position supported by the two support frames; and a posture changing step in which the postures of the two support frames and the two clamps are changed while the two support frames and the two clamps are in contact with the substrate, thereby changing the substrate from the vertical position to the tilted position.

[0018] The substrate processing method further includes: a posture change process in which the substrate changes between a vertical posture and an inclined posture by means of a plurality of parallel movement actuators; and a lifting process in which the substrate in the vertical posture or the inclined posture is moved parallel in the vertical direction by means of the plurality of parallel movement actuators.

[0019] Another embodiment of the present invention provides a substrate processing apparatus, comprising: a lift that holds the substrate in an inclined posture with the substrate having a pattern including protrusions and recesses formed on its surface, inclined relative to a vertical plane; an impregnation tank that stores a processing liquid for impregnating the substrate held by the lift; and a parallel movement actuator that causes the substrate held by the lift to move vertically between an impregnation position in which the substrate held by the lift is disposed in the impregnation tank and a non-impregnation position above the impregnation tank. The substrate processing apparatus includes: parallel movement; a drain valve for discharging the processing liquid from the impregnation tank; and a control device that, by performing at least one of the following actions—raising the substrate, which is held in the inclined position by the elevator, by raising the substrate, and discharging the processing liquid from the impregnation tank by the drain valve—changes the substrate from an impregnated state in the processing liquid within the impregnation tank to a non-impregnated state above the surface of the processing liquid within the impregnation tank. At least one of the features associated with the above-described substrate processing method may also be incorporated into the substrate processing apparatus.

[0020] In the above embodiments, at least one of the following features may also be added to the substrate processing apparatus.

[0021] The lifting mechanism includes: two support frames that support the substrate by contacting the outer periphery of the substrate and move according to the weight of the substrate; and two clamps that press against the end face of the substrate in a vertical position supported by the two support frames by moving together with the two support frames. The substrate processing apparatus further includes a posture change actuator that changes the posture of the substrate from the vertical position to the tilted position by changing the posture of the two support frames and the two clamps.

[0022] The parallel movement actuator includes a plurality of parallel movement actuators that cause the substrate held by the elevator to move parallel in the vertical direction between the immersion position and the non-immersion position, and to change the substrate held by the elevator between a vertical posture and the tilted posture. Attached Figure Description

[0023] Figure 1 This is a schematic diagram illustrating an example of substrate processing in one embodiment.

[0024] Figure 2A This is a schematic cross-sectional view illustrating an example of the structure of the substrate to be processed.

[0025] Figure 2BThis is a schematic cross-sectional view of a substrate containing a water-repellent liquid.

[0026] Figure 2C This is a schematic cross-sectional view of a substrate supplied with DIW (pure water).

[0027] Figure 3A This is a schematic cross-sectional view showing an example of a droplet in a Wenzel state in contact with a rough surface.

[0028] Figure 3B This is a schematic cross-sectional view showing an example of a droplet in Cassie-Baxter form in contact with a rough surface.

[0029] Figure 4A This is a schematic diagram showing the state of a substrate in an inclined position intersecting with the liquid surface.

[0030] Figure 4B This is a schematic cross-sectional view used to illustrate the receding contact angle when the substrate is in a vertical position.

[0031] Figure 4C This is a schematic cross-sectional view used to illustrate the retraction contact angle when the substrate is in an inclined position.

[0032] Figure 5 It is a schematic cross-sectional view used to illustrate the state of a droplet at rest while it is in contact with a rough surface larger than the droplet at a contact angle of more than 90 degrees.

[0033] Figure 6 This is a schematic top view showing the layout of a batch substrate processing apparatus according to one embodiment.

[0034] Figure 7 It is a schematic diagram showing the cross-section of the liquid treatment tank cut by a vertical plane.

[0035] Figure 8 This is a rough side view of the elevator.

[0036] Figure 9 This is a general front view of the elevator.

[0037] Figure 10A This is the front view of the elevator with the base plate omitted.

[0038] Figure 10B This is the front view of the elevator with the base plate omitted.

[0039] Figure 11 It means along Figure 10B A schematic cross-sectional view of the XI-XI line shown.

[0040] Figure 12It is a schematic cross-sectional view of multiple substrates in an inclined position, showing them moving from the impregnated position to the non-impregnated position. Detailed Implementation

[0041] Hereinafter, the embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0042] Figure 1 This is a schematic diagram illustrating an example of the processing of a substrate W in one embodiment. Figure 2A This is a schematic cross-sectional view illustrating an example of the structure of the substrate W to be processed. Figure 2B This is a schematic cross-sectional view of a substrate W containing a water-repellent liquid. Figure 2C This is a schematic cross-sectional view of the substrate W supplied with DIW (pure water).

[0043] The substrate W to be processed includes a surface and a back surface that are parallel to each other, and an annular end face that connects the outer edges of the surface and the back surface to each other over the entire outer periphery of the surface and the back surface. Figure 2A This indicates that the substrate W is facing upwards. The surface of the substrate W is equivalent to the upper surface of the substrate W. The surface of the substrate W is the component forming surface for forming components. The back surface of the substrate W is the non-component forming surface where no components are formed. Alternatively, both the surface and the back surface of the substrate W can be component forming surfaces.

[0044] The front and back surfaces of substrate W are flat surfaces parallel to each other. When pattern PA is formed on the surface of substrate W, the surface of substrate W is strictly speaking a surface with irregularities. The thickness direction of substrate W is perpendicular to the flat surface of substrate W before pattern PA is formed, and the surface direction of substrate W is parallel to that surface. Figure 2A In this diagram, the vertical direction of the paper surface corresponds to the thickness direction of the substrate W, and the horizontal direction of the paper surface corresponds to the surface direction of the substrate W. The pattern PA can be applied in the substrate processing apparatus 1 (see reference 1). Figure 6 It can be formed before processing the substrate W, or it can be formed when the substrate processing apparatus 1 processes the substrate W.

[0045] Figure 2A This example illustrates a cross-section of substrate W cut by a plane perpendicular to the flat surface of substrate W before pattern PA is formed. In this example, multiple protrusions P1 are formed extending from the surface of the bottom layer s4 of substrate W in the thickness direction of substrate W. The bottom layer s4 may be part of a disc-shaped substrate made of semiconductor material or a thin film formed on the substrate. Pattern PA includes multiple protrusions P1 and multiple recesses Q1. The multiple protrusions P1 are spaced apart from each other in the planar direction of substrate W. Recesses Q1 are formed between two protrusions P1 that are opposite each other in the planar direction of substrate W, spaced apart by a distance, and recessed from the front ends of the two protrusions P1 in the thickness direction of substrate W.

[0046] Figure 2AThis example illustrates a rectangular cross-section for the protrusion P1 extending along the thickness direction of the substrate W. The protrusion P1 can also be cylindrical, prism-shaped, or plate-shaped, or any other shape. The recess Q1 can be a hole or a groove. Both the protrusion P1 and the recess Q1 can extend not only along the thickness direction of the substrate W but also along the surface direction of the substrate W. The width of the protrusion P1 can be fixed from its root to its front end, or it can vary. The width of the recess Q1 can be fixed from its bottom to its entrance, or it can vary.

[0047] The protrusion P1 can be composed of a single layer or multiple layers stacked along the height direction of the protrusion P1. Figure 2A This illustrates the former example. In the latter case, all layers contained in a protrusion P1 can be made of the same or different materials, or some of the layers can be made of the same material, different from the remaining layers. The material of the protrusion P1 can be one or more of semiconductors, insulators, and metals, or something other than these. The material of the end face s1 of the protrusion P1 can be a material including silicon, such as silicon dioxide, or something else.

[0048] The surface of pattern PA includes the surface of protrusion P1 and the inner surface of recess Q1. The surface of protrusion P1 includes an end face s1 corresponding to the front end of protrusion P1 and a side face s2 extending from the end face s1 to the root of protrusion P1. The end face s1 of protrusion P1 corresponds to the front end face and the top surface of protrusion P1. Multiple end faces s1 of protrusion P1 are arranged on a plane. The multiple end faces s1 of protrusion P1 correspond to part or all of the surface of substrate W. The inner surface of recess Q1 includes a bottom face s3 corresponding to the bottom of recess Q1 and a side face extending from the bottom face s3 to the entrance of recess Q1. The side face of recess Q1 may also serve as the side face s2 of protrusion P1, or may be different from the side face s2. Figure 2A An example representing the former. The side of the recess Q1 forms the entrance to the recess Q1.

[0049] When processing such Figure 2A When the substrate W is shown, one or more substrates W are held in a vertical position where the substrate W is in a vertical position. Figure 1The upper left end shows an example of holding multiple substrates W in a vertical position. After holding one or more substrates W in a vertical position, the substrates W are lowered relative to the impregnation tank 21 storing the processing liquid, thereby changing the substrates W from a non-impregnated state to an impregnated state. The non-impregnated state is when the entire substrate W is positioned above the surface of the processing liquid in the impregnation tank 21, i.e., the liquid surface LS. The impregnated state is when the entire substrate W is positioned in the processing liquid in the impregnation tank 21. When one or more substrates W are changed to the impregnated state, all areas of the surface, back surface, and end face of the substrate W are in contact with the processing liquid. Thus, the processing liquid is supplied to the one or more substrates W in the vertical position.

