SUBSTRATE PROCESSING APPARATUS AND SUBSTRATE PROCESSING METHOD

Abstract

Provided are a substrate processing apparatus and a substrate processing method that can reduce the risk of clogging a drainage pipe, reduce liquid consumption, and contribute to reducing environmental load and running costs. The substrate processing apparatus includes a film fragment discharge unit (71) that uses a first liquid to guide film fragments of a processing film peeled from the surface of a substrate to a drainage pipe (60), a second liquid supply unit that supplies a second liquid to the drainage pipe, a separation mechanism (110) that separates the first and second liquids, and a first liquid storage mechanism (151) and a second liquid storage mechanism (152) that receive the separated first and second liquids, respectively. The processing film is soluble in one of the first and second liquids and insoluble or poorly soluble in the other. The separation mechanism may include a drainage trap tank (111) and a valve mechanism (112) that opens one of a first discharge port (PA) and a second discharge port (PB) and closes the other by vertical movement of a float (113).

Description

[Technical Field]

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

[0002] Patent Document 1 discloses a substrate processing apparatus and a substrate processing method capable of removing a target object present on a substrate. A processing liquid is supplied to the surface of the substrate, and the processing liquid is solidified or hardened to form a processing film. The processing film holds the target object on the substrate. By supplying a stripping liquid to the substrate, the processing film holding the target object is peeled off and removed from the substrate. This allows the target object on the substrate to be removed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-053166 Summary of the Invention [Problem to be solved by the invention]

[0004] The treated film that has been stripped from the substrate by the stripping solution breaks into film fragments that are then drained together with the stripping solution through a drainage pipe, which may clog the drainage pipe.

[0005] By flowing a dissolving solution capable of dissolving the treated film into the drainage pipe, the film fragments can be dissolved and reduced in size, reducing the risk of pipe clogging. However, the stripper and dissolving solution are mixed in the drainage pipe, making them unreusable. For example, if a mixture of stripper and dissolving solution is used in the process of removing the treated film, the treated film will be dissolved by the dissolving solution. This can release the target material from the treated film and potentially reattach it to the substrate surface. Therefore, it is difficult to reuse the stripper and dissolving solution mixed in the drainage pipe. This results in a large consumption of the stripper and dissolving solution, which creates issues such as a heavy environmental burden and high running costs.

[0006] Therefore, one embodiment of the present invention provides a substrate processing apparatus and a substrate processing method that can reduce the risk of clogging of the drainage pipe, reduce liquid consumption, and contribute to reducing the environmental load and running costs. [Means for solving the problem]

[0007] One embodiment of the present invention provides a substrate processing apparatus including: a substrate processing unit for processing a substrate; a processing liquid nozzle for supplying a processing liquid containing a solute and a solvent to a surface of the substrate in the substrate processing unit; a processing film forming unit for solidifying or curing the processing liquid to form a processing film on the surface of the substrate in the substrate processing unit; a peeling unit for peeling the processing film from the surface of the substrate in the substrate processing unit; and a drainage pipe for discharging waste liquid from the substrate processing unit. The substrate processing apparatus includes: a film fragment discharge unit for guiding film fragments of the processing film peeled from the surface of the substrate by the peeling unit from the substrate processing unit to the drainage pipe with a first liquid; a second liquid supply unit for supplying a second liquid different from the first liquid to the drainage pipe; a separation mechanism provided in the drainage pipe for separating the first liquid from the second liquid; a first liquid storage mechanism for receiving the first liquid separated by the separation mechanism; and a second liquid storage mechanism for receiving the second liquid separated by the separation mechanism. The treatment film is soluble in one of the first liquid and the second liquid, and is insoluble or hardly soluble in the other of the first liquid and the second liquid.

[0008] In one embodiment, the second liquid supply unit supplies the second liquid to the substrate in the substrate processing unit.

[0009] In one embodiment, the treatment film is insoluble or poorly soluble in the first liquid and soluble in the second liquid. The peeling unit peels the treatment film from the surface of the substrate by supplying the first liquid as a stripping liquid to the surface of the substrate in the substrate processing unit. The film fragment discharge unit guides the stripping liquid (the first liquid) discharged from the surface of the substrate together with the treatment film fragments to the drainage pipe.

[0010] In one embodiment, the second liquid supply unit includes a residue removal processing unit in the substrate processing unit that supplies the second liquid as a residue removal liquid to the surface of the substrate from which the treatment film has been peeled by the peeling unit, and dissolves and removes residue of the treatment film remaining on the surface of the substrate. The residue removal liquid (the second liquid) discharged from the surface of the substrate is led to the drainage pipe.

[0011] In one embodiment, the treatment film is soluble in the first liquid and insoluble or poorly soluble in the second liquid. The film fragment discharge unit includes a residue removal processing unit in the substrate processing unit that supplies the first liquid to the surface of the substrate as a residue removal liquid and dissolves residues of the treatment film remaining on the surface of the substrate from which the treatment film has been peeled by the peeling unit, and guides the residue removal liquid (the first liquid) discharged from the surface of the substrate together with the film fragments of the treatment film to the drainage pipe. The second liquid supply unit includes a replacement processing unit in the substrate processing unit that supplies the second liquid to the surface of the substrate and replaces the residue removal liquid remaining on the surface of the substrate with the second liquid, and the second liquid discharged from the surface of the substrate is guided to the drainage pipe.

[0012] In one embodiment, the peeling unit peels off the processing film from the surface of the substrate by blowing gas toward the surface of the substrate in the substrate processing unit.

[0013] In one embodiment, the first liquid and the second liquid are incompatible with each other and have different densities. The separation mechanism includes a waste liquid trap tank that stores the first liquid and the second liquid and dissolves membrane fragments of the treatment membrane, a first discharge port for discharging the first liquid from the waste liquid trap tank, and a second discharge port for discharging the second liquid from the waste liquid trap tank. The separation mechanism has a float that moves up and down in accordance with the interface between the first liquid and the second liquid in the waste liquid trap tank, and includes a valve mechanism that opens one of the first discharge port and the second discharge port and closes the other of the first discharge port and the second discharge port due to the up and down movement of the float.

[0014] In one embodiment, the first liquid and the second liquid are immiscible with each other, have different densities, and have different melting points. The separation mechanism includes a waste liquid trap tank that stores the first liquid and the second liquid and dissolves the membrane fragments of the treatment membrane, a cooling unit that freezes one of the first liquid layer and the second liquid layer formed by separation of the first liquid and the second liquid into a solid phase and maintains the other of the first liquid layer and the second liquid layer in a liquid phase, and a discharge unit that discharges the other of the first liquid layer and the second liquid layer, maintained in a liquid phase, from the waste liquid trap tank while the other is in a solid phase.

[0015] In one embodiment, the separation mechanism includes an ion exchange resin unit that selectively extracts the first liquid or the second liquid from a mixture of the first liquid and the second liquid.

[0016] In one embodiment, either the first liquid or the second liquid contains water, and the separation mechanism includes a dehydration unit that extracts water from a mixture of the first liquid and the second liquid.

[0017] In one embodiment, the apparatus further includes a waste liquid trap tank provided in the waste liquid piping, for storing the first liquid and the second liquid and dissolving membrane fragments of the treatment membrane, and a mixture of the first liquid and the second liquid is supplied from the waste liquid trap tank to the separation mechanism.

[0018] One embodiment of the present invention provides a substrate processing method including: a processing liquid supply step of supplying a processing liquid containing a solute and a solvent to a surface of a substrate in a substrate processing unit; a processing film formation step of solidifying or curing the processing liquid in the substrate processing unit to form a processing film on the surface of the substrate; and a peeling step of peeling the processing film from the surface of the substrate in the substrate processing unit. The substrate processing method includes: a film fragment discharge step of guiding film fragments of the processing film peeled from the surface of the substrate in the peeling step from the substrate processing unit to a drainage pipe using a first liquid; a second liquid supply step of supplying a second liquid different from the first liquid to the drainage pipe; a separation step of separating the first liquid and the second liquid using a separation mechanism provided in the drainage pipe; and a storage step of storing the first liquid and the first liquid separated by the separation mechanism in a first liquid storage mechanism and a second liquid storage mechanism, respectively. The processing film is soluble in one of the first liquid and the second liquid and is insoluble or poorly soluble in the other of the first liquid and the second liquid.

[0019] In one embodiment, the treatment film is insoluble or poorly soluble in the first liquid and soluble in the second liquid. The peeling step peels the treatment film from the surface of the substrate by supplying the first liquid as a stripping liquid to the surface of the substrate in the substrate processing unit. The film fragment discharge step guides the stripping liquid (the first liquid) discharged from the surface of the substrate together with the treatment film fragments to the drainage pipe.

[0020] In one embodiment, the second liquid supplying step includes a residue removing step in which the second liquid is supplied to the surface of the substrate as a residue removing liquid in the substrate processing unit, and the residue of the processing film remaining on the surface of the substrate from which the processing film has been peeled in the peeling step is dissolved and removed. The residue removing liquid (the second liquid) discharged from the surface of the substrate is led to the drainage pipe.

[0021] In one embodiment, the treatment film is soluble in the first liquid and insoluble or poorly soluble in the second liquid. The film fragment discharging step includes a residue removing step in the substrate processing unit, in which the first liquid is supplied to the surface of the substrate as a residue removing liquid to dissolve residues of the treatment film remaining on the surface of the substrate from which the treatment film has been peeled in the peeling step, and the residue removing liquid (the first liquid) discharged from the surface of the substrate together with the film fragments of the treatment film is guided to the drainage pipe. The second liquid supplying step includes a replacement step in the substrate processing unit, in which the second liquid is supplied to the surface of the substrate to replace the residue removing liquid remaining on the surface of the substrate with the second liquid, and the second liquid discharged from the surface of the substrate is guided to the drainage pipe.

[0022] In one embodiment, the removing step includes a gas removing step of removing the processing film from the surface of the substrate by blowing a gas toward the surface of the substrate in the substrate processing unit.

[0023] In one embodiment, the first liquid and the second liquid are immiscible with each other and have different densities. The separation mechanism includes a wastewater trap tank that stores the first liquid and the second liquid and dissolves membrane fragments of the treatment membrane, a first discharge port for discharging the first liquid from the wastewater trap tank, a second discharge port for discharging the second liquid from the wastewater trap tank, and a valve mechanism having a float that moves up and down following the interface between the first liquid and the second liquid in the wastewater trap tank, and that opens one of the first discharge port and the second discharge port and closes the other of the first discharge port and the second discharge port by the up and down movement of the float. The separation process includes a membrane fragment dissolving process in the wastewater trap tank, a first discharge process in which the valve mechanism opens the first discharge port to discharge the first liquid from the wastewater trap tank, and a second discharge process in which the valve mechanism opens the second discharge port to discharge the second liquid from the wastewater trap tank.