[0050] After supplying all the required processing liquid to one or more substrates W, such as from Figure 1 As shown in the second image from the left on the lower layer, one or more substrates W in the impregnated state are changed from a vertical position to an inclined position. An inclined position is one in which the substrate W is tilted relative to the vertical plane. More specifically, an inclined position is one in which the surface of the substrate W is tilted relative to the vertical plane at an angle θi less than 90 degrees around a horizontal line parallel to the surface of the substrate W, with the surface facing upwards or downwards (see reference). Figure 4A The tilted orientation. The tilt angle θi is the angle between the surface of substrate W and the vertical plane. The tilt angle θi can be less than 45 degrees. When multiple substrates W are held in a tilted orientation, all substrates W are parallel to each other in a separated state, and the centers of all substrates W are arranged along a straight line. The spacing between two horizontally adjacent substrates W can be fixed or varied.

[0051] After changing one or more substrates W from a vertical position to an inclined position while they are in an impregnated state, such as from Figure 1 As shown in the second, third, and fourth figures from the left on the lower layer, one or more substrates W in an inclined position are changed from an impregnated state to a non-impregnated state. The change to a non-impregnated state can be achieved by raising one or more substrates W relative to the impregnation tank 21, or by discharging the processing liquid from the impregnation tank 21, or by both raising the substrates W and discharging the processing liquid. If the processing liquid is discharged from the impregnation tank 21 while one or more substrates W are positioned within it, the horizontal liquid level LS moves downwards parallel to the bottom within the impregnation tank 21. As a result, the liquid level LS in the impregnation tank 21 decreases from a position above the upper end of the substrate W to a position below the lower end of the substrate W, thus changing the substrate W from an impregnated state to a non-impregnated state. The relative speed of the vertical movement between the surface of the substrate W and the liquid level LS in the impregnation tank 21 during the change from an impregnated state to a non-impregnated state can be fixed or varied.

[0052] After changing one or more substrates W from an impregnated state to a non-impregnated state while in an inclined position, the one or more substrates W are dried. The method for drying the substrates W can be vacuum drying or other methods. Before changing one or more substrates W to a non-impregnated state and drying, the one or more substrates W can 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-impregnated state, one or more substrates W can be changed from an inclined position to a vertical position and maintained in a vertical position. Then, the one or more substrates W in a vertical position can be horizontally moved to a drying treatment tank 2d for drying the substrates W (see reference). Figure 6 ).

[0053] The processing solution to be supplied to substrate W may be at least one of a chemical solution and a rinsing solution, or may be based on or replace at least one of a chemical solution and a rinsing solution, including liquids other than chemical solutions and rinsing solutions. The chemical solution may be at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia, hydrogen peroxide solution, organic acids (e.g., citric acid, oxalic acid, etc.), organic bases (e.g., TMAH (Tetramethylammonium hydroxide), etc.), surfactants, and corrosion inhibitors, or may be a liquid other than these. The rinsing solution may be any one of pure water (deionized water: DIW (Deionized Water)), carbonated water, electrolyzed ionized water, hydrogen water, ozone water, hydrochloric acid solution diluted to a concentration of, for example, 1 to 100 ppm, and ammonia solution diluted to a concentration of, for example, 1 to 100 ppm, or may be a liquid other than these. The rinsing solution is an example of an aqueous liquid. Aqueous liquids can be liquids containing 100% or substantially 100% (e.g., more than 99%) water, or liquids that also contain substances other than water.

[0054] The amount of processing liquid supplied to substrate W before drying can be one or more. Figure 1 An example is shown where multiple processing liquids are sequentially supplied to one or more substrates W. In this example, the multiple processing liquids are supplied to one or more substrates W in the following order: DHF, DIW (pure water), SCI, DIW, IPA, toluene, liquid containing a water-repellent agent, toluene, IPA, DIW. When multiple processing liquids are sequentially supplied to one or more substrates W, it is possible that when any processing liquid comes into contact with one or more substrates W, the substrate W is kept in an inclined position while changing from an immersed state to a non-immersed state; or it is possible that only when a specific processing liquid comes into contact with one or more substrates W, the substrate W is kept in an inclined position while changing from an immersed state to a non-immersed state.

[0055] When multiple processing solutions are sequentially supplied to one or more substrates W, the processing solution in one impregnation tank 21 can be replaced with other processing solutions, or one or more substrates W can be moved from an impregnation tank 21 containing a certain processing solution to an impregnation tank 21 containing other processing solutions. Hereinafter, an example of the former will be described. Figure 1 In the example shown, such as Figure 1 As shown in the second image from the left on the upper layer, one or more substrates W are immersed in DHF in the immersion tank 21. DHF (hydrofluoric acid) is a solution used to remove the native oxide film of silicon. Thus, the native oxide film of substrate W is removed.

[0056] After supplying DHF from the impregnation tank 21 to one or more substrates W, the DHF is drained from the impregnation tank 21, and pure water is supplied to the impregnation tank 21, thereby replacing the processing solution (DHF) in the impregnation tank 21 with another processing solution (pure water). The supply of pure water to the impregnation tank 21 can begin either after the DHF has been drained from the impregnation tank 21 or before the DHF has been drained from the impregnation tank 21. In the latter case, the supply of pure water to the impregnation tank 21 can begin before the liquid level LS of the DHF in the impregnation tank 21 moves downward relative to the upper end of one or more substrates W, or it can begin after the liquid level LS has moved downward relative to the upper end of the substrate W. The content of this paragraph also applies when performing replacements other than the replacement from DHF to pure water.

[0057] As from Figure 1 As shown in the third figure from the left on the upper layer, after replacing the DHF in the impregnation tank 21 with pure water, the treatment solutions in the impregnation tank 21 are replaced with other treatment solutions in the following order: SC1, DIW, IPA, toluene, liquid containing water-repellent agent, toluene, IPA, DIW. For example, when replacing the pure water in the impregnation tank 21 with SC1, as described above, pure water is discharged from the impregnation tank 21, and SC1 is supplied to the impregnation tank 21. Thus, as from... Figure 1 As shown in the fourth figure from the left on the upper layer, SC1 in the impregnation tank 21 is supplied to one or more substrates W. SC1 (a mixture of ammonia, hydrogen peroxide, and water) is a solution used to remove particulate matter and organic matter from the substrate W. SC1 is an example of a solution used to oxidize the surface of the substrate W.

[0058] Toluene is an example of a hydrophobic liquid. IPA (isopropanol) is an example of an amphiphilic liquid. A hydrophobic liquid is a liquid that can fuse with a liquid containing a water-repellent agent. An amphiphilic liquid is a liquid that can fuse with both a hydrophobic liquid and an aqueous liquid. An amphiphilic liquid can also be a liquid that can fuse with a liquid containing a water-repellent agent. A hydrophobic liquid can also be a liquid that can fuse with an aqueous liquid, provided that the solubility of water relative to the hydrophobic liquid is less than the solubility of water relative to the amphiphilic liquid. The solubility of water relative to the amphiphilic liquid is less than the solubility of water relative to the aqueous liquid. The surface tension of an amphiphilic liquid is lower than the surface tension of an aqueous liquid. The surface tension of an amphiphilic liquid can be equal to, higher than, or lower than the surface tension of a hydrophobic liquid. The surface tension of a hydrophobic liquid can be equal to, higher than, or lower than the surface tension of an aqueous liquid.

[0059] Hydrophobic and amphiphilic liquids can be organic solvents. In this case, the hydrophobic liquid can be at least one of the following: ethanol derivatives such as IPA (isopropanol); ethylene glycol monomethyl ethers, ethylene glycol monoethyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol monomethyl ether acetates, ethylene glycol monoethyl ether acetates, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetates, lactates such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as monotoluene 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.

[0060] The water-repellent liquid is a liquid that modifies the surface of substrate W. The water-repellent liquid makes the surface of substrate W hydrophobic. The surface of substrate W after being supplied with the water-repellent liquid is a hydrophobic surface. The surface of substrate W has a pattern PA (see reference) formed with a protrusion P1 and a recess Q1. Figure 2A The rough surface of the surface. The water-repellent liquid is a liquid that increases the contact angle of water with respect to a smooth, horizontal surface made of the same material as the end face s1 of the protrusion P1 to a value exceeding 90 degrees.

[0061] The water-repellent liquid can be a liquid containing 100% or substantially 100% water-repellent, or it can be a liquid that also contains substances other than the water-repellent. In the latter case, the water-repellent liquid can be a solution containing the water-repellent as a solute and a solvent fused with the water-repellent. In this case, the solvent of the water-repellent liquid can be at least one of the aforementioned specific examples of organic solvents such as IPA. The solvent contained in the water-repellent liquid can be a liquid with the same composition as the hydrophobic liquid.

[0062] The water-repellent agent can be at least one of 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (FDTS), 3-aminopropyltriethoxysilane (APTES), benzyltrichlorosilane (Bn-TS), 11-cyanoethyltrichlorosilane, 11-undecyltrichlorosilane, 11-bromoethyltrichlorosilane, 11-triisopropoxytrichlorosilane, and trichlorosilane (H-UTS). In other words, the water-repellent agent can be a silylating agent.

[0063] If one or more substrates W are immersed in a hydrophobic liquid such as toluene and then immersed in a liquid containing a water-repellent agent, the water-repellent agent liquid mixes with the hydrophobic liquid in the recess Q1 while entering the recess Q1. As a result, the hydrophobic liquid in contact with the substrate W is replaced by the water-repellent agent liquid. The water-repellent agent liquid contacts not only the end face s1 and side face s2 of the protrusion P1, but also the bottom face s3 of the recess Q1. Figure 2B As shown, the water-repellent agent contained in the liquid adheres to the surface of the substrate W, such as the end face s1 of the protrusion P1, forming a water-repellent film R1 on at least a portion of the surface of the substrate W. When the water-repellent agent is a silylating agent, the hydrogen atoms of the hydroxyl groups exposed on the surface of the substrate W are replaced by silyl groups containing silicon atoms and multiple methyl groups, and these multiple silyl groups form the water-repellent film R1. This improves the water repellency of the substrate W surface. It should be noted that... Figure 2B as well as Figure 2C It is presented as having a boundary between the water-repellent liquid and the water-repellent film R1, but in reality, such a boundary does not exist.

[0064] The water-repellent agent contained in the liquid is a substance that increases the contact angle of water with respect to a smooth, level surface made of the same material as the end face s1 of the protrusion P1 to a value exceeding 90 degrees. Assuming the surface of the substrate W is smooth, if the liquid containing the water-repellent agent is supplied to the surface of the substrate W, the contact angle of water with respect to the surface of the substrate W exceeds 90 degrees. According to the Wenzel formula, when comparing the contact angle of water with respect to a smooth surface and a rough surface 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 that with respect to the smooth surface. The surface of the substrate W is a rough surface with fine patterns PA formed thereon. Therefore, the contact angle of water with respect to the surface of the substrate W is larger compared to the case where the surface of the substrate W is smooth.

[0065] After the water-repellent liquid is supplied, the liquids are supplied in the following order: hydrophobic liquid (toluene), amphiphilic liquid (IPA), and pure water. The hydrophobic liquid mixes with the water-repellent liquid in the recess Q1 while entering the recess Q1. The same applies to the amphiphilic liquid and pure water. Therefore, if one or more substrates W are immersed in pure water, the pure water mixes with the amphiphilic liquid in the recess Q1 while entering the recess Q1. Figure 2C This indicates that the recess Q1 is filled with pure water and all areas of the surface, back, and end faces of the substrate W are in contact with pure water.

[0066] Figure 3A This is a schematic cross-sectional view showing an example of a droplet in a Wenzel state in contact with a rough surface. Figure 3B This is a schematic cross-sectional view showing an example of a droplet in Cassie-Baxter form contacting a rough surface. (See diagram below.) Figure 3A As shown, the rough surface is a solid surface with multiple recesses Q1 and multiple protrusions P1. Recesses Q1 are recessed from the front end of protrusions P1. Protrusions P1 protrude from the bottom of recesses Q1. The bottom of recesses Q1 corresponds to the root of protrusions P1. The front ends of two adjacent protrusions P1 form the entrance to a recess Q1 located between them.

[0067] like Figure 3A As shown, the Wenzel (high adhesion) state (hereinafter also referred to as the W state) is the state in which water droplets on a horizontal, rough surface enter the recess Q1. Figure 3B As shown, the Cassie-Baxter (low adhesion) 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 front end of the protrusion P1. In the CB state, the water droplet is supported by the air in the recess Q1 and the front end of the protrusion P1. That is, if the water droplet is placed on a horizontal rough surface under normal temperature and pressure conditions (room temperature and one atmosphere), the front end of the protrusion P1 is in contact with the water droplet while the bottom of the recess Q1 is separated from the water droplet. Room temperature is, for example, a constant or nearly constant temperature in the range of 10 to 30°C.

[0068] The choice between the W state and the CB state for a water droplet on a rough surface is primarily influenced by factors such as the surface tension of the liquid, the surface free energy of the rough surface (solid), and the surface texture. It is generally believed that the higher the surface tension of the liquid and the lower the surface free energy of the rough surface (the higher the water repellency of the rough surface), the more likely the water droplet on the rough surface is to be in the CB state.

[0069] Pure water is a liquid with high surface tension. The water-repellent agent contained in the liquid is a substance that increases the contact angle of water with respect to a smooth, horizontal surface made of the same material as the end face s1 of the protrusion P1 to a value exceeding 90 degrees. The surface of the substrate W is a rough surface. Therefore, the surface free energy of the substrate W is low (the surface of the substrate W has high water repellency). Therefore, if the amphiphilic liquid in contact with the surface of the substrate W is replaced by pure water, the pure water can contact the surface of the substrate W in a CB state. In other words, during 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 pure water is discharged from the recess Q1, and at least a portion of the recess Q1 is filled with air.

[0070] After the liquid containing a water-repellent agent in contact with the surface of the substrate W is replaced with pure water, which is an example of an aqueous liquid, through a hydrophobic liquid and an amphiphilic liquid, the pure water in contact with the surface of the substrate W can be in either the W state or the CB state. When one or more substrates W in an inclined position are changed from an impregnated state to a non-impregnated state, the pure water in the impregnation tank 21 can change from the W state to the CB state at the position where the surface of the substrate W intersects with the liquid surface LS in the impregnation tank 21. Figure 4B as well as Figure 4C An example is shown where pure water in a CB state contacts the surface of substrate W at the location where substrate W intersects with liquid surface LS. When water in a CB state contacts the surface of the horizontal substrate W, the contact angle of the water relative to the surface of substrate W can be 100 degrees or more, preferably 140 degrees or more.

[0071] Figure 4A This is a schematic diagram showing the state in which the tilted substrate W intersects with the liquid surface LS. Figure 4B This is a schematic cross-sectional view used to illustrate the receding contact angle θr when the substrate W is in a vertical position. Figure 4C This is a schematic cross-sectional view used to illustrate the receding contact angle θr when the substrate W is in an inclined position. Figure 5 It is a schematic cross-sectional view used to illustrate the state of a droplet at rest while it is in contact with a rough surface larger than the droplet at a contact angle of more than 90 degrees.

[0072] like Figure 4A As shown, if the substrate W is changed from an impregnated state to a non-impregnated state, the liquid surface LS in the impregnation tank 21 intersects with the surface, back surface, and end face of the substrate W. Thus, the boundary line BL between the substrate W and the liquid surface LS is formed by the processing liquid in the impregnation tank 21 on the surface, back surface, and end face of the substrate W. Figure 4AOn the right side, the boundary line BL is represented by a thick line. The boundary line BL is a horizontal or nearly horizontal closed curve that encloses 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). The substrate W and the processing liquid are pulled against each other at their interface, so when the substrate W and the liquid surface LS move relative to each other in the vertical direction, the boundary line BL is positioned slightly above the liquid surface LS.

[0073] If the substrate W and the liquid surface LS in the impregnation tank 21 move relative to each other in the vertical direction while the substrate W is intersecting with the liquid surface LS, the surface tension of the processing liquid in the impregnation tank 21 is applied to the surface of the substrate W through the boundary line BL. When the substrate W and the liquid surface LS move relative to each other at the same speed in the vertical direction, if the substrate W is tilted from the impregnation state to the non-impregnation state, the time for the substrate W and the liquid surface LS to intersect can be shortened compared to the case where the substrate W is vertically tilted from the impregnation state to the non-impregnation state. Therefore, the time for the surface tension of the processing liquid in the impregnation tank 21 to apply to the pattern PA on the surface of the substrate W can be shortened. Furthermore, if the substrate W in contact with the processing liquid in the impregnation tank 21 is raised, resistance is applied to the substrate W from the processing liquid in the impregnation tank 21. In other words, a portion of the force that raises the substrate W is converted into resistance applied to the substrate W from the processing liquid. The pattern PA bears this resistance. If the substrate W is tilted from the impregnation state to the non-impregnation state, the time for this resistance to apply to the pattern PA can also be shortened.

[0074] If the substrate W and the liquid surface LS in the immersion tank 21 move relative to each other in the vertical direction while the liquid surface LS intersects with the substrate W, the processing liquid in the immersion tank 21 moves downward relative to the substrate W. That is, 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. Figure 4B as well as Figure 4C The thick black arrow in the figure indicates the direction of travel of the processing liquid flowing along the surface of the substrate W. When the substrate W moves upward relative to the liquid surface LS in the immersion tank 21 with the liquid surface LS intersecting, the angle formed by the substrate W and the liquid surface LS is equivalent to the retreat contact angle θr. Figure 4B The backward contact angle θr represents the angle of retreat when the substrate W is in a vertical position. Figure 4C This represents the retraction contact angle θr when the substrate W is in an inclined position. For comparison... Figure 4B as well as Figure 4C As is known, if the substrate W is tilted relative to the vertical plane, the retreat contact angle θr increases. When the substrate W is in a tilted position, the retreat contact angle θr can be 90 degrees, or it can be larger or smaller than 90 degrees.