[0024] In one embodiment, the first liquid and the second liquid are immiscible with each other, have different densities, and have different melting points. The separation mechanism includes a waste liquid trap tank that stores the first liquid and the second liquid and dissolves the membrane fragments of the treatment membrane, and a cooling unit that freezes one of the first liquid layer and the second liquid layer formed by separation of the first liquid and the second liquid into upper and lower layers in the waste liquid trap tank, causing the first liquid layer and the second liquid layer to transition to a solid phase, and maintains the other of the first liquid layer and the second liquid layer in a liquid phase. The separation process includes a membrane fragment dissolving process in which membrane fragments of the treatment membrane are dissolved in the drain trap tank; a freezing process in which one of the first liquid layer and the second liquid layer is frozen and transitioned to a solid phase by the cooling unit, and the other of the first liquid layer and the second liquid layer is maintained in a liquid phase; a first discharge process in which one of the first liquid layer and the second liquid layer is discharged from the drain trap tank while the other of the first liquid layer and the second liquid layer is in a solid phase; a melting process in which one of the first liquid layer and the second liquid layer is melted and transitioned to a liquid phase after the first discharge process; and a second discharge process in which one of the first liquid layer and the second liquid layer that has transitioned to a liquid phase is discharged from the drain trap tank after the melting process.

[0025] In one embodiment, the separation mechanism includes an ion exchange resin unit that selectively extracts the first liquid or the second liquid from a mixture of the first liquid and the second liquid.

[0026] In one embodiment, either the first liquid or the second liquid contains water, and the separation mechanism includes a dehydration unit that extracts water from a mixture of the first liquid and the second liquid.

[0027] In one embodiment, the substrate processing method further includes a film fragment dissolving step of storing the first liquid and the second liquid in a waste liquid trap tank provided in the waste liquid piping and dissolving film fragments of the processing film, and a mixed liquid of the first liquid and the second liquid is supplied from the waste liquid trap tank to the separation mechanism. [Brief explanation of the drawings]

[0028] [Figure 1] FIG. 1 is a schematic plan view of a substrate processing apparatus according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic diagram illustrating an example of the configuration of the processing unit. [Figure 3] FIG. 3 is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus. [Figure 4] FIG. 4 is a flowchart illustrating an example of a substrate processing method. [Figure 5A] FIG. 5A shows the processing liquid supplying step. [Figure 5B] FIG. 5B shows the treatment film forming step. [Figure 5C] FIG. 5C shows the peeling process. [Figure 5D] FIG. 5D shows the removal process. [Figure 5E] FIG. 5E shows the residue removal step. [Figure 5F] FIG. 5F shows the rinsing step. [Figure 5G] FIG. 5G shows the drying process. [Figure 6A] FIG. 6A shows a first example of the configuration of the drainage system. [Figure 6B] FIG. 6B shows a first example of the configuration of the drainage system. [Figure 6C] FIG. 6C shows a first example of the configuration of the drainage system. [Figure 7A] FIG. 7A shows a second example of the drainage system. [Figure 7B] FIG. 7B shows a second example of the drainage system. [Figure 8A] FIG. 8A shows a third example configuration of the drainage system. [Figure 8B] FIG. 8B shows a third example of the drainage system. [Figure 9] FIG. 9 shows a fourth example of the configuration of the drainage system. [Figure 10] FIG. 10 shows an example of the configuration of a processing unit according to another embodiment of the present invention. [Figure 11]FIG. 11 is a flowchart illustrating an example of a substrate processing method performed by the processing unit. [Figure 12A] FIG. 12A shows the processing liquid supplying step. [Figure 12B] FIG. 12B shows the treatment film forming step. [Figure 12C] FIG. 12C shows the peeling process. [Figure 12D] FIG. 12D shows the residue removal step. [Figure 12E] FIG. 12E shows the substitution process. [Figure 12F] FIG. 12F shows the drying process. [Figure 13A] FIG. 13A is a diagram for explaining the peeling of a processing film by a peeling gas. [Figure 13B] FIG. 13B is a diagram for explaining the peeling of the processing film by the peeling gas. [Figure 14] FIG. 14 shows an example of the configuration of the drainage system. DETAILED DESCRIPTION OF THE INVENTION

[0029] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0030] FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to an embodiment of the present invention.

[0031] The substrate processing apparatus 1 is a single-wafer processing apparatus that processes substrates W, such as silicon wafers, one by one. In this embodiment, the substrate W is a disk-shaped substrate. Typically, a fine concave-convex pattern is formed on the surface (main surface) of the substrate W.

[0032] The substrate processing apparatus 1 includes a plurality of processing units 2 that process substrates W with a fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W to be processed in the processing units 2 is placed, transport robots IR and CR that transport the substrates W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.

[0033] The transport robot IR is an indexer robot that transports substrates W between the carrier C and the transport robot CR. The transport robot CR is a main transport robot that transports substrates W between the transport robot IR and the processing units 2. The multiple processing units 2 have, for example, the same configuration.

[0034] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and performs processing on the substrate W in the processing cup 7. The chamber 4 is formed with an entrance / exit (not shown) through which the transfer robot CR loads and unloads the substrate W. The chamber 4 is provided with a shutter unit (not shown) that opens and closes this entrance / exit.

[0035] FIG. 2 is a schematic diagram for explaining an example of the configuration of the processing unit 2. As shown in FIG.

[0036] The processing unit 2 includes a spin chuck 5 , a processing cup 7 , a first moving nozzle 9 , a second moving nozzle 10 , and a bottom nozzle 12 .

[0037] The spin chuck 5 rotates the substrate W around a rotation axis A1 while holding the substrate W horizontally. The rotation axis A1 is a vertical axis that passes through the center of the substrate W. The spin chuck 5 includes a plurality of chuck pins 20, a spin base 21, a rotation shaft 22, and a spin motor 23. The spin chuck 5 provides a substrate processing section that processes the substrate W.

[0038] The spin base 21 has a horizontally extending disk shape. On the upper surface of the spin base 21, a plurality of chuck pins 20 for gripping the peripheral edge of the substrate W are arranged at intervals in the circumferential direction of the spin base 21. The spin base 21 and the plurality of chuck pins 20 constitute a substrate holding unit that holds the substrate W horizontally. The substrate holding unit is also called a substrate holder.

[0039] The rotation shaft 22 extends vertically along the rotation axis A1. The upper end of the rotation shaft 22 is coupled to the center of the lower surface of the spin base 21. The spin motor 23 applies a rotational force to the rotation shaft 22. The rotation of the rotation shaft 22 by the spin motor 23 rotates the spin base 21. This causes the substrate W to rotate around the rotation axis A1. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

[0040] The processing cup 7 is housed in the chamber 4 (see FIG. 1). The processing cup 7 includes a plurality of guards 71 ​​that catch liquid splashed outward from the substrate W held on the spin chuck 5, a plurality of cups 72 that catch liquid guided downward by the plurality of guards 71, and a cylindrical outer wall member 73 that surrounds the plurality of guards 71 ​​and the plurality of cups 72.

[0041] In this embodiment, an example is shown in which two guards 71 ​​(a first guard 71A and a second guard 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided. Each of the first cup 72A and the second cup 72B has the form of an annular groove that is open upward. The first guard 71A is arranged to surround the spin base 21. The second guard 71B is arranged to surround the spin base 21 on the inner side of the first guard 71A in the radial direction of rotation of the substrate W. The first guard 71A and the second guard 71B each have a substantially cylindrical shape, and the upper end of each guard 71A, 71B is inclined inward toward the spin base 21.

[0042] The first cup 72A is formed integrally with the second guard 71B and receives the liquid guided downward by the first guard 71A. The second cup 72B receives the liquid guided downward by the second guard 71B. The liquid received in the cup 72 is guided to the drainage system 200 through the drainage piping 60. The drainage piping 60 includes a first drainage piping 60A and a second drainage piping 60B. The liquid received in the first cup 72A is guided to the drainage system 200 through the first drainage piping 60A. The liquid received in the second cup 72B is guided to the drainage system 200 through the second drainage piping 60B.

[0043] The processing unit 2 includes a guard lifting unit 74 that raises and lowers the first guard 71A and the second guard 71B separately. The guard lifting unit 74 raises and lowers the first guard 71A between a lower position and an upper position. The guard lifting unit 74 raises and lowers the second guard 71B between a lower position and an upper position. When the first guard 71A and the second guard 71B are both in the upper position, liquid splashed from the substrate W is received by the second guard 71B. When the second guard 71B is in the lower position and the first guard 71A is in the upper position, liquid splashed from the substrate W is received by the first guard 71A.

[0044] The guard lifting unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first guard 71A, a first motor (not shown) that provides a driving force to the first ball screw, a second ball screw mechanism (not shown) coupled to the second guard 71B, and a second motor (not shown) that provides a driving force to the second ball screw mechanism. The guard lifting unit 74 is also called a guard lifter.

[0045] The first moving nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (discharges) a processing liquid toward the upper surface of the substrate W held on the spin chuck 5. The first moving nozzle 9 is also an example of a residue removing liquid nozzle (residue removing liquid supply unit, residue removal processing unit) that supplies (discharges) a first organic solvent as a residue removing liquid toward the upper surface of the substrate W held on the spin chuck 5. Of course, the processing liquid supply unit and the residue removing liquid supply unit may be provided with separate nozzles.

[0046] The first movable nozzle 9 is moved horizontally and vertically by the first nozzle movement unit 37. The first movable nozzle 9 can move between a central position and a home position (retracted position). When the first movable nozzle 9 is located at the central position, it faces the center of rotation of the upper surface of the substrate W. The center of rotation of the upper surface of the substrate W is the position at which the upper surface of the substrate W intersects with the rotation axis A1.

[0047] When the first movable nozzle 9 is located at the home position, it does not face the upper surface of the substrate W, and is located outside the processing cup 7 in a plan view. The first movable nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0048] The first nozzle moving unit 37 includes, for example, a rotating shaft (not shown) along the vertical direction, an arm (not shown) connected to the rotating shaft and the first moving nozzle 9 and extending horizontally, and a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

[0049] The rotary shaft drive unit swings the arm by rotating the rotary shaft around a vertical axis of rotation. Furthermore, the rotary shaft drive unit moves the arm up and down by raising and lowering the rotary shaft along the vertical direction. The first movable nozzle 9 is fixed to the arm. As the arm swings and rises and falls, the first movable nozzle 9 moves horizontally and vertically.

[0050] The first moving nozzle 9 is connected to a processing liquid pipe 41 that guides the processing liquid. When a processing liquid valve 51 installed in the processing liquid pipe 41 is opened, the processing liquid is continuously discharged downward from the first moving nozzle 9. The first moving nozzle 9 is further connected to a residue removing liquid pipe 40. When a residue removing liquid valve 50 installed in the residue removing liquid pipe 40 is opened, a first organic solvent as a residue removing liquid is continuously discharged downward from the first moving nozzle 9.

[0051] The processing liquid discharged from the first moving nozzle 9 contains a solute and a solvent. This processing liquid is solidified or hardened by volatilization (evaporation) of at least a portion of the solvent. This processing liquid solidifies or hardens on the substrate W to form a processing film that retains objects to be removed (foreign matter), such as particles, present on the substrate W. The solute typically contains a polymer. Therefore, the processing film is typically a polymer film. The solvent typically contains an organic solvent.

[0052] Here, "solidification" refers to the solidification of a solute due to forces acting between molecules or atoms, for example, as a result of the volatilization (evaporation) of a solvent. "Hardening" refers to the solidification of a solute due to chemical changes such as polymerization or crosslinking. Therefore, "solidification or hardening" refers to the "solidification" of a solute due to various factors.

[0053] The solute in the processing liquid discharged from the first moving nozzle 9 may include, for example, a first component and a second component. For example, the amount (content) of the first component contained in the processing liquid is less than the amount (content) of the second component contained in the processing liquid. The first component is a highly soluble component that has a relatively high solubility (solubility) in the stripping liquid described below (i.e., is soluble in the stripping liquid). The second component is a low-solubility component that has a relatively low solubility (solubility) in the stripping liquid described below (e.g., is insoluble or poorly soluble in the stripping liquid).

[0054] The first component and the second component are, for example, synthetic resins having properties different from each other. The solvent contained in the treatment liquid discharged from the first moving nozzle 9 may be any liquid that dissolves the first component and the second component.

[0055] Examples of synthetic resins used as the solute include acrylic resins, phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethane, polyimide, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, polyamide, polyacetal, polycarbonate, polyvinyl alcohol, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polysulfone, polyether ether ketone, and polyamide imide.

[0056] Examples of solvents that can dissolve synthetic resins include IPA, PGEE (propylene glycol monoethyl ether), PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), and EL (ethyl lactate).

[0057] The first organic solvent used as the residue removal liquid is an organic solvent capable of dissolving the treatment film formed when the treatment liquid solidifies, i.e., a dissolving liquid. Therefore, the residue removal liquid supply unit is an example of a dissolving liquid supply unit. Typically, it is preferable to use the solvent of the treatment liquid as the first organic solvent (residue removal liquid). In other words, the treatment film is soluble in the residue removal liquid. In this embodiment, the residue removal liquid (dissolving liquid) is an example of the "second liquid."

[0058] The second moving nozzle 10 is an example of a stripping liquid supply unit that supplies (discharges) a stripping liquid toward the upper surface of the substrate W held by the spin chuck 5, and is an example of a processed film removal unit that supplies the stripping liquid to strip a processed film 100 on the substrate W and remove it outside the substrate W. In this embodiment, the second moving nozzle 10 is also an example of a rinsing liquid supply unit that supplies (discharges) a second organic solvent as a rinsing liquid toward the upper surface of the substrate W held by the spin chuck 5. Of course, the stripping liquid supply unit and the rinsing liquid supply unit may be provided with separate nozzles.

[0059] The second movable nozzle 10 is moved in the horizontal and vertical directions by the second nozzle moving unit 38. The second movable nozzle 10 can move between a central position and a home position (retracted position).

[0060] When the second movable nozzle 10 is located at the central position, it faces the center of rotation of the upper surface of the substrate W. When the second movable nozzle 10 is located at the home position, it does not face the upper surface of the substrate W, and is located outside the processing cup 7 in a plan view. The second movable nozzle 10 can move closer to the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0061] The second nozzle moving unit 38 has a configuration similar to that of the first nozzle moving unit 37. That is, the second nozzle moving unit 38 includes, for example, a rotating shaft (not shown) along the vertical direction, an arm (not shown) that is connected to the rotating shaft and the second moving nozzle 10 and extends horizontally, and a rotating shaft drive unit (not shown) that raises and lowers the rotating shaft and rotates it.

[0062] The second moving nozzle 10 is connected to a remover liquid pipe 42 that guides the remover liquid to the second moving nozzle 10. When a remover liquid valve 52 installed in the remover liquid pipe 42 is opened, the remover liquid is continuously discharged downward from the discharge port of the second moving nozzle 10.

[0063] The second moving nozzle 10 is also connected to a rinse liquid pipe 43 that guides a second organic solvent as a rinse liquid to the second moving nozzle 10. When a rinse liquid valve 53 installed in the rinse liquid pipe 43 is opened, the rinse liquid (second organic solvent) is continuously discharged downward from the discharge port of the second moving nozzle 10.

[0064] The stripping liquid is a liquid for stripping the treatment film on the substrate W from the upper surface of the substrate W. The stripping liquid is a liquid that dissolves the first component contained in the solute of the treatment liquid more easily than the second component contained in the solute of the treatment liquid. In other words, the stripping liquid is a liquid in which the solubility (solubility) of the first component in the stripping liquid is higher than the solubility (solubility) of the second component in the stripping liquid. The stripping liquid is preferably a liquid that can be stripped from the surface of the substrate W and discharged outside the substrate W while suppressing dissolution of the treatment film formed by solidifying the treatment liquid (for example, specifically, without dissolving anything other than a small amount of the first component). In other words, it is preferable that the majority of the treatment film (i.e., the solid second component) is substantially insoluble or poorly soluble in the stripping liquid. In this case, the treatment film is referred to as being insoluble or poorly soluble in the stripping liquid in this specification. In this embodiment, the stripping liquid is an example of a "first liquid."

[0065] The stripping liquid is, for example, a water-based stripping liquid. Examples of water-based stripping liquids include DIW (deionized water), carbonated water, electrolytic ionized water, hydrogen water, ozone water, diluted hydrochloric acid water (for example, about 10 ppm to 100 ppm), alkaline aqueous solution, etc. Examples of alkaline aqueous solution include SC1 liquid, ammonia aqueous solution, aqueous solution of quaternary ammonium hydroxide such as TMAH, choline aqueous solution, etc.

[0066] The rinse liquid (second organic solvent) is a liquid that can replace the residue removal liquid (first organic solvent) on the substrate W. The second organic solvent is preferably a volatile liquid that volatilizes due to the rotation (spin drying) of the substrate W. Examples of the second organic solvent preferably include at least one of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene, and may be a mixture of at least one of these with DIW. Typically, the second organic solvent includes IPA, and may be a mixture of IPA and DIW.

[0067] The lower surface nozzle 12 is inserted into a through-hole 21a that opens in the center of the upper surface of the spin base 21. The outlet 12a of the lower surface nozzle 12 is exposed from the upper surface of the spin base 21. The outlet 12a of the lower surface nozzle 12 faces a central region of the lower surface of the substrate W from below. The central region of the lower surface of the substrate W is a region on the lower surface of the substrate W that includes the center of rotation of the substrate W.

[0068] A heat medium pipe 83 that guides a heat medium to the lower surface nozzle 12 is connected to the lower surface nozzle 12. When a heat medium valve 88 provided in the heat medium pipe 83 is opened, the heat medium is continuously discharged from the lower surface nozzle 12 toward the central region of the lower surface of the substrate W.

[0069] The lower surface nozzle 12 is an example of a heat medium supply unit that supplies a heat medium to the substrate W for heating the substrate W. The lower surface nozzle 12 is also a heating unit that heats the substrate W, thereby heating the processing film on the substrate W. The heating unit is an example of an evaporation promotion unit that promotes evaporation of the solvent in the processing film.

[0070] The heat medium discharged from the lower nozzle 12 is, for example, high-temperature DIW having a temperature (e.g., 60°C to 80°C) higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid. The heat medium discharged from the lower nozzle 12 is not limited to high-temperature DIW, and may be a high-temperature gas such as a high-temperature inert gas or high-temperature air having a temperature (e.g., 60°C to 80°C) higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid.

[0071] Instead of heating the substrate W with a heat medium, the substrate W may be heated by a heater 25. For example, the heater 25 may be an electric heater embedded in the spin base 21. Such a heater 25 is an example of a heating unit that heats a processing film on the substrate W, and is therefore an example of an evaporation promotion unit that promotes evaporation of a solvent in the processing film.

[0072] Although not shown in the figure, the lower surface nozzle 12 may be further connected to another pipe that guides a stripping liquid, a residue removal liquid, etc. for cleaning the lower surface of the substrate W, and these liquids may be capable of being ejected from the lower surface nozzle 12 toward the lower surface of the substrate W.

[0073] FIG. 3 is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus 1. As shown in FIG.

[0074] The controller 3 includes a microcomputer, and controls the control objects provided in the substrate processing apparatus 1 according to a predetermined control program.

[0075] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B that stores a control program. The controller 3 is configured to perform various controls for substrate processing by the processor 3A executing the control program.

[0076] In particular, the controller 3 is programmed to control the transfer robots IR and CR, the spin motor 23, the first nozzle moving unit 37, the second nozzle moving unit 38, the guard lifting unit 74, the valves 50, 51, 52, 53, 88, the heater 25, and the like.

[0077] FIG. 4 is a flowchart illustrating an example of a substrate processing method executed by the substrate processing apparatus 1, and FIGS. 5A to 5G are views illustrating the main steps.

[0078] This substrate processing method performs a foreign matter removal process to remove foreign matter (particles) adhering to a main surface Wf of a substrate W, which has a patterned main surface Wf on which a concave-convex pattern is formed. A typical example of the substrate W is a semiconductor wafer. In this case, the substrate processing method of this embodiment is mainly performed for the purpose of removing foreign matter from the main surface of a semiconductor wafer (such as a silicon wafer) in the front-end (FEOL (front-end-of-line) process). The concave-convex pattern includes, for example, fine convex structures formed on the main surface of the substrate W and concave portions (grooves) formed between adjacent structures. The structures forming the convex portions may include an insulating film or a conductive film. Alternatively, the structures may be a laminated film formed by stacking multiple films. The concave-convex pattern is, for example, a fine pattern with an aspect ratio of 3 or more. The aspect ratio of the concave-convex pattern is, for example, 10 to 50 (e.g., 25). The width of the structures forming the convex portions may be approximately 10 nm to 45 nm (e.g., 20 nm). The distance between the structures, i.e., the width of the recesses, may be about 10 nm to several μm (for example, 30 nm). The height of the structures constituting the protrusions (pattern height) may be about 50 nm to 5 μm (for example, 500 nm).

[0079] In this example, the treatment liquid uses a water-insoluble organic solvent (e.g., PGMEA) as its solvent. Therefore, the treatment film formed when the treatment liquid solidifies on the substrate W is insoluble or poorly soluble in DIW. Therefore, a water-based liquid that does not dissolve the treatment film, specifically DIW, is used as the stripper liquid. The stripper liquid may contain a liquid other than DIW that does not easily dissolve the treatment film (e.g., IPA). The first organic solvent used as the residue removal liquid (dissolving liquid) is an organic solvent that can dissolve the treatment film. In this example, the same organic solvent (e.g., PGMEA) as the solvent of the treatment liquid is used. That is, the treatment film is soluble in the first organic solvent used as the residue removal liquid. The second organic solvent used as a rinse liquid to replace the residue removal liquid (first organic solvent) on the substrate W can be, for example, IPA. The second organic solvent may be a liquid that does not easily dissolve the treatment film on the substrate W. For example, when the solvent of the treated film is PGMEA, the treated film is insoluble or poorly soluble in IPA.

[0080] The substrate processing method includes a processing liquid supply process 171 (see FIG. 5A) for supplying a processing liquid 91 to a main surface Wf of the substrate W, and a processing film formation process 172 (see FIG. 5B) for solidifying or curing the processing liquid 91 on the main surface Wf to form a processing film 100 on the main surface Wf.