[0075] Consider the state of a droplet that remains stationary while in contact with a rough, horizontal surface larger than itself at a contact angle exceeding 90 degrees. The component (Fs) of the surface tension exerted by the droplet's surface on the smooth surface in the direction perpendicular to the smooth surface 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) between the droplet's surface and the smooth surface at their intersection (refer to...). Figure 5 ).like Figure 5 As shown, if the smooth surface is replaced with a rough surface in this state, that is, the surface of the horizontal substrate W (strictly speaking, the end faces s1 of the multiple protrusions P1), then the component (Fr) of the surface tension exerted by the droplet on the surface of the substrate W in the direction perpendicular to the surface of the substrate W can be defined as (Equation 2) Fr=2πrγsinθ×w / p. Here, w is the width of the protrusion P1, and p is the spacing (the distance between the centers of two adjacent protrusions P1), otherwise it is the same as Equation 1.

[0076] In Equation 2, Fr = 2πrγsinθ × w / p, Fr is at its maximum when θ = 90°. In other words, when θ = 90° in Equation 2, the component of the surface tension exerted by the droplet on the substrate W in the direction perpendicular to the surface of the substrate W (the perpendicular component of the surface tension) is at its maximum, and the component of the surface tension in the direction parallel to the surface of the substrate W (the parallel component of the surface tension) is zero. Therefore, if θ is made close to 90 degrees, that is, if the angle between the surface of the droplet and the surface of the substrate W at their intersection is close to 90 degrees, the parallel component of the surface tension can be reduced. If this angle is set to 90 degrees, the parallel component of the surface tension can theoretically be set to zero.

[0077] As described above, when the liquid surface LS in the impregnation tank 21 intersects with the substrate W, and the substrate W moves upward relative to the liquid surface LS, the liquid surface LS in the impregnation tank 21 contacts the surface of the substrate W in a state of tilt relative to the surface of the substrate W with a retreat contact angle θr. The tilting posture of the substrate W is such that the surface of the substrate W is tilted relative to the vertical plane around a horizontal line parallel to the surface of the substrate W with a tilt angle θi of less than 90 degrees, either upward or downward. Regardless of whether the surface of the substrate W is facing upward or downward, if the substrate W is tilted at this time, the retreat contact angle θr will increase. The increase in the retreat contact angle θr corresponds to the increase in the tilt angle θi of the substrate W.

[0078] When transferring one or more substrates W in an inclined position from an impregnated state to a non-impregnated state, the tilt angle θi of the substrates W can be set so that the retreat contact angle θr is close to or consistent with 90 degrees. Doing so eliminates or reduces the component of the surface tension exerted on the surface of the substrates W from the liquid surface LS in the impregnation tank 21 in the direction parallel to the surface of the substrates W (parallel component of surface tension). 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.

[0079] Next, the substrate processing apparatus 1 for performing the above-described substrate W processing will be described.

[0080] Figure 6 This is a schematic top view showing the layout of a batch substrate processing apparatus 1 according to one embodiment.

[0081] The substrate processing apparatus 1 is a batch processing apparatus for batch processing multiple substrates W. The substrate processing apparatus 1 includes: a loading boat LP that holds a carrier CA containing a disc-shaped substrate W such as a semiconductor wafer; a processing unit 2 that processes the substrates W transferred from the loading boat LP with a processing liquid such as a chemical solution and a rinsing liquid; a transport system 8 that transports the substrates W between the loading boat LP and the processing unit 2; and a control device 3 that controls the substrate processing apparatus 1.

[0082] Processing unit 2 includes multiple liquid treatment tanks 2L for storing processing liquid for immersing multiple substrates W; and a drying treatment tank 2d for drying the multiple substrates W by a drying method such as depressurized drying. Depressurized drying is a drying method that evaporates the liquid adhering to the substrates W by reducing the air pressure. When viewed from above, the multiple liquid treatment tanks 2L are located in the depth direction of the substrate processing apparatus 1. Figure 6 The components are arranged in a straight line along the left and right sides of the paper. When viewed from above, the drying treatment tank 2d is positioned between the conveying system 8 and the multiple liquid treatment tanks 2L in the depth direction of the substrate processing apparatus 1.

[0083] Each liquid treatment tank 2L can be a dedicated liquid treatment tank that supplies only one type of treatment liquid to multiple substrates W, or a general-purpose liquid treatment tank that sequentially supplies multiple types of treatment liquids to multiple substrates W. Alternatively, both dedicated liquid treatment tanks and general-purpose liquid treatment tanks can be included in multiple liquid treatment tanks 2L. Figure 6 This indicates that the 2L liquid treatment tank is an example of a general-purpose liquid treatment tank.

[0084] The transport system 8 includes: a carrier transport device 9 that transports carriers CA between the loading boat LP and the processing unit 2 and accommodates multiple carriers CA; and a posture conversion robot arm 10 that moves multiple substrates W into and out relative to the carriers CA held by the carrier transport device 9 and changes the posture of the substrates W between a horizontal posture and a vertical posture. The posture conversion robot arm 10 performs batch composition operations, which form a batch from multiple substrates W taken from multiple carriers CA, and batch decomposition operations, which accommodate multiple substrates W contained in a batch in multiple carriers CA.

[0085] The conveying system 8 also includes: a main conveying robot arm 11 that conveys multiple substrates W between the posture conversion robot arm 10 and the processing unit 2; and multiple auxiliary conveying robots 12 that convey multiple substrates W between the main conveying robot arm 11 and the processing unit 2. Figure 6 This example illustrates an arrangement of two auxiliary transfer robotic arms 12 and two pairs of liquid treatment tanks 2L. The auxiliary transfer robotic arms 12 respectively transfer multiple substrates W into and out of the pairs of liquid treatment tanks 2L, and transfer multiple substrates W between the pairs of liquid treatment tanks 2L.

[0086] The main transfer robot arm 11 receives a batch of substrates W, consisting of multiple (e.g., 50) substrates W, from the posture conversion robot arm 10, and transfers the received batch of substrates W to any one of the multiple auxiliary transfer robot arms 12. Among the multiple substrates W constituting a batch, all substrates W may have the same surface orientation, or one or more substrates W may have a different surface orientation than the others. The auxiliary transfer robot arm 12 immerses the batch of substrates W received from the main transfer robot arm 11 in a processing liquid within at least one liquid treatment tank 2L. Then, the main transfer robot arm 11 receives a batch of substrates W from the auxiliary transfer robot arm 12 and moves the received batch of substrates W into a drying treatment tank 2d.

[0087] The control device 3 controls the electrical and electronic equipment included in the substrate processing apparatus 1. The control device 3 includes at least one computer capable of communicating with itself. The computer includes a memory 3b storing information such as programs, and a CPU (central processing unit) 3a that controls the substrate processing apparatus 1 according to the programs stored in the memory 3b. The control device 3 performs tasks such as transporting and processing the substrate W by controlling the substrate processing apparatus 1. In other words, the control device 3 executes programs in a manner that involves transporting and processing the substrate W.

[0088] The control device 3 can also store multiple process recipes. That is, the data 3c stored in the control device 3 can also contain multiple process recipes. This data 3c can also be based on or replace multiple process recipes, including the tilt angle θi (see below).Figure 4A The setting value of the tilt angle θi can be part of the process recipe or different from the process recipe. The process recipe is information that specifies the processing content, processing conditions, and processing sequence of the substrate W. Multiple process recipes differ from each other in at least one of the processing content, processing conditions, and processing sequence of the substrate W. The control device 3 controls the substrate processing device 1 to process the substrate W according to the process recipe specified by the host computer. The control device 3 executes the program to perform the transport and processing of the substrate W.

[0089] Next, the liquid treatment tank 2L will be described.

[0090] Figure 7 This is a schematic diagram showing a cross-section of the liquid treatment tank 2L cut by 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 closing 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 passing downward from 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 within the immersion tank 21. The liquid treatment tank 2L may or may not include an overflow tank 22 for storing the treatment liquid overflowing from the immersion tank 21. Figure 7 Examples of the former are shown.

[0091] The substrate processing apparatus 1 includes: two processing liquid nozzles 23 that spray processing liquid into an immersion tank 21; two independent pipes 24i that guide the processing liquid toward the two processing liquid nozzles 23; and a common pipe 24c that guides the processing liquid toward the two independent pipes 24i. The processing liquid flowing in the common pipe 24c passes through the two independent pipes 24i and is supplied to the two processing liquid nozzles 23. Each processing liquid nozzle 23 sprays processing liquid from an outlet 23p disposed in the immersion tank 21, supplies processing liquid into the immersion tank 21, and forms an upflow of processing liquid in the processing liquid within the immersion tank 21.