[0081] 5A, while the substrate W is held and rotated by the spin chuck 5 (at a rotation speed of, for example, several tens of rpm to 200 rpm), the processing liquid valve 51 is opened and the processing liquid 91 is discharged from the first moving nozzle 9 toward the center of the main surface Wf (upper surface) of the substrate W. The discharged processing liquid 91 is subjected to centrifugal force on the main surface Wf of the substrate W and spreads over the entire main surface Wf, forming a processing liquid film 101 (a liquid film of the processing liquid 91) that covers the entire main surface Wf. That is, the processing liquid film 101 that covers the entire main surface Wf of the substrate W is formed by so-called spin coating. At this time, for example, the second guard 71B of the guard 71 may be disposed at a position where it receives the liquid that is spun outward from the substrate W.

[0082] In the treatment film forming process 172, as shown in FIG. 5B , the solvent component of the treatment liquid film 101 formed on the main surface Wf evaporates, solidifying or curing the treatment liquid film 101 to form a treatment film 100. Specifically, the treatment liquid valve 51 is closed to stop the discharge of the treatment liquid 91 from the first moving nozzle 9. The spin motor 23 drives the spin chuck 5 to continue rotating the substrate W, and the rotation may be accelerated as necessary (for example, to about 1000 rpm). This evaporates the solvent in the treatment liquid film 101. To promote evaporation of the solvent, the substrate W may also be heated. The substrate W can be heated by opening the heat medium valve 88 and discharging a heat medium from the discharge port 12a of the lower nozzle 12 toward the lower surface of the substrate W (the main surface opposite the main surface Wf). Alternatively, the substrate W can be heated by energizing the heater 25 provided in the spin base 21. The processed film 100 may be formed in a semi-solidified or semi-cured state by rotating the substrate W using the spin chuck 5, and then the processed film 100 may be heated via the substrate W to promote evaporation of the solvent, thereby forming a completely solidified or cured processed film 100. The spin motor 23, the lower nozzle 12, the heat medium valve 88, the heater 25, etc. are examples of the "processed film forming unit."

[0083] After the treatment film forming step 172, the substrate processing method includes a peeling step 173 in which the treatment film 100 is peeled off from the main surface Wf and removed outside the substrate W (see FIG. 5C ). The peeling step 173 includes, for example, a stripping liquid supplying step in which a stripping liquid 93 (e.g., DIW) for peeling the treatment film 100 from the main surface Wf is supplied toward the main surface Wf of the substrate W.

[0084] In the peeling step 173, as shown in FIG. 5C , the remover liquid valve 52 is opened, and the remover liquid 93 is discharged from the second moving nozzle 10 toward the upper surface of the substrate W. The discharged remover liquid 93 is subjected to centrifugal force on the substrate W and spreads over the entire main surface Wf of the substrate W. The remover liquid 93 reaches the interface between the substrate W and the treatment film 100 formed on the main surface Wf of the substrate W, and spreads along the interface over the entire main surface Wf of the substrate W. This allows the treatment film 100 to be peeled off from the substrate W. The remover liquid piping 42, the remover liquid valve 52, the second moving nozzle 10 (removal liquid nozzle), etc. are examples of a "removal unit."

[0085] For example, the substrate W may be held and rotated by the spin chuck 5 (at a rotation speed of, for example, 800 rpm) while the second moving nozzle 10 discharges the remover liquid 93 onto the center of the upper surface of the substrate W, and after the remover liquid 93 has spread over the entire main surface Wf of the substrate W, the rotation of the substrate W may be slowed down or stopped to perform a puddle step in which a liquid film of the remover liquid 93 is maintained on the substrate W. It is preferable to perform the puddle step for a time sufficient for the remover liquid 93 to reach the interface between the processing film 100 and the substrate W and to spread over the entire interface.

[0086] After the treatment film 100 has been peeled off, the substrate W is rotated by the spin chuck 5, and the peeled treatment film 100 is removed from the substrate W together with the stripping solution 93 by centrifugal force in a removal step 174 (see FIG. 5D). The peeled treatment film 100 is typically separated into multiple film fragments, but the treatment film 100 does not necessarily have to be separated, and may remain as a single film fragment and be removed from the substrate W together with the stripping solution 93.

[0087] In the peeling step 173 and the removal step 174, for example, the guard 71 may be positioned so that the first guard 71A receives the liquid that is spun outward from the substrate W. As a result, in the peeling step 173, the stripping liquid (DIW) discharged from the substrate W is received by the first guard 71A and guided to the first drainage pipe 60A. Also, in the removal step 174, film fragments of the processing film 100 peeled from the surface of the substrate W are carried away by the stripping liquid, received by the first guard 71A, and guided to the first drainage pipe 60A. In this way, the removal step 174 is an example of a "film fragment discharge step" in which film fragments of the processing film are guided to the drainage pipe by the stripping liquid, which is an example of a "first liquid." Also, the guard 71 and the like are an example of a "film fragment discharge unit."

[0088] Before or during the stripping step 173, a path for the stripping liquid to reach the interface between the treatment film 100 and the substrate W is formed.

[0089] For example, a peripheral portion removing step may be performed before the peeling step 173 to selectively remove the peripheral portion (bevel portion) of the treated film 100. Specifically, a dissolving liquid (e.g., a first organic solvent) capable of dissolving the treated film may be supplied toward the peripheral portion of the treated film 100 to selectively dissolve and remove the peripheral portion of the treated film 100. In this way, when the stripping liquid is supplied in the peeling step 173, it can be made to enter the interface between the treated film 100 and the substrate W from the peripheral portion of the substrate W.

[0090] Alternatively, before the peeling step 173, a dissolving liquid (e.g., a first organic solvent) may be ejected, for example, in the form of a mist, toward the treated film 100 to partially dissolve the treated film 100 and form a path penetrating the treated film 100. Alternatively, before or during the peeling step 173, high-pressure water may be supplied from a nozzle to form a cut in the treated film 100. Alternatively, the solute in the treatment liquid may contain a small amount of a crack-promoting component (the first component described above) that is soluble in the stripping liquid. In this case, during the peeling step 173, a path penetrating the treated film 100 and reaching the interface with the substrate W is formed, and the stripping liquid travels through this path to the interface between the treated film 100 and the substrate W and spreads along the interface.

[0091] The substrate processing method includes a residue removing step 175 (see FIG. 5E) of supplying a first organic solvent (e.g., PGMEA) as a residue removing solution 94 to the main surface Wf of the substrate W to dissolve and remove residues of the processed film 100 from the main surface Wf after the removing step 174. The first organic solvent as the residue removing solution 94 is a dissolving solution that dissolves the residues of the processed film 100 and is a residue removing solution for removing the residues.

[0092] In the residue removal process 175, as shown in FIG. 5E, the residue removal solution valve 50 is opened, and a first organic solvent (PGMEA, dissolving solution) is discharged as a residue removal solution 94 from the first movable nozzle 9 toward the upper surface of the substrate W. The discharged residue removal solution 94 is subjected to centrifugal force on the substrate W and spreads across the entire main surface Wf of the substrate W. The residue removal solution 94 dissolves residues of the processing film 100 remaining on the main surface Wf of the substrate W and removes them from the substrate W. For example, the substrate W may be held and rotated by the spin chuck 5 (for example, at a rotation speed of approximately 300 rpm) while the residue removal solution 94 is discharged from the first movable nozzle 9 toward the center of the upper surface of the substrate W. After the residue removal solution 94 has spread across the entire main surface Wf of the substrate W, the rotation of the substrate W may be slowed or stopped, thereby performing a puddling process to maintain a liquid film of the residue removal solution 94 on the substrate W. The puddling process is preferably performed for a time sufficient for the residue removal solution 94 to dissolve the residues of the processing film 100. Thereafter, the substrate W is rotated by the spin chuck 5, whereby the residue removal liquid 94 containing the dissolved residue is removed from the substrate W in an elimination step.

[0093] In the residue removal process 175, for example, the guard 71 may be positioned so that the second guard 71B receives the liquid that is spun outward from the substrate W. As a result, in the residue removal process 175, the residue removal liquid 94 discharged from the substrate W is received by the second guard 71B and guided to the second drainage pipe 60B. In this manner, the residue removal process 175 is an example of a "second liquid supply process" in which a residue removal liquid (first organic solvent, for example, PGMEA), which is an example of a "second liquid," is supplied to the drainage pipe. In addition, the residue removal liquid pipe 40, the residue removal liquid valve 50, the first moving nozzle 9 (residue removal liquid nozzle), the guard 71, etc. are examples of a "second liquid supply unit."

[0094] The substrate processing method also includes, after the residue removing step 175, a rinsing step 176 for removing the residue removing liquid 94 (first organic solvent) from the substrate W (see FIG. 5F). Specifically, a second organic solvent (e.g., IPA) is supplied as a rinsing liquid 95 to the main surface Wf of the substrate W to which the residue removing liquid 94 has adhered, and the residue removing liquid 94 (first organic solvent) is replaced with the rinsing liquid 95 (second organic solvent) and removed from the substrate W.

[0095] In the rinsing step 176, the rinsing liquid valve 53 is opened, and a rinsing liquid 95 (second organic solvent) is discharged from the second moving nozzle 10 toward the main surface Wf (upper surface) of the substrate W. The discharged rinsing liquid 95 is subjected to centrifugal force on the substrate W and spreads over the entire main surface Wf. The rinsing liquid 95 replaces the residue removal liquid 94 (first organic solvent) remaining on the main surface Wf of the substrate W and removes it from the substrate W. For example, while the substrate W is held and rotated by the spin chuck 5 (for example, at a rotation speed of 800 rpm), the rinsing liquid 95 is discharged from the second moving nozzle 10 onto the center of the upper surface of the substrate W. After the rinsing liquid 95 has spread over the entire surface of the substrate W (more precisely, over the entire upper surface of the processing film 100), the rotation of the substrate W may be slowed or stopped, and a puddle step may be performed in which a liquid film of the rinsing liquid 95 is maintained on the substrate W. The puddle step is preferably performed for a time sufficient for the rinsing liquid 95 to replace the residue removal liquid 94 on the substrate W. Thereafter, the substrate W is rotated by the spin chuck 5, whereby the residue removal liquid 94 can be removed from the substrate W together with the rinsing liquid 95.

[0096] In the rinsing step 176, for example, the guard 71 may be disposed in a position where the first guard 71A receives the liquid spun outward from the substrate W. As a result, in the rinsing step 176, the rinsing liquid 95 discharged from the substrate W is received by the first guard 71A and guided to the first drainage pipe 60A.

[0097] The substrate processing method also includes, after the rinsing step 176, a drying step 177 (typically a spin-drying step) for shaking off the liquid on the surface of the substrate W and drying it (see FIG. 5G). The rinsing liquid 95 (second organic solvent) on the surface of the substrate W is expelled outside the substrate W by centrifugal force and disappears from the surface of the substrate W by volatilization into the atmosphere. As in the rinsing step 176, the first guard 71A of the guard 71 may be positioned to receive the liquid that is shaken off outward from the substrate W.

[0098] 6A, 6B, and 6C show a first example configuration of the drainage system 200. Also, FIGS. 7A and 7B show a second example configuration of the drainage system 200.

[0099] The drainage system 200 includes a drainage pipe 60, a separation mechanism 110 provided in the drainage pipe 60, a first liquid storage mechanism 151, and a second liquid storage mechanism 152. The drainage pipe 60 includes a first drainage pipe 60A that guides the drainage received by the first guard 71A, and a second drainage pipe 60B that guides the drainage received by the second guard 71B.

[0100] The separation mechanism 110 is connected to the first drainage pipe 60A and the second drainage pipe 60B, and includes a drainage trap tank 111 that commonly accommodates and stores the drainage from the first drainage pipe 60A and the second drainage pipe 60B.

[0101] In the removal process 174 (see FIG. 5D), the stripping liquid (DIW) and film fragments of the treated film 100 are received by the first guard 71A and flow into the drain trap tank 111 through the first drain pipe 60A. In the residue removal process 175 (see FIG. 5E), the residue removal liquid (first organic solvent, PGMEA) that has dissolved the residue of the treated film 100 is received by the second guard 71B and flows into the drain trap tank 111 through the second drain pipe 60B. Therefore, the stripping liquid (DIW) and the residue removal liquid (first organic solvent, PGMEA) are mixed in the drain trap tank 111. In the rinsing process 176 (see FIG. 5F), the rinse liquid (second organic solvent, IPA) is received by the first guard 71A and flows into the drain trap tank 111 through the first drain pipe 60A. Therefore, in the waste liquid trap tank 111, the stripping liquid (for example, DIW), the residue removal liquid (first organic solvent, PGMEA), and the rinse liquid (second organic solvent, IPA) are mixed.

[0102] The membrane fragments of the treated membrane 100 that flow into the waste liquid trap tank 111 together with the stripping liquid are dissolved by the residue removal liquid (first organic solvent, PGMEA) that also flows into the waste liquid trap tank 111 (membrane fragment dissolving process). Therefore, the membrane fragments of the treated membrane 100 disappear in the waste liquid trap tank 111, thereby reducing the risk of clogging the waste liquid piping 60.

[0103] In this example, the first organic solvent (PGMEA), which is the residue removal liquid, is water-insoluble, and therefore the residue removal liquid and the stripper liquid (DIW) are incompatible with each other. The second organic solvent (IPA), which is the rinse liquid, is water-soluble, and therefore the rinse liquid and the stripper liquid (DIW) are compatible with each other. Furthermore, the treatment film 100 is soluble in the residue removal liquid (first organic solvent, PGMEA) and insoluble or poorly soluble in the stripper liquid (DIW). Furthermore, the treatment film 100 is also insoluble or poorly soluble in the rinse liquid (second organic solvent, IPA).

[0104] 6B, a first liquid layer 121 in which the stripping liquid and the rinsing liquid (second organic solvent) are dissolved in each other, and a second liquid layer 122 of the residue removal liquid (first organic solvent) in which the treatment film has been dissolved are formed in the waste liquid trap tank 111, and an interface 120 is formed to separate them into upper and lower layers. For example, if the density of the stripping liquid is greater than the density of the residue removal liquid (first organic solvent), the first liquid layer 121 will be located on the lower side, and the second liquid layer 122 will be located on the upper side.

[0105] The separation mechanism 110 further includes a first discharge port PA for discharging mainly the stripping liquid (an example of a first liquid) from the drainage trap tank 111, and a second discharge port PB for discharging mainly the residue removal liquid (a first organic solvent (an example of a second liquid)) from the drainage trap tank 111, which are connected to the bottom surface of the drainage trap tank 111. The separation mechanism 110 also includes a valve mechanism 112 that opens one of the first discharge port PA and the second discharge port PB and closes the other of the first discharge port PA and the second discharge port PB. The valve mechanism 112 has a float 113 that moves up and down following an interface 120 between a first liquid layer 121 and a second liquid layer 122 in the drainage trap tank 111, and is configured to be operated by the up and down movement of the float 113.

[0106] The drainage piping 60 further includes a third drainage piping 60C connecting the first drain port PA of the drainage trap tank 111 to the first liquid storage mechanism 151, and a fourth drainage piping 60D connecting the second drain port PB of the drainage trap tank 111 to the second liquid storage mechanism 152. A pump 161 and a valve 162 are provided in the third drainage piping 60C. By opening the valve 162 and operating the pump 161, the liquid discharged from the first drain port PA can be sent through the third drainage piping 60C to the first liquid storage mechanism 151. Similarly, a pump 163 and a valve 164 are provided in the fourth drainage piping 60D. By opening the valve 164 and operating the pump 163, the liquid discharged from the second drain port PB can be sent through the fourth drainage piping 60D to the second liquid storage mechanism 152. The pumps 161 and 163 and the valves 162 and 164 are controlled by a controller 3 (see FIG. 3).

[0107] The first liquid storage mechanism 151 includes a first tank 153. The first tank 153 primarily stores a liquid including a used stripping liquid (DIW). The liquid stored in the first tank 153 may be reused as a stripping liquid. That is, a stripping liquid pipe 42 may be connected to the first tank 153, and a pump 154 ​​and a filter 155 may be interposed in the stripping liquid pipe 42. By driving the pump 154, the stripping liquid stored in the first tank 153 is pumped out. After foreign matter (particles) is removed by the filter 155, the stripping liquid is supplied to the second moving nozzle 10 via the stripping liquid valve 52. In this case, the stripping liquid to be reused contains a rinsing liquid (a second organic solvent, for example, IPA). However, since the rinsing liquid (second organic solvent) hardly dissolves the processing film 100, it has almost no effect on the stripping action of the processing film 100. The pump 154 ​​is controlled by the controller 3 (see FIG. 3).

[0108] The second liquid storage mechanism 152 includes a second tank 156. The second tank 156 mainly stores a used residue removal liquid (a first organic solvent, for example, PGMEA). The liquid stored in the second tank 156 is preferably reused as the residue removal liquid. That is, a residue removal liquid pipe 40 may be connected to the second tank 156, and a pump 157 and a filter 158 may be interposed in the residue removal liquid pipe 40. When the pump 157 is driven, the residue removal liquid (first organic solvent) stored in the second tank 156 is pumped out, and after foreign matter (particles) are removed by the filter 158, the residue removal liquid is supplied to the first moving nozzle 9 via the residue removal liquid valve 50. In this case, the solute of the processing liquid (dissolved processing film 100) is dissolved in the reused residue removal liquid (first organic solvent), but this has almost no effect on the action of dissolving and removing residues of the processing film 100 on the substrate W. The pump 157 is controlled by the controller 3 (see FIG. 3).

[0109] In this way, the first liquid (mainly the stripping liquid) contained in the first liquid containing mechanism 151 can be reused in the stripping step. Similarly, the second liquid (mainly the residue removal liquid) contained in the second liquid containing mechanism 152 can be reused in the residue removal step, as described above. This allows for a reduction in the amounts of stripping liquid and residue removal liquid (first organic solvent) used, thereby reducing liquid consumption and contributing to a reduction in environmental impact and running costs.

[0110] 6A, 6B, and 6C, the valve mechanism 112 includes a lever 115 rotatably supported on a fulcrum 114 that is immovable relative to the drainage trap tank 111, a first valve member 116A and a second valve member 116B coupled to the lever 115, and a float 113 coupled to the lever 115. The lever 115 is supported at the fulcrum 114 so as to be rotatable about a horizontal rotation axis 114a. The first valve member 116A and the second valve member 116B are coupled to the lever 115 at positions opposite each other with respect to the fulcrum 114. The float 113 is coupled to the lever 115 on the opposite side of the fulcrum 114 from the first valve member 116A.

[0111] The first valve member 116A includes a first valve stem 117A whose base end (upper end in the illustrated example) is connected to the lever 115, and a first valve body 118A fixed to the tip end (lower end in the illustrated example) of the first valve stem 117A. The first valve body 118A is capable of seating on a first valve seat 119A provided in the first discharge port PA. The first valve member 116A and the first valve seat 119A constitute a first valve VA. The first valve VA is opened and closed by the up and down movement of the first valve member 116A, and connects the storage space of the drain trap tank 111 with the first discharge port PA (third drain pipe 60C).

[0112] Similarly, the second valve member 116B includes a second valve stem 117B whose base end (upper end in the illustrated example) is coupled to the lever 115, and a second valve body 118B fixed to the tip end (lower end in the illustrated example) of the second valve stem 117B. The second valve body 118B can be seated on a second valve seat 119B provided in the second drain port PB. The second valve member 116B and the second valve seat 119B form a second valve VB. The second valve VB is opened and closed by the up and down movement of the second valve member 116B, and connects the storage space of the drain trap tank 111 with the second drain port PB (fourth drain piping 60D).

[0113] The float 113 is configured so that its average density is between the density of the residue removal liquid (first organic solvent) and the density of the stripping liquid. The average density refers to the value obtained by dividing the mass of the float 113 by the volume of the float 113. Here, the float 113 is configured so that its average density is greater than the density of the residue removal liquid (first organic solvent) and less than the density of the stripping liquid. As a result, the float 113 rises to the liquid surface in the stripping liquid and sinks in the residue removal liquid (first organic solvent). Therefore, when the first liquid layer 121 and the second liquid layer 122 are present in the waste liquid trap tank 111, the float 113 is located near the interface 120. When the interface 120 moves up and down due to the inflow of the stripping liquid, the residue removal liquid (first organic solvent), the rinse liquid (second organic solvent), and film fragments of the treatment film, the float 113 moves up and down to follow the interface 120.

[0114] 6A, when no liquid is stored in the drainage trap tank 111, the float 113 is in a position in contact with the bottom surface of the drainage trap tank 111. In this state, the valve mechanism 112 is designed so that the first valve VA closes the first discharge port PA and the second valve VB opens the second discharge port PB.

[0115] 6B, when the first liquid layer 121 and the second liquid layer 122 are present in the drainage trap tank 111, the float 113 is positioned above the bottom surface of the drainage trap tank 111, causing the lever 115 to lift the first valve member 116A and push down the second valve member 116B. As a result, the first valve VA opens the first discharge port PA, and the second valve VB closes the second discharge port PB. As a result, the liquid (mainly the stripping liquid) constituting the lower first liquid layer 121 flows out from the first discharge port PA into the third drainage pipe 60C and is drained into the first liquid storage mechanism 151 (first discharge step).

[0116] As a result of this drainage, the interface 120 between the first liquid layer 121 and the second liquid layer 122 descends, and the float 113 is displaced downward accordingly. The lever 115 then lowers the first valve member 116A and raises the second valve member 116B. When the first liquid layer 121 disappears, the float 113 abuts against the bottom surface of the drain trap tank 111, as shown in FIG. 6C . The first valve VA then closes the first drain port PA, and the second valve VB opens the second drain port PB. As a result, the liquid (mainly the residue removal liquid (first organic solvent)) that constitutes the second liquid layer 122 flows out of the second drain port PB into the fourth drain pipe 60D and is drained into the second liquid storage mechanism 152 (second drainage step).

[0117] In this way, the liquid (such as a stripping liquid) constituting the first liquid layer 121 and the liquid (such as a residue removal liquid) constituting the second liquid layer 122 can be separated by the separation mechanism 110 (separation process 178, see Figure 4), and stored in the first liquid storage mechanism 151 and the second liquid storage mechanism 152, respectively (storage process 179, see Figure 4).