[0092] The substrate processing apparatus 1 includes one or more processing liquid pipes that guide processing liquid toward two processing liquid nozzles 23. Figure 7Examples of treatment fluid piping include a first solution piping 26a, a second solution piping 26b, a rinsing fluid piping 26c, a water-repellent agent piping 26d, a hydrophobic liquid piping 26e, and an amphiphilic liquid piping 26f. The first solution piping 26a directs DHF, an example of a first solution, to the two treatment fluid nozzles 23. The second solution piping 26b directs SC1, an example of a second solution, to the two treatment fluid nozzles 23. The rinsing fluid piping 26c directs pure water, an example of a rinsing fluid, to the two treatment fluid nozzles 23. The water-repellent agent piping 26d directs a liquid containing a water-repellent agent to the two treatment fluid nozzles 23. The hydrophobic liquid piping 26e directs toluene, an example of a hydrophobic liquid, to the two treatment fluid nozzles 23. The amphiphilic liquid piping 26f directs IPA, an example of an amphiphilic liquid, to the two treatment fluid nozzles 23. These piping connections are connected to two treatment fluid nozzles 23 via a common piping 24c and two separate piping 24i.

[0093] The substrate processing apparatus 1 includes one or more processing liquid valves that switch between an open state and a closed state. In the open state, processing liquid flowing downstream in one or more processing liquid pipes is allowed to pass through, and in the closed state, the processing liquid is stopped. Figure 7 Examples of treatment fluid valves include a first chemical valve 25a, a second chemical valve 25b, a flushing fluid valve 25c, a water-repellent valve 25d, a hydrophobic liquid valve 25e, and an amphiphilic liquid valve 25f. If the first chemical valve 25a is open, i.e., if the first chemical valve 25a switches from a closed state to an open state, both treatment fluid nozzles 23 spray DHF. Similarly, if the second chemical valve 25b is open, both treatment fluid nozzles 23 spray SC1. If the flushing fluid valve 25c is open, both treatment fluid nozzles 23 spray pure water. If the water-repellent valve 25d is open, both treatment fluid nozzles 23 spray a liquid containing a water-repellent agent. If the hydrophobic liquid valve 25e is open, both treatment fluid nozzles 23 spray toluene. If the amphiphilic liquid valve 25f is open, both treatment fluid nozzles 23 spray IPA.

[0094] Although not illustrated, the first liquid valve 25a includes a valve body with an annular valve seat for the passage of liquid medicine, a valve core movable relative to the valve seat, and an actuator that moves the valve core between a closed position where the valve core contacts the valve seat and an open position where the valve core leaves the valve seat. The same applies to other valves. The actuator can be a pneumatic actuator, an electric actuator, or any other type of actuator. The control device 3 opens and closes the first liquid valve 25a by controlling the actuator. The contents of this paragraph also apply to valves other than the first liquid valve 25a.

[0095] The substrate processing apparatus 1 includes a discharge pipe 27p for guiding the processing liquid discharged from the impregnation tank 21, and a drain valve 27v that switches between an open state for discharging the processing liquid from the impregnation tank 21 to the discharge pipe 27p and a closed state for stopping the discharge of the processing liquid from the impregnation tank 21 to the discharge pipe 27p. The discharge pipe 27p is connected to a drain outlet in the bottom opening on the inner surface of the impregnation tank 21. When the liquid processing tank 2L includes an overflow tank 22, the substrate processing apparatus 1 also 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 for discharging the processing liquid from the overflow tank 22 to the discharge pipe 28p and a closed state for stopping the discharge of the processing liquid from the overflow tank 22 to the discharge pipe 28p.

[0096] If the drain valve 27v is opened, that is, if the drain valve 27v switches from the closed state to the open state, the treatment liquid in the impregnation tank 21 is discharged through the drain outlet at the bottom opening on the inner surface of the impregnation tank 21 to the discharge pipe 27p. As a result, the liquid level LS in the impregnation tank 21 moves parallel downwards. When the treatment liquid in the impregnation tank 21 is replaced with another treatment liquid, the control device 3 opens any one of the following valves simultaneously with or before and after opening the drain valve 27v: the first chemical solution valve 25a, the second chemical solution valve 25b, the rinsing liquid valve 25c, the water-repellent valve 25d, the hydrophobic liquid valve 25e, and the amphiphilic liquid valve 25f. For example, when replacing the DHF in the impregnation tank 21 with pure water, the control device 3 opens the rinsing liquid valve 25c simultaneously with or before and after opening the drain valve 27v. As a result, DHF is discharged from the impregnation tank 21, and pure water is supplied to the impregnation tank 21.

[0097] Next, the elevator 13 will be described.

[0098] Figure 8 This is a schematic side view of elevator 13. Figure 9 This is a general front view of elevator 13. Figure 10A as well as Figure 10B This is the front view of the elevator 13 with the base plate 14 omitted. Figure 11 It means along Figure 10B A schematic cross-sectional view of the XI-XI line shown. Figure 12 This is a schematic cross-sectional view of multiple substrates W in an inclined posture, showing their movement from the impregnated position to the non-impregnated position. Figure 10A This indicates that the support frame 16 and the clamp 17 are configured in the open position. Figure 10B This indicates that the support frame 16 and the clamp 17 are configured in the closed position. Figure 10A as well as Figure 10B This indicates that the substrate W is in a vertical orientation.

[0099] In the following description, the vertical direction is the direction perpendicular to the substrate W held by the elevator 13, and the lateral direction is the horizontal direction orthogonal to the vertical direction. The elevator 13 varies between a vertical position where the substrate W fixed to the elevator 13 is in a vertical posture and an inclined position where the substrate W fixed to the elevator 13 is in an inclined posture. Hereinafter, unless otherwise specified, the vertical posture of the elevator 13 will be described. When the elevator 13 is in a vertical posture, the vertical direction is horizontal. When the elevator 13 is in an inclined posture, the vertical direction is inclined relative to the horizontal plane. The lateral direction is horizontal regardless of the posture of the elevator 13. Multiple substrates W are fixed to the elevator 13 in a state of being arranged along the vertical direction. The vertical direction corresponds to the thickness direction of the substrate W. The lateral direction can be the depth direction of the substrate processing apparatus 1 or a direction different from the depth direction.

[0100] The auxiliary conveying robotic arm 12 includes a lift 13 for holding one or more substrates W, and two parallel motion actuators 19 for vertically and parallelly moving the lift 13. The two parallel motion actuators 19 move the lift 13 from the upper position (…). Figure 7 From the position indicated by the solid line in the middle to the position below ( Figure 7 The upper position is a non-immersion position where one or more substrates W held by the elevator 13 are entirely disposed above the opening 21o of the immersion tank 21. The lower position is an immersion position where one or more substrates W held by the elevator 13 are entirely disposed in the immersion tank 21, i.e., within the storage space 21s.

[0101] The lift 13 is an example of a substrate holder that holds one or more substrates W. The lift 13 is capable of holding multiple substrates W of the same shape and size. The number of substrates W held by the lift 13 can be 50, or more or fewer. The multiple substrates W are fixed to the lift 13 to prevent movement relative to it. When the multiple substrates W are fixed to the lift 13, all substrates W are parallel to each other in a separated state, and the centers of all substrates W are arranged along a straight line extending in the vertical direction.

[0102] like Figure 8 as well as Figure 9As shown, the lifting mechanism 13 includes two base plates 14, two support shafts 15, two support frames 16, and two clamps 17. The two base plates 14 are arranged vertically opposite each other on both sides of one or more base plates W. The two support shafts 15 are supported on the two base plates 14 in a vertical direction extending from one of the base plates 14 to the other. The two support frames 16 are supported on the two base plates 14 via the two support shafts 15 in a manner that allows them to rotate relative to the two base plates 14. When the two support frames 16 rotate relative to the two base plates 14, the two clamps 17 press against the end faces of the one or more base plates W supported by the two support frames 16. The one or more base plates W are fixed by the two clamps 17 in a state supported between the two base plates 14 by the two support frames 16.

[0103] like Figure 10A as well as Figure 10B As shown, two support shafts 15 are arranged laterally at intervals, extending vertically. The two support shafts 15 are parallel to each other and arranged at equal heights. The two support shafts 15 are positioned between two base plates 14. Each support shaft 15 is supported by its respective base plate 14. One support shaft 15 is rotatable relative to the two base plates 14 about its centerline. The other support shaft 15 is similarly rotatable. Even when the support frame 16 is rotatable relative to the support shafts 15, each support shaft 15 can also be fixed to its respective base plate 14.

[0104] Two support frames 16 are supported by two support shafts 15. Each support frame 16 includes a lower frame 16L disposed below the support shafts 15 and an upper frame 16u disposed above the support shafts 15. A clamp 17 is fixed to the upper frame 16u. The clamp 17 is disposed above the support shafts 15. The upper frame 16u and the clamp 17 are disposed to the side of the substrate W. The lower frame 16L is disposed below the substrate W. The substrate W is supported by the two lower frames 16L. When multiple substrates W are supported by the two lower frames 16L, the outer peripheries of the multiple substrates W are inserted one by one into multiple retaining slots 16a provided in the lower frames 16L (see reference). Figure 10B The retaining groove 16a is an arc-shaped groove extending 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.