[0118] In the second configuration example shown in Figures 7A and 7B, the valve mechanism 112 includes a float 113 that moves up and down within the drain trap tank 111 while being guided by a guide rail 124, a lifting member 125 that is connected to the float 113 and moves up and down together with the float 113, and a first valve member 126A and a second valve member 126B that are connected to the lifting member 125.

[0119] The first valve member 126A includes a first valve stem 127A whose base end (upper end in the illustrated example) is connected to the lifting member 125, and a first valve body 128A fixed to the tip end (lower end in the illustrated example) of the first valve stem 127A. The first valve body 128A can be seated from above on a first valve seat 129A provided in the first discharge port PA. The first valve member 126A and the first valve seat 129A constitute a first valve VA. The first valve VA is opened by the upward movement of the first valve member 126A and closed by the downward movement of the first valve member 126A, thereby opening and closing the storage space of the drain trap tank 111 and the first discharge port PA (third drain piping 60C).

[0120] The second valve member 126B includes a second valve stem 127B whose base end (upper end in the illustrated example) is connected to the lifting member 125, and a second valve body 128B fixed to the tip end (lower end in the illustrated example) of the second valve stem 127B. The second valve body 128B can be seated from below on a second valve seat 129B provided in the second drain port PB. The second valve member 126B and the second valve seat 129B form a second valve VB. The second valve VB is opened by the downward movement of the second valve member 126B and closed by the upward movement of the second valve member 126B, thereby opening and closing the storage space of the drain trap tank 111 and the second drain port PB (fourth drain piping 60D).

[0121] The relationship between the average density of the float 113, the density of the residue removal liquid (first organic solvent), and the density of the stripping liquid is the same as in the first configuration example. As a result, the float 113 rises to the liquid surface in the stripping liquid and sinks in the residue removal liquid (first organic solvent). Therefore, when the first liquid layer 121 and the second liquid layer 122 are present in the waste liquid trap tank 111, the float 113 moves toward the vicinity of the interface 120. When the interface 120 moves up and down due to the inflow of the stripping liquid, the residue removal liquid (first organic solvent), the rinse liquid (second organic solvent), and pieces of the treatment film, the float 113 moves up and down to follow the interface 120. However, downward movement of the float 113 is restricted by the first valve member 126A seating on the first valve seat 129A from above, and upward movement of the float 113 is restricted by the second valve member 126B seating on the second valve seat 129B from below.

[0122] 7A, when the first liquid layer 121 and the second liquid layer 122 are present in the drain trap tank 111, the float 113 is positioned above the lowest position, causing the lifting member 125 to lift the first valve member 126A and the second valve member 126B. As a result, the first valve VA opens the first drain port PA, and the second valve VB closes the second drain port PB. As a result, the liquid (mainly the stripping liquid) constituting the lower first liquid layer 121 flows out from the first drain port PA into the third drain pipe 60C and is drained into the first liquid storage mechanism 151 (first drain step).

[0123] As a result of this drainage, the interface 120 between the first liquid layer 121 and the second liquid layer 122 descends, and the lifting member 125 descends along with the float 113, which in turn causes the first valve member 126A and the second valve member 126B to descend accordingly. When the first liquid layer 121 is removed, the float 113 is positioned at its lowest position, as shown in FIG. 7B . The first valve VA then closes the first discharge port PA, and the second valve VB opens the second discharge port PB. As a result, the liquid (mainly the residue removal liquid (first organic solvent)) that constitutes the second liquid layer 122 flows out of the second discharge port PB into the fourth drainage pipe 60D and is drained into the second liquid storage mechanism 152 (second discharge step).

[0124] In this way, the first liquid (such as a stripping liquid) constituting the first liquid layer 121 and the second liquid (such as a residue removal liquid) constituting the second liquid layer 122 can be separated by the separation mechanism 110 (separation process 178, see Figure 4), and stored in the first liquid storage mechanism 151 and the second liquid storage mechanism 152, respectively (storage process 179, see Figure 4).

[0125] Figures 8A and 8B show a third configuration example of the drainage system 200. In Figures 8A and 8B, parts corresponding to those shown in Figures 6A to 6C and 7A to 7B described above are given the same reference numerals, and descriptions thereof will be omitted.

[0126] The drainage system 200 includes a drainage pipe 60, a separation mechanism 110 provided in the drainage pipe 60, a first liquid storage mechanism 151, and a second liquid storage mechanism 152. The drainage pipe 60 includes a first drainage pipe 60A that guides the drainage received by the first guard 71A (see FIG. 2), and a second drainage pipe 60B that guides the drainage received by the second guard 71B (see FIG. 2).

[0127] In this configuration example, the separation mechanism 110 is also connected to the first drainage pipe 60A and the second drainage pipe 60B, and includes a drainage trap tank 111 that commonly accommodates and stores the drainage from the first drainage pipe 60A and the second drainage pipe 60B. As in the first and second configuration examples, dissolution of membrane fragments progresses in the drainage trap tank 111 (membrane fragment dissolving step).

[0128] On the other hand, in this configuration example, the separation mechanism 110 does not include the valve mechanism 112 (see FIGS. 6A and 7A), but instead includes a cooling unit 131 attached to the drainage trap tank 111. In this configuration example, the separation mechanism 110 further includes a heating unit 132 attached to the drainage trap tank 111. The cooling unit 131 cools the liquid contained in the drainage trap tank 111. More specifically, the cooling unit 131 is operated to freeze the liquid with a higher melting point of the first liquid layer 121 and the second liquid layer 122, which are separated into upper and lower liquid layers in the drainage trap tank 111, and transition it to a solid phase, while maintaining the liquid with a lower melting point in a liquid phase. The heating unit 132 heats the liquid layer (one of the first liquid layer 121 and the second liquid layer 122) that has transitioned to a solid phase by the cooling unit 131, thereby returning it to a liquid phase.

[0129] For example, if the density of the stripping liquid is greater than the density of the residue removal liquid (first organic solvent), the first liquid layer 121 will be located on the lower side and the second liquid layer 122 will be located on the upper side. This density relationship also applies when the stripping liquid is DIW and the first organic solvent used as the residue removal liquid is PGMEA. The melting point of DIW is 0°C, and the melting point of PGMEA is −67°C. Therefore, the cooling unit 131 cools the liquid in the waste liquid trap tank 111 to a temperature higher than −67°C and lower than 0°C, freezing the stripping liquid (DIW) that forms the first liquid layer 121 and maintaining the residue removal liquid (PGMEA) that forms the second liquid layer 122 in a liquid phase. Because the first liquid layer 121 is located on the lower side, the cooling unit 131 is disposed in a relatively lower region of the waste liquid trap tank 111, enabling efficient cooling of the first liquid layer 121. The heating unit 132 is also arranged in a similar manner, so that the first liquid layer 121 that has transitioned to the solid phase can be efficiently heated.

[0130] The cooling unit 131 is preferably provided in the effluent trap tank 111 in a position that allows easy contact with the first liquid layer 121 or the second liquid layer 122, whichever has a higher melting point (i.e., the liquid layer to be transitioned to a solid phase), thereby enabling efficient cooling. Similarly, the heating unit 132 is preferably provided in the effluent trap tank 111 in a position that allows easy contact with the first liquid layer 121 or the second liquid layer 122, whichever has a higher melting point (i.e., the liquid layer to be transitioned to a solid phase), thereby enabling efficient heating. However, as described below, the heating unit 132 heats the liquid layer that has transitioned to a solid phase after the liquid layer maintained in the liquid phase is drained out of the effluent trap tank 111. If the liquid layer that has transitioned to a solid phase moves downward in the effluent trap tank 111 due to gravity as the liquid layer maintained in the liquid phase is drained, the heating unit 132 is preferably provided in a relatively lower region of the effluent trap tank 111, thereby enabling increased heating efficiency. Incidentally, since the solid phase may be changed to the liquid phase by natural thawing, the provision of the heating unit 132 is not essential.

[0131] The cooling unit 131 and the heating unit 132 are controlled by a controller 3 (see FIG. 3). The cooling unit 131 may be a rod-shaped cooler, such as the Chiller series from Sanox Corporation or the Coolant Chiller from Takaki Kaisan Co., Ltd. The heating unit 132 may be a rod-shaped heater.

[0132] The separation mechanism 110 further includes a discharge port P for discharging mainly the stripping liquid (first liquid: a liquid with a relatively high melting point) from the waste liquid trap tank 111, and this discharge port P is connected to the bottom of the waste liquid trap tank 111. The separation mechanism 110 also includes a suction unit 133 for sucking mainly the residue removal liquid (first organic solvent (second liquid: a liquid with a relatively low melting point and maintained in a liquid phase) from the waste liquid trap tank 111. The suction unit 133 includes a suction pipe 134. The suction pipe 134 has a suction head 135 at its tip that is introduced into the waste liquid trap tank 111, and is provided with a head lifting mechanism 136 for moving the suction head 135 up and down. The suction pipe 134 may have an expansion pipe section 137 in the middle that absorbs the up and down movement caused by the head lifting mechanism 136. The head lifting mechanism 136 is controlled by the controller 3 (see FIG. 3).

[0133] The drainage pipe 60 includes a third drainage pipe 60C that connects the discharge port P of the drainage trap tank 111 to the first liquid storage mechanism 151, and a fourth drainage pipe 60D that connects the suction unit 133 to the second liquid storage mechanism 152.

[0134] As described above, a first liquid layer 121 in which the stripping liquid and the rinsing liquid (second organic solvent) are dissolved in each other and a second liquid layer 122 of the residue removal liquid (first organic solvent) in which the treatment film has been dissolved are formed in the waste liquid trap tank 111, and an interface 120 is formed to separate them into upper and lower layers. For example, if the density of the stripping liquid is greater than the density of the residue removal liquid (first organic solvent), the first liquid layer 121 is located on the lower side and the second liquid layer 122 is located on the upper side.

[0135] In this state where the liquid layer is separated into the first liquid layer 121 and the second liquid layer 122, the controller 3 operates the cooling unit 131. As a result, the first liquid layer 121, which mainly contains the stripping liquid (DIW), is frozen and transitions from the liquid phase to the solid phase (freezing process).

[0136] After the first liquid layer 121 freezes, the controller 3 operates the head lifting mechanism 136, which lowers the suction head 135 from above the interface 120 within the drain trap tank 111. The suction head 135 is lowered until it hits the surface of the frozen first liquid layer 121, and is thereby positioned at the interface 120. In this state, the suction unit 133 is operated. Specifically, the controller 3 opens the valve 164 arranged in the fourth drainage pipe 60D and operates the pump 163. As a result, the liquid (mainly the residue removal liquid) that constitutes the second liquid layer 122, which is maintained in the liquid phase, is sucked from the suction head 135 into the suction pipe 134, guided to the fourth drainage pipe 60D, and then guided through this fourth drainage pipe 60D to the second liquid storage mechanism 152. In this way, the suction unit 133 sucks the liquid that constitutes the second liquid layer 122 and drains it from the drain trap tank 111 to the second liquid storage mechanism 152 (first discharge step). When the second liquid layer 122 is gone, the controller 3 closes the valve 164 and stops the pump 163, thereby stopping the suction operation of the suction unit 133. Note that the suction unit 133 may be provided with a pump other than the pump 163 as a suction source.