[0105] One support frame 16 is rotatable relative to the two base plates 14, along with one support shaft 15 and one clamp 17, about one support shaft 15. Similarly, the other support frame 16 is rotatable relative to the two base plates 14, along with the other support shaft 15 and the other clamp 17, about the other support shaft 15. Each support frame 16 is in an open position relative to the two base plates 14.Figure 10A The position shown) and the closed position ( Figure 10B The substrate W can move between the positions shown. The open position is when the substrate W can pass vertically between the two clamps 17. The closed position is when the two clamps 17 press 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 can return to the closed position by the weight of the support frames 16 and the clamps 17, or by the restoring force of an elastic body such as a spring that holds the support frames 16 in the closed position.

[0106] like Figure 10A As shown, the main conveying robotic arm 11 includes a pair of support rods 11b that support multiple substrates W by contacting them in a vertical position, an opening / closing actuator (not shown) that increases or decreases the spacing between the pair of support rods 11b, and a transfer arm 11a that transmits the power of the opening / closing actuator to the pair of support rods 11b. The pair of support rods 11b extend vertically and are laterally opposed, spaced apart. The pair of support rods 11b are parallel to each other. The pair of support rods 11b contact the outer periphery of all substrates W at a position below the center of all substrates W, thereby supporting the multiple substrates W in a vertical position.

[0107] If the pair of support rods 11b of the main conveying robotic arm 11 places one or more substrates W on the two support frames 16, the outer periphery of one or more substrates W is 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 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 one or more substrates W supported by each support frame 16, two clamps 17 press against the end face of one or more substrates W. Thus, one or more substrates W are fixed to the elevator 13.

[0108] The pair of support rods 11b of the main conveying robotic arm 11 can hold the substrate W while the two clamps 17 are pressing against the end face of the substrate W. If the pair of support rods 11b lifts one or more substrates W fixed to the elevator 13, the two support frames 16 rotate from the closed position to the open position, and the two clamps 17 leave the end face of one or more substrates W. Then, one or more substrates W are lifted by the pair of support rods 11b of the main conveying robotic arm 11, and one or more substrates W move upward from the two support frames 16.

[0109] like Figure 11 As shown, the clamp 17 includes a pressing surface 17a that contacts the end face of the substrate W. The pressing surface 17a may have a vertical cross-section in the shape of an arc or a cylinder, or it may have a horizontal cross-section in the shape of a V. Figure 11An example illustrating 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 V-shaped horizontal cross-section that opens towards the substrate W side.

[0110] The substrate W is supported by the support frame 16 with a portion of its outer periphery disposed within the holding groove 16a of the support frame 16. When the clamp 17 moves away from the substrate W, the substrate W can move relative to the support frame 16 within the gap between the substrate W and the holding groove 16a. When the substrate W is tilted, if the support frame 16 approaches the closed position, the end face of the substrate W moves along the pressing surface 17a while in contact with the pressing surface 17a of the clamp 17. As a result, the substrate W changes to a vertical position and is fixed to the lift 13 in this state.

[0111] As described above, the auxiliary conveying robot arm 12 includes two parallel movement actuators 19 that move the elevator 13 vertically in parallel. The two parallel movement actuators 19 also function as posture-changing actuators that change the position of the base plate W between a vertical and an inclined position by altering the posture of the elevator 13. The two parallel movement actuators 19 are connected to two base plates 14 via two connectors 18, such as bearings. Figure 9 This illustrates an example where connector 18 includes a laterally extending central shaft and a bearing surrounding the central shaft. The bearing is mounted on a parallel motion actuator 19, and the central shaft is mounted on a base plate 14. One base plate 14 is rotatable relative to one parallel motion actuator 19 about a laterally extending axis of rotation. The other base plate 14 is rotatable relative to the other parallel motion actuator 19 about a laterally extending axis of rotation.

[0112] Figure 8 , Figure 9 as well as Figure 12 The parallel motion actuator 19 is an example of a telescopic electric cylinder. An actuator is a device that converts driving energy, representing electrical, fluid, magnetic, thermal, or chemical energy, into mechanical work. Actuators include electric motors (rotary motors), linear motors, cylinders, and other devices. When the motion of the actuator differs from the motion of the object, a motion converter that converts the actuator's motion into linear or rotary motion can be provided. When the actuator is an electric motor and causes the object to move linearly, a motion converter such as a ball screw or ball nut can convert the rotation of the electric motor into linear motion.

[0113] Two parallel motion actuators 19 operate independently, raising and lowering the two base plates 14. When the two parallel motion actuators 19 move the two base plates 14 in the same direction, at the same speed, and by the same amount of movement, the lift 13 moves parallel to the ground in either the upward or downward direction. Thus, while the posture of the base plate W remains fixed, one or more base plates W fixed to the lift 13 move parallel to the ground in either the upward or downward direction. Figure 12 As shown, if two parallel motion actuators 19 cause the two base plates 14 to move relative to each other in the vertical direction, then one or more base plates W fixed to the elevator 13 will change between a vertical posture and an inclined posture. The inclination angle θi of the base plate W (refer to...) Figure 4A The value increases as the relative movement of the two base plates 14 in the vertical direction increases, and decreases as the movement decreases.

[0114] like Figure 12 As shown, with one or more substrates W fixed to the elevator 13, the control device 3 uses two parallel motion actuators 19 to move two base plates 14 relative to each other in the vertical direction. This changes the position of one or more substrates W fixed to the elevator 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, allowing the substrates W to tilt at any angle θi within a range of less than 90 degrees (refer to...). Figure 4A The substrate W is tilted relative to the vertical plane. The control device 3 tilts the elevator 13 via two parallel movement actuators 19 so that the tilt angle θi of the substrate W matches the preset value stored in the control device 3. When performing the above-described processing of the substrate W, the tilt angle θi of the substrate W is set to the retraction contact angle θr (refer to...). Figure 4C Approximately 90 degrees or consistent with that angle.

[0115] When substrate W is processed by substrate processing apparatus 1, control device 3 places a batch of substrate W in elevator 13 via main conveyor arm 11. Thus, a batch of substrate W is fixed vertically in elevator 13. Then, control device 3 moves two base plates 14 downwards at the same speed and by the same amount via two parallel movement actuators 19. As a result, a batch of substrate W fixed vertically in elevator 13 moves horizontally downwards, passing through the liquid surface LS in impregnation tank 21. That is, a batch of substrate W fixed vertically in elevator 13 changes from a non-impregnated state to an impregnated state, and processing liquid in impregnation tank 21 is supplied to each substrate W.

[0116] In the aforementioned processing of substrate W, multiple processing solutions are sequentially supplied to one or more substrates W in the order of DHF, DIW (pure water), SCI, DIW, IPA, toluene, liquid containing a water-repellent agent, toluene, IPA, and DIW. In this case, the control device 3, while positioning a batch of substrates W in a vertical position fixed to the elevator 13 within the immersion tank 21, replaces the processing solution (DHF) in the immersion tank 21 with another processing solution (pure water). Then, before replacing the IPA in the immersion tank 21 with pure water, the control device 3, while positioning a batch of substrates W in a vertical position fixed to the elevator 13 within the immersion tank 21, replaces the processing solution in the immersion tank 21 with another processing solution.

[0117] After supplying all the required processing liquid to one or more substrates W, as follows Figure 12 As shown, the control device 3 uses two parallel motion actuators 19 to move the two base plates 14 relative to each other in the vertical direction, thereby changing a batch of substrates W from a vertical posture to an inclined posture. In this state, the control device 3 uses the two parallel motion actuators 19 to move the two base plates 14 upward at the same speed and by the same amount. As a result, a batch of substrates W, fixed to the inclined posture of the elevator 13, moves parallel upward in the direction, changing from an impregnated state to a non-impregnated state. That is, a batch of substrates W, while maintaining an inclined posture, passes upward through the liquid surface LS in the impregnation tank 21. Therefore, compared to the case where the substrates W change from an impregnated state to a non-impregnated state in a vertical posture, the time for the substrates W and the liquid surface LS to intersect can be shortened.

[0118] After the control device 3 changes a batch of substrates W, which is fixed in an inclined position to the elevator 13, to a non-impregnated state, the two parallel motion actuators 19 move the two base plates 14 relative to each other in the vertical direction, thereby changing the batch of substrates W fixed to the elevator 13 from an inclined position to a vertical position. Then, the control device 3 lifts the batch of substrates W from the elevator 13 by the main transfer robot arm 11. As a result, the fixation of the batch of substrates W relative to the elevator 13 is released, and the batch of substrates W leaves the elevator 13 upwards. Then, the control device 3, by the main transfer robot arm 11, moves the batch of substrates W into the drying treatment tank 2d, where the batch of substrates W is dried.

[0119] Next, the effects of this implementation method will be explained.

[0120] In this embodiment, the substrate W, tilted relative to the vertical plane, moves vertically relative to the surface of the processing liquid, i.e., the liquid surface LS, within the impregnation tank 21. As a result, the tilted substrate W passes upwards through the liquid surface LS, changing from an impregnated state to a non-impregnated state. Since the substrate W changes from an impregnated state to a non-impregnated state in a tilted position, the time for the substrate W and the liquid surface LS to intersect is shortened compared to the case where the substrate W changes from an impregnated state to a non-impregnated state in a vertical position. Therefore, the time it takes for the surface tension of the processing liquid within the impregnation tank 21 to apply to the pattern PA on the surface of the substrate W is reduced.

[0121] In this embodiment, with an aqueous liquid such as pure water stored in the impregnation tank 21, the substrate W, which is in an inclined position, and the liquid surface LS are moved relative to each other in the vertical direction. Therefore, compared to the case where the substrate W is changed from a non-impregnated state to an impregnated state in a vertical position, the time for the surface tension of the aqueous liquid in the impregnation tank 21 to be applied to the pattern PA can be shortened. Water has the highest surface tension among all liquids, except for liquid metals such as mercury. Therefore, the time for a relatively large surface tension to be applied to the pattern PA can be shortened.

[0122] In this embodiment, the substrate W is immersed in a water-repellent liquid in the immersion tank 21. Assuming the surface of the substrate W is smooth, if the water-repellent liquid is supplied to the surface of the substrate W, the contact angle of water relative to the surface of the substrate W exceeds 90 degrees. According to the Wenzel formula, when comparing the contact angle of water relative to a smooth surface and a rough surface made of the same material, when the contact angle of water relative to a smooth surface exceeds 90 degrees, the contact angle of water relative to a rough surface is greater than that of water relative to a smooth surface. The surface of the substrate W is a rough surface with fine patterns PA formed thereon. Therefore, the contact angle of water relative to the surface of the substrate W to which the water-repellent liquid has been supplied significantly exceeds 90 degrees. That is, when a water droplet is placed on the horizontal surface of the substrate W, the contact angle (static contact angle) of water relative to the surface of the substrate W significantly exceeds 90 degrees.

[0123] After immersing the substrate W in the water-repellent liquid in the immersion tank 21, with the aqueous liquid such as pure water stored in the immersion tank 21, the tilted substrate W and the liquid surface LS are moved relative to each other in the vertical direction, thereby changing the tilted substrate W from an immersed state to a non-immersed state. By supplying the water-repellent liquid and tilting the substrate W, the retreat contact angle θr is made close to or consistent with 90 degrees, thus eliminating or reducing the component of the surface tension exerted from the aqueous liquid on the surface of the substrate W in the direction parallel to the surface of the substrate W (parallel component of surface tension). 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.

[0124] In this embodiment, with at least a portion of the recess Q1 filled with air and an aqueous liquid such as pure water supported by the air in the recess Q1 and the protrusion P1, the tilted substrate W and the liquid surface LS are moved relative to each other in the vertical direction. That is, the surface of the substrate W has high water repellency, and the surface tension of water is high, so the aqueous liquid contacts the surface of the substrate W in a CB state. If the aqueous liquid in contact with the surface of the substrate W changes from the W state to the CB state, the contact angle of the aqueous liquid relative to the surface of the substrate W increases. As a result, the receding contact angle θr approaches or matches 90 degrees, thus eliminating or reducing the parallel component of surface tension.

[0125] In this embodiment, the water-repellent liquid on the surface of the substrate W is replaced with a hydrophobic liquid such as toluene, and the hydrophobic liquid on the surface of the substrate W is replaced with an amphiphilic liquid such as IPA. Then, the amphiphilic liquid on the surface of the substrate W is replaced with an aqueous liquid such as pure water. If the water-repellent contained in the water-repellent liquid comes into contact with water, unwanted substances may be generated in the water-repellent liquid. By replacing the water-repellent liquid with a hydrophobic liquid whose solubility in water is lower than that in the amphiphilic liquid, the generation of such unwanted substances can be prevented, or the amount of such substances generated can be reduced. Furthermore, compared to replacing the water-repellent liquid on the surface of the substrate W with an amphiphilic liquid, the amount of water-repellent liquid remaining in the aqueous liquid can be reduced.

[0126] In this embodiment, the surface of substrate W is oxidized by supplying a chemical solution to it. As a result, at least a portion of the surface of substrate W is terminated with hydroxyl (OH) groups. Oxidation of the surface of substrate W by the chemical solution increases the number of hydroxyl groups exposed on the surface of substrate W. When the water-repellent agent is a silylating agent, the hydrogen atoms of the hydroxyl groups are replaced by the silyl groups of the water-repellent agent. Therefore, by supplying the chemical solution to the surface of substrate W, the water-repellent properties of the substrate W surface can be effectively improved.

[0127] Furthermore, the solution on the surface of substrate W is not replaced by a water-repellent liquid, but rather by an aqueous liquid used as a rinsing solution. Then, the aqueous liquid on the surface of substrate W is replaced by an amphiphilic liquid, and then by a hydrophobic liquid. Even if some aqueous liquid remains after the amphiphilic liquid is replaced, it diffuses into the amphiphilic liquid on the surface of substrate W. Then, the amphiphilic liquid is replaced by a hydrophobic liquid. The hydrophobic liquid is a liquid with lower water solubility than the amphiphilic liquid. Therefore, water remaining on the surface of substrate W can be eliminated or reduced.

[0128] If the water-repellent agent in the liquid comes into contact with water, unwanted substances may be generated in the liquid. By using a water-containing liquid as a rinsing solution for phased replacement with an amphiphilic liquid and a hydrophobic liquid, the water-repellent agent liquid can be supplied to the surface of the substrate W with little or no water residue. Therefore, the generation of such unwanted substances can be prevented or the amount of such substances generated can be reduced, while improving the water repellency of the substrate W surface.

[0129] In this embodiment, the tilt angle θi of the substrate W relative to the vertical plane is set such that the retreat contact angle θr is close to 90 degrees or consistent with that angle. The retreat contact angle θr is the angle between the surface of the substrate W and the liquid surface LS when the substrate W moves upward relative to the liquid surface LS in a state where the substrate W intersects with the liquid surface LS. By doing so, the component of the surface tension exerted on the surface of the substrate W by the processing liquid in the immersion tank 21 in the direction parallel to the surface of the substrate W (parallel component of surface tension) can be eliminated or reduced, thereby reducing the collapse rate of the pattern PA.

[0130] In this embodiment, while fixing the substrate W in an inclined position, the inclined substrate W and the liquid surface LS are moved relative to each other in the vertical direction. If the substrate W and the liquid surface LS are moved relative to each other in the vertical direction while the substrate W is intersecting the liquid surface LS, a force such as resistance is applied to the substrate W from the processing liquid. Because the substrate W is fixed in an inclined position, it is possible to prevent the posture of the substrate W from changing due to this force, and the variation of surface tension applied to the pattern PA from the processing liquid in the impregnation tank 21 can be reduced.

[0131] In this embodiment, the substrate W is placed on two support frames 16. When the outer periphery of the substrate W contacts the two support frames 16, the weight of the substrate W is applied to the two support frames 16, causing them to move. Simultaneously, two clamps 17 actuate, pressing against the end face of the substrate W, which is supported vertically by the two support frames 16. Thus, the posture of the substrate W relative to the two support frames 16 and the two clamps 17 (hereinafter referred to as the two support frames 16, etc.) is fixed. The posture of the two support frames 16, etc., is changed in this state. If the posture of the two support frames 16, etc., changes, the posture of the substrate W also changes. Thus, the substrate W changes from a vertical posture to an inclined posture and is fixed in an inclined posture. Therefore, it is possible to fix the substrate W in an inclined posture while simultaneously moving the inclined substrate W and the liquid surface LS relative to each other in the vertical direction.

[0132] In this embodiment, the power of multiple parallel movement actuators 19 is transmitted to the substrate W, thereby causing the substrate W to change between a vertical posture and a tilted posture. Furthermore, the power of the multiple parallel movement actuators 19 is transmitted to the substrate W, thereby causing the substrate W, in either a vertical or tilted posture, to move horizontally in the up-down direction. In other words, the multiple parallel movement actuators 19 also function as posture-changing actuators for changing the posture of the substrate W. Therefore, a dedicated posture-changing actuator is not required.

[0133] Next, other implementation methods will be described.

[0134] Alternatively, when the processing liquid is supplied to the substrate W, instead of lowering one or more substrates W in a vertical position into the immersion tank 21, one or more substrates W in an inclined position are lowered into the immersion tank 21. That is, one or more substrates W can be changed from a vertical position to an inclined position before being changed into an immersion state. If this is done, the time for the surface tension of the processing liquid in the immersion tank 21 to apply to the pattern PA can be shortened compared to the case where the substrate W is changed from a vertical position from a non-immersion state to an immersion state.

[0135] When multiple processing liquids are supplied to one or more substrates W, the substrates W can be changed from a vertical position to an inclined position while they are in contact with the final processing liquid, or the substrates W can be changed from a vertical position to an inclined position while they are in contact with a processing liquid other than the final processing liquid.