[0137] Next, the controller 3 stops the cooling by the cooling unit 131 and causes the heating unit 132 to heat the solid first liquid layer 121. This causes the first liquid layer 121 to melt and transition from the solid phase to the liquid phase (melting step). Thereafter, the controller 3 opens the valve 162 of the third drainage pipe 60C and operates the pump 161. This causes the liquid (mainly the stripping liquid) that constitutes the first liquid layer 121 to be drained from the discharge port P of the drainage trap tank 111 through the third drainage pipe 60C to the first liquid storage mechanism 151 (second discharge step).

[0138] In this case, the discharge port P and the valve 162 are an example of a "discharge unit." The pump 161 disposed in the third discharge pipe 60C also contributes to the discharge of the liquid, and therefore constitutes a discharge unit. However, since the liquid constituting the first liquid layer 121 can be discharged using gravity, the pump 161 may be omitted in some cases.

[0139] In this way, the first liquid (such as a stripping liquid) constituting the first liquid layer 121 and the second liquid (such as a residue removal liquid) constituting the second liquid layer 122 can be separated by the separation mechanism 110 (separation process 178, see Figure 4), and stored in the first liquid storage mechanism 151 and the second liquid storage mechanism 152, respectively (storage process 179, see Figure 4).

[0140] Figure 9 shows a fourth configuration example of the drainage system. In Figure 9, parts corresponding to those shown in Figures 6A to 6C, 7A to 7B, and 8A to 8B are given the same reference numerals, and descriptions thereof will be omitted.

[0141] The drainage system 200 includes a drainage pipe 60, a separation mechanism 110 provided in the drainage pipe 60, a first liquid storage mechanism 151, and a second liquid storage mechanism 152. The drainage pipe 60 includes a first drainage pipe 60A that guides the drainage received by the first guard 71A, and a second drainage pipe 60B that guides the drainage received by the second guard 71B.

[0142] In this configuration example, the separation mechanism 110 is also connected to the first drainage pipe 60A and the second drainage pipe 60B, and includes a drainage trap tank 111 that commonly accommodates and stores the drainage from the first drainage pipe 60A and the second drainage pipe 60B. As in the first to third configuration examples, dissolution of membrane fragments progresses in the drainage trap tank 111 (membrane fragment dissolving step).

[0143] On the other hand, in this configuration example, the separation mechanism 110 does not include a valve mechanism 112 (see FIGS. 6A and 7A) or a suction unit 133 (see FIG. 8A), but includes an ion exchange resin unit 140 connected to the discharge port P via a fifth drainage pipe 60E. A valve 142 controlled by the controller 3 (see FIG. 3) is installed in the fifth drainage pipe 60E. The ion exchange resin unit 140 includes one or more ion exchange resin columns 141. The ion exchange resin column 141 contains, for example, a cation exchange resin that adsorbs acetate ions, thereby selectively extracting one of the first liquid (e.g., water) and the second liquid (e.g., an organic solvent) to separate them. The ion exchange resin column 141 discharges the first liquid from a first port 141a and the second liquid from a second port 141b. Therefore, the third drainage pipe 60C is connected to the first port 141a, and the fourth drainage pipe 60D is connected to the second port 141b. If necessary, a plurality of ion exchange resin columns 141 can be connected in parallel between the fifth drainage pipe 60E and the drainage pipes 60C and 60D to increase the liquid separation processing capacity.

[0144] When the valve 142 is opened and the liquid in the drain trap tank 111 is supplied to the ion exchange resin unit 140 from the discharge port P, the stripping liquid (DIW) and the rinse liquid (second organic solvent, IPA) are discharged from the first port 141a of the ion exchange resin column 141, and the residue removal liquid (first organic solvent) is discharged from the second port 141b of the ion exchange resin column 141. This allows the stripping liquid (DIW) to be guided to the first liquid storage mechanism 151, and the residue removal liquid (first organic solvent, PGMEA) to be guided to the second liquid storage mechanism 152.

[0145] In this way, the first liquid (stripping liquid) and the second liquid (residue removal liquid) can be separated by the separation mechanism 110 (ion exchange resin unit 140) (separation step 178, see Figure 4), and stored in the first liquid storage mechanism 151 and the second liquid storage mechanism 152, respectively (storage step 179, see Figure 4).

[0146] Specific examples of the ion exchange resin column 141 that constitutes the ion exchange resin unit 140 include AG 50W-X8 and AG 50W-X12 provided by Bio-Rad, Ionac AG-1 provided by Merck Millipore, the XBridge series provided by Waters, and the Eclipse series provided by Agilent Technologies.

[0147] In addition, since the two types of liquids separated in the ion exchange resin unit 140 do not need to separate into two liquid layers in the drain trap tank 111, they may be compatible with each other, may have similar densities, and may have similar melting points.

[0148] Fig. 10 shows an example of the configuration of a processing unit according to another embodiment of the present invention. In describing this embodiment, reference will be made again to Fig. 1 described above. That is, Fig. 10 shows another example of the configuration of a processing unit 2 provided in a substrate processing apparatus 1. In Fig. 10, parts corresponding to those in Fig. 2 are designated by the same reference numerals, and descriptions thereof will be omitted.

[0149] In this embodiment, the processing film is stripped without using a stripping liquid. That is, a stripping liquid supply unit is not provided. Instead, a stripping gas nozzle 250 is provided that ejects a stripping gas toward the upper surface of the substrate W. The stripping gas nozzle 250 is an example of a gas stripping unit and an example of a "stripping section."

[0150] The stripping gas nozzle 250 is moved in the horizontal and vertical directions by a third nozzle movement unit 251. The third nozzle movement unit 251 moves the stripping gas nozzle 250 along an arc-shaped path that is approximately along the diameter of the substrate W along the upper surface of the substrate W. The third nozzle movement unit 251 has a configuration similar to that of the first nozzle movement unit 37. That is, the third nozzle movement unit 251 includes, for example, a vertical rotation shaft (not shown), an arm (not shown) that is connected to the rotation shaft and the stripping gas nozzle 250 and extends horizontally, and a rotation shaft drive unit (not shown) that raises and lowers the rotation shaft and rotates it.

[0151] The stripping gas nozzle 250 is connected to a stripping gas pipe 252 that guides stripping gas to the stripping gas nozzle 250. When an opening / closing valve 253 attached to the stripping gas pipe 252 is opened, the stripping gas is continuously discharged downward from the outlet of the stripping gas nozzle 250 at a flow rate that corresponds to the opening of a flow rate adjustment valve 254 that changes the flow rate of the stripping gas. Figure 10 shows an example in which the stripping gas nozzle 250 discharges nitrogen gas, which is an example of a stripping gas. The stripping gas may be an inert gas other than nitrogen gas, or may be a gas other than an inert gas.

[0152] As in the previous embodiment, the first moving nozzle 9 is connected to a processing liquid pipe 41 that guides the processing liquid. When a processing liquid valve 51 provided in the processing liquid pipe 41 is opened, the processing liquid is continuously discharged downward from the first moving nozzle 9.

[0153] However, in this example, the processing liquid uses a water-soluble solvent, and therefore the processing film formed when the processing liquid solidifies on the substrate W is soluble in DIW. Therefore, DIW is not used to strip the processing film, and the processing film is stripped by spraying a stripping gas.

[0154] The treatment liquid (polymer solution) is a solution containing a polymer, which corresponds to the solute, and a solvent in which the polymer dissolves. The polymer is a water-soluble polymer (hydrophilic polymer) that dissolves in water. The solvent is, for example, water. Therefore, the treatment liquid is an aqueous polymer solution. The treatment liquid may contain components other than the water-soluble polymer and water. The solvent may be a liquid of an amphiphilic substance that has a hydrophilic group and a hydrophobic group in one molecule. A water-soluble organic solvent (for example, PGME) may be used as the solvent.

[0155] A water-soluble polymer is a polymer in which a hydrophilic group such as a carboxyl group, a hydroxyl group, or a sulfonic acid group is located at the end of the molecule. The water-soluble polymer may include at least one of a water-soluble acrylic resin, a water-soluble polyester, and a water-soluble polyurethane, or may include other polymers. The water-soluble acrylic resin may be at least one of an OH-group acrylic resin and a hydroxyl-group acrylic resin. The water-soluble polymer may be a polymer that is insoluble or almost insoluble in oil, or a polymer that is soluble in oil. In the latter case, the solubility of the water-soluble polymer in water is greater than the solubility of the water-soluble polymer in oil.

[0156] In this embodiment, the second moving nozzle 10 is an example of a residue removing liquid supply unit (residue removal processing unit) that supplies (discharges) a residue removing liquid (e.g., DIW) toward the upper surface of the substrate W held by the spin chuck 5. In this embodiment, the second moving nozzle 10 is also an example of a substitution liquid supply unit (replacement processing unit) that supplies (discharges) a substitution liquid (e.g., IPA) toward the upper surface of the substrate W held by the spin chuck 5. Of course, the residue removing liquid supply unit and the substitution liquid supply unit may be provided with separate nozzles.

[0157] The second moving nozzle 10 is connected to a residue removing liquid pipe 255 that guides the residue removing liquid to the second moving nozzle 10. When a residue removing liquid valve 257 installed in the residue removing liquid pipe 255 is opened, the residue removing liquid is continuously discharged downward from the discharge port of the second moving nozzle 10.

[0158] The second moving nozzle 10 is also connected to a substitution liquid pipe 256 that guides the substitution liquid to the second moving nozzle 10. When a substitution liquid valve 258 provided in the substitution liquid pipe 256 is opened, a rinse liquid (second organic solvent) is continuously discharged downward from the discharge port of the second moving nozzle 10.

[0159] The residue removal liquid is a liquid that dissolves and removes residues of the processing film from the substrate W, and is a dissolving liquid that can dissolve the processing film. When the processing film is water-soluble, a water-based liquid, such as DIW, can be used. The substitute liquid is a liquid that replaces the residue removal liquid on the substrate W, and when the residue removal liquid is DIW, for example, IPA can be used.

[0160] The controller 3 controls the spin motor 23 , the valves 88 , 253 , 257 , 258 , the nozzle moving units 37 , 38 , 251 , the guard lifting / lowering unit 74 , the heater 25 , and the like, and also controls the drainage system 200 .

[0161] 11 is a flowchart illustrating an example of a substrate processing method performed by the processing unit 2 in this embodiment, and FIGS. 12A to 12F are views illustrating the main steps. The substrate W to be processed is as described in the above embodiment.

[0162] The substrate processing method includes a processing liquid supply process 271 (see FIG. 12A) for supplying a processing liquid 96 to a main surface Wf of the substrate W, and a processing film formation process 272 (see FIG. 12B) for solidifying or curing the processing liquid 96 on the main surface Wf to form a processing film 300 on the main surface Wf.