[0136] The final processing liquid supplied to the substrate W can be an aqueous liquid other than pure water, or a liquid other than an aqueous liquid. That is, when the substrate W intersects with the liquid surface LS, the liquid surface LS can be the surface of an aqueous liquid other than pure water, or the surface of a liquid other than an aqueous liquid.

[0137] If it doesn't matter if the posture of the substrate W changes when it intersects with the liquid surface LS, then the substrate W does not need to be fixed in a tilted posture.

[0138] Alternatively, multiple parallel translation actuators 19 may not serve as attitude change actuators, but rather be dedicated attitude change actuators independent of the parallel translation actuators 19.

[0139] The aqueous liquid supplied to the substrate W may not be pure water, but rather a foaming aqueous liquid such as carbonated water that foams under normal temperature and pressure. In this case, the transfer of the foaming aqueous liquid from the Wenzel state to the Cassie-Baxter state can be promoted by the gas generated from the foaming aqueous liquid.

[0140] Alternatively, after supplying a hydrophobic liquid such as toluene, the supply of a liquid containing a water-repellent agent may not be performed; instead, the liquid containing a water-repellent agent may be supplied to the substrate W in contact with an amphiphilic liquid such as IPA. That is, the supply of the hydrophobic liquid performed between the supply of the amphiphilic liquid and the supply of the liquid containing the water-repellent agent may be omitted.

[0141] Alternatively, after supplying the water-repellent liquid, the hydrophobic liquid may not be supplied; instead, an amphiphilic liquid may be supplied to the substrate W in contact with the water-repellent liquid. That is, the supply of the hydrophobic liquid performed between the supply of the water-repellent liquid and the supply of the amphiphilic liquid may be omitted.

[0142] The processing solution to be supplied to the substrate W may also exclude the water-repellent liquid. For example, the solution other than the water-repellent liquid may be rinsed off by a rinsing solution after it has been supplied to the substrate W.

[0143] The substrate processing apparatus 1 is not limited to an apparatus for processing a circular substrate W, but may also be an apparatus for processing a polygonal substrate W.

[0144] Two or more of the above-described components can be combined. Two or more of the above-described processes can be combined.

[0145] The embodiments of the present invention have been described in detail, but these are merely specific examples used to clarify the technical content of the present invention. The present invention should not be interpreted as limited to these specific examples, and the spirit and scope of the present invention are limited only by the additional technical solutions.

Claims

1. A substrate processing method, comprising processing a substrate having a pattern including protrusions and recesses formed on its surface, wherein, The process includes a de-immersion step, in which the substrate, which is in an inclined position relative to the vertical plane, and the surface of the processing liquid in the immersion tank, i.e., the liquid surface, are moved relative to each other in the vertical direction, thereby changing the substrate from an immersed state in the processing liquid in the immersion tank to a non-immersion state in which the substrate is entirely disposed above the liquid surface.

2. The substrate processing method according to claim 1, wherein, The unimmersion process is a process in which the substrate in the tilted position and the liquid surface are moved relative to each other in the vertical direction while the substrate is in the immersion tank with an aqueous liquid as the treatment liquid, thereby changing the substrate from the immersion state to the non-immersion state.

3. The substrate processing method according to claim 2, wherein, Also includes: A water-repellent supply process in which the substrate is immersed in the water-repellent liquid in the immersion tank while the immersion tank contains a water-repellent liquid, wherein the water-repellent liquid increases the contact angle of water with respect to a horizontal, smooth surface made of the same material as the end face of the protrusion to a value greater than 90 degrees; and After immersing the substrate in the water-repellent liquid in the immersion tank, and with the water-containing liquid stored in the immersion tank, the substrate is immersed in the water-containing liquid in the immersion tank in a water supply process.

4. The substrate processing method according to claim 3, wherein, The process of removing the impregnation includes a process of moving the substrate in an inclined position and the liquid surface relative to each other in the vertical direction, with at least a portion of the recess filled with air and the aqueous liquid supported by the air in the recess and the protrusion.

5. The substrate processing method according to claim 3 or 4, wherein, The substrate processing method further includes: After immersing the substrate in the water-repellent liquid in the immersion tank, and with a hydrophobic liquid fused with the water-repellent liquid stored in the immersion tank, the substrate is immersed in the hydrophobic liquid in the immersion tank for water repellency and then supplied with hydrophobic liquid; and After immersing the substrate in the hydrophobic liquid in the immersion tank, and with the immersion tank containing an amphiphilic liquid in which water has a higher solubility than the hydrophobic liquid and is compatible with the hydrophobic liquid, the substrate is immersed in the amphiphilic liquid in the immersion tank for a water-removal process followed by the supply of the amphiphilic liquid. The water supply process is a process in which, after immersing the substrate in the amphiphilic liquid in the immersion tank, the substrate is immersed in the aqueous liquid in the immersion tank while the immersion tank contains an aqueous liquid with a surface tension greater than that of the amphiphilic liquid and which is compatible with the amphiphilic liquid.

6. The substrate processing method according to claim 3 or 4, wherein, The substrate processing method further includes: In a process of supplying a solution to immerse the substrate in the solution stored in the immersion tank to oxidize the surface of the substrate; After immersing the substrate in the solution in the immersion tank, and with the aqueous liquid as rinsing liquid stored in the immersion tank, the substrate is immersed in the aqueous liquid in the immersion tank for a rinsing liquid supply process. After immersing the substrate in the aqueous liquid in the immersion tank, and with the immersion tank containing an amphiphilic liquid that is fused with the aqueous liquid, a process of supplying the amphiphilic liquid before immersing the substrate in the amphiphilic liquid in the immersion tank and then supplying it with the amphiphilic liquid before water removal; and After immersing the substrate in the amphiphilic liquid in the immersion tank, and with the immersion tank containing a hydrophobic liquid whose solubility in water is less than that in the amphiphilic liquid and which is compatible with the amphiphilic liquid, a process of supplying the hydrophobic liquid before immersing the substrate in the hydrophobic liquid in the immersion tank is performed. The water-repellent supply process is a process in which, after immersing the substrate in the hydrophobic liquid in the immersion tank, the substrate is immersed in the water-repellent liquid in the immersion tank while the immersion tank contains the water-repellent liquid.

7. The substrate processing method according to any one of claims 1 to 4, wherein, The tilting posture is a posture in which, when the substrate moves upward relative to the liquid surface while the substrate is intersecting the liquid surface, the angle formed between the surface of the substrate and the liquid surface, i.e., the retreating contact angle, is close to 90 degrees or consistent with that angle.

8. The substrate processing method according to any one of claims 1 to 4, wherein, The process of removing the immersion is a process in which the substrate is fixed in the tilted position while the substrate and the liquid surface in the tilted position are moved relative to each other in the vertical direction, thereby changing the substrate from the immersion state to the non-immersion state.

9. The substrate processing method according to claim 8, wherein, Also includes: The process involves moving the two support frames by the weight of the substrate itself through contact between the outer periphery of the substrate and the two support frames, thereby pressing two clamps that move together with the two support frames against the end face of the substrate in a vertical position supported by the two support frames. and A posture change process that involves changing the posture of the two support frames and the two clamps while they are in contact with the substrate, thereby changing the substrate from the vertical posture to the inclined posture.

10. The substrate processing method according to any one of claims 1 to 4, wherein, Also includes: A posture change process in which the substrate is changed between a vertical posture and a tilted posture by multiple parallel motion actuators; and A lifting process in which the substrate in a vertical or tilted position is moved parallel to each other in the vertical direction by the plurality of parallel movement actuators.

11. A substrate processing apparatus, wherein, include: An elevator that holds the substrate in an inclined posture relative to a vertical plane, wherein the substrate has a pattern of protrusions and recesses formed on its surface. An immersion tank that stores a treatment solution for immersing the substrate held by the elevator; A parallel movement actuator that causes the substrate held by the elevator to move parallel in the vertical direction between an immersion position in the immersion tank and a non-immersion position above the immersion tank. A drain valve that discharges the treatment liquid from the immersion tank; as well as The control device changes the substrate from an immersed state in the treatment liquid within the immersion tank to a non-immersion state above the surface of the treatment liquid within the immersion tank by at least one of the following: raising the substrate by the parallel movement actuator, which raises the substrate in the tilted position held by the elevator, and discharging the treatment liquid from the immersion tank by the drain valve.

12. The substrate processing apparatus according to claim 11, wherein, The elevator includes: Two support frames support the substrate by contacting its outer periphery and move according to the substrate's own weight; and Two clamps, moving together with the two support frames, press against the end face of the substrate in a vertical position supported by the two support frames. The substrate processing apparatus further includes a posture change actuator that changes the substrate from the vertical posture to the tilted posture by changing the posture of the two support frames and the two clamps.

13. The substrate processing apparatus according to claim 11 or 12, wherein, The parallel movement actuator includes a plurality of parallel movement actuators that cause the substrate held by the elevator to move parallel in the vertical direction between the immersion position and the non-immersion position, and to change the substrate held by the elevator between a vertical posture and the tilted posture.

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