[0163] 12A, while the substrate W is held and rotated by the spin chuck 5 (at a rotation speed of, for example, several tens of rpm to 200 rpm), the processing liquid valve 51 is opened and the processing liquid 96 is discharged from the first moving nozzle 9 toward the center of the upper surface of the substrate W. The discharged processing liquid 96 is subjected to centrifugal force on the substrate W and spreads over the entire surface of the substrate W, forming a processing liquid film 301 (a liquid film of the processing liquid 96) that covers the entire surface of the substrate W. That is, the processing liquid film 301 that covers the entire main surface Wf of the substrate W is formed by so-called spin coating. At this time, for example, the second guard 71B of the guard 71 may be disposed in a position where it receives the liquid that is spun outward from the substrate W.

[0164] In the treatment film forming process 272, as shown in FIG. 12B , the solvent component of the treatment liquid film 301 formed on the main surface Wf evaporates, solidifying or curing the treatment liquid film 301 to form a treatment film 300. Specifically, the treatment liquid valve 51 is closed to stop the discharge of the treatment liquid 96 from the first moving nozzle 9. The spin motor 23 drives the spin chuck 5 to continue rotating the substrate W, and the rotation may be accelerated as needed (for example, to about 1000 rpm). This evaporates the solvent in the treatment liquid film 301. To promote evaporation of the solvent, the substrate W may also be heated. The substrate W can be heated by opening the heat medium valve 88 and discharging a heat medium from the discharge port 12a of the lower nozzle 12 toward the lower surface of the substrate W (the main surface opposite the main surface Wf). Alternatively, the substrate W can be heated by energizing the heater 25 provided in the spin base 21. The processed film 300 may be formed in a semi-solidified or semi-cured state by rotating the substrate W using the spin chuck 5, and then the processed film 300 may be heated via the substrate W to promote evaporation of the solvent, thereby forming a completely solidified or cured processed film 300. The spin motor 23, the lower nozzle 12, the heat medium valve 88, the heater 25, etc. are examples of the "processed film forming unit."

[0165] After the treatment film forming step 272, the substrate processing method includes a stripping step 273 (see FIG. 12C) in which the treatment film 300 is stripped from the main surface Wf and removed outside the substrate W. The stripping step 273 is a gas stripping step performed by discharging a stripping gas.

[0166] Specifically, for example, with the first guard 71A facing the edge surface of the substrate W, the spin motor 23 rotates the substrate W held by the spin chuck 5 at a stripping speed (for example, a rotation speed of about several tens of rpm). In this state, the third nozzle moving unit 251 moves the stripping gas nozzle 250 from the standby position to the processing position. Thereafter, the opening / closing valve 253 is opened, and the stripping gas nozzle 250 starts to discharge the stripping gas. When a predetermined time has elapsed since the opening / closing valve 253 was opened, the opening / closing valve 253 is closed, and the discharge of the stripping gas is stopped. Thereafter, the third nozzle moving unit 251 moves the stripping gas nozzle 250 to the standby position.

[0167] When the stripping gas nozzle 250 discharges a stripping gas toward the upper surface of the substrate W covered with the processing film 300, the processing film 300 that has adhered to the entire upper surface of the substrate W is peeled off and removed from the substrate W.

[0168] More specifically, as shown in FIG. 13A, the stripping gas nozzle 250 starts discharging the stripping gas while stationary at a first discharging position P1 where the stripping gas is sprayed onto the upper surface of the substrate W between the center and the outer periphery of the substrate W. The substrate W is in a rotating state. As the substrate W rotates while the stripping gas is being sprayed, the thickness of the treatment film 300 is locally reduced on a circumference concentric with the substrate W, eventually forming through-holes 310. The stripping gas enters between the treatment film 300 and the substrate W through the through-holes 310 and applies a stripping force to the treatment film 300, which strips the treatment film 300 from the substrate W. This stripping force causes the treatment film 300 to further peel off from the substrate W (see FIG. 13B). The third nozzle moving unit 251 may move the stripping gas nozzle 250 toward the rotation center as needed. In this way, the treatment film 300 can be completely stripped from the surface of the substrate W by discharging the stripping gas from the stripping gas nozzle 250 without using a stripping solution. The peeled treated film is received by the guard 71 (for example, the first guard 71A).

[0169] 11, in this example, the substrate processing method includes a residue removing step 274 (see FIG. 12D) in which DIW is supplied as a residue removing liquid 97 to the main surface Wf of the substrate W to dissolve and remove residues of the processed film 300 from the pattern surface after the peeling step 273. In this case, the DIW as the residue removing liquid 97 also serves as a dissolving liquid that dissolves residues of the processed film 300.

[0170] In the residue removal process 274, the residue removal liquid valve 257 is opened, and a residue removal liquid 97 (DIW) is discharged from the second movable nozzle 10 toward the upper surface of the substrate W. The discharged residue removal liquid 97 is subjected to centrifugal force on the substrate W and spreads across the entire surface of the substrate W. The residue removal liquid 97 dissolves residues of the processing film 300 remaining on the main surface Wf of the substrate W and removes them from the substrate W. For example, while the substrate W is held and rotated by the spin chuck 5, the residue removal liquid 97 may be discharged from the second movable nozzle 10 toward the center of the upper surface of the substrate W. After the residue removal liquid 97 has spread across the entire main surface Wf, the rotation of the substrate W may be slowed or stopped, thereby performing a puddling process to maintain a liquid film of the residue removal liquid 97 on the substrate W. The puddling process is preferably performed for a time sufficient for the residue removal liquid 97 to dissolve the residues of the processing film 300. Thereafter, the substrate W is rotated by the spin chuck 5, whereby the residue removal solution 97 containing the dissolved treatment film 300 is removed from the substrate W in an evacuating step.

[0171] In the residue removal process 274, for example, the guard 71 is positioned so that the first guard 71A receives the liquid that is thrown off from the substrate W. As a result, the residue removal liquid 97 flows into the same guard as the film fragments of the treatment film 300 that have been peeled off by the peeling gas, and the residue removal liquid 97 dissolves the film fragments of the peeled treatment film 300 while discharging the film fragments into the drainage system 200 via the first drainage pipe 60A. In other words, the residue removal process 274 is an example of a "film fragment discharge process" in which the film fragments of the treatment film 300 are guided to the drainage pipe 60 by the residue removal liquid 97 (DIW), which is an example of a "first liquid." The guard 71 and the like are also examples of a "film fragment discharge unit."

[0172] 12E, after the residue removing step 274, the substrate processing method also includes a replacing step 275 in which the residue removing liquid 97 on the substrate W is replaced with a replacing liquid 98 (an organic solvent, for example, IPA), which is an example of the "second liquid." Specifically, the replacing liquid 98 (IPA) is supplied to the main surface Wf of the substrate W to which the residue removing liquid 97 has adhered, and the residue removing liquid 97 (DIW) is replaced with the replacing liquid 98 (IPA) and removed from the substrate W.

[0173] In the substitution step 275, the substitution liquid valve 258 is opened, and the substitution liquid 98 (IPA) is discharged from the second moving nozzle 10 toward the upper surface of the substrate W. The discharged substitution liquid 98 (IPA) is subjected to centrifugal force on the substrate W and spreads over the entire main surface Wf. The substitution liquid 98 (IPA) replaces the residue removal liquid 97 (DIW) remaining on the main surface Wf of the substrate W and removes it from the substrate W. For example, the substitution liquid 98 may be discharged from the second moving nozzle 10 toward the center of the upper surface of the substrate W while the substrate W is held and rotated by the spin chuck 5 (for example, at a rotation speed of about 800 rpm). After the substitution liquid 98 has spread over the entire main surface Wf, the rotation of the substrate W may be slowed or stopped, thereby performing a puddling step in which a liquid film of the substitution liquid 98 is maintained on the substrate W. It is preferable to perform the puddling step for a time sufficient for the substitution liquid 98 to replace the residue removal liquid 97 on the substrate W. Thereafter, the substrate W is rotated by the spin chuck 5, whereby the substitute liquid 98 is expelled from the substrate W.

[0174] In the substitution step 275, for example, the guard 71 may be disposed in a position where the second guard 71B receives the liquid spun outward from the substrate W. As a result, in the substitution step 275, the substitution liquid 98 (IPA) discharged from the substrate W is received by the second guard 71B and guided to the second drainage pipe 60B.

[0175] 12F, after the substitution step 275, the substrate processing method also includes a drying step 276 (typically a spin-drying step) for shaking off the liquid on the surface of the substrate W and drying it. The substitution liquid 98 (IPA) on the surface of the substrate W is expelled outside the substrate W by centrifugal force and disappears from the surface of the substrate W by volatilization into the atmosphere. As in the substitution step 275, the second guard 71B of the guard 71 may be positioned to receive the liquid shaken off outward from the substrate W.

[0176] Figure 14 shows an example of the configuration of the drainage system 200 in this embodiment. In Figure 14, the same reference numerals are used to designate parts corresponding to those shown in Figure 6A etc., and the description will be simplified.

[0177] The drainage system 200 includes a drainage pipe 60, a separation mechanism 110 provided in the drainage pipe, a first liquid storage mechanism 151, and a second liquid storage mechanism 152. The drainage pipe 60 includes a first drainage pipe 60A that guides the drainage received by the first guard 71A, and a second drainage pipe 60B that guides the drainage received by the second guard 71B.

[0178] The separation mechanism 110 is connected to the first drainage pipe 60A and the second drainage pipe 60B and includes a drainage trap tank 111 that commonly accommodates and stores the drainage from the first drainage pipe 60A and the second drainage pipe 60B. In the residue removal step 274 (see FIG. 12D), the residue removal liquid (DIW) is received by the first guard 71A, and the residue removal liquid dissolves the fragments of the treatment membrane 300 that were previously received by the first guard 71A in the peeling step 273 (see FIG. 10C). The residue removal liquid dissolves the fragments of the treatment membrane 300 and flows into the drainage trap tank 111 together with the fragments through the first drainage pipe 60A. In the drainage trap tank 111, the dissolution of the fragments of the treatment membrane 300 by the residue removal liquid (DIW) further progresses (membrane fragment dissolving step). In addition, in the substitution step 275 (see FIG. 12E), the substitution liquid (organic solvent, IPA) is received by the second guard 71B, passes through the second drainage pipe 60B, and flows into the drainage trap tank 111. Therefore, in the drainage trap tank 111, the residue removal liquid (DIW) and the substitution liquid (organic solvent, IPA) are mixed.

[0179] In this example, the treatment film 300 is water-soluble and therefore dissolved by the residue removal liquid (DIW). On the other hand, the treatment film 300 is insoluble or poorly soluble in the replacement liquid (IPA). Therefore, in order to reuse the residue removal liquid (DIW), it is preferable to separate and remove the replacement liquid (IPA). However, because DIW and IPA are mutually soluble, the configuration examples shown in FIGS. 6A to 8B are not necessarily suitable for separating them. The configuration example using the ion exchange resin unit 140 shown in FIG. 9 may be applicable by appropriately selecting an ion exchange resin column 141 capable of separating DIW and IPA.

[0180] In this embodiment, the separation mechanism 110 separates the DIW from the IPA using a separation membrane 146 (dehydration membrane) that is permeable to water but not to IPA. The separation membrane 146 may be a polymer membrane made of a polymer material, an inorganic membrane made of an inorganic material, or other membranes. A specific example of the separation membrane 146 is a zeolite membrane made of zeolite.

[0181] More specifically, in this configuration example, the separation mechanism 110 includes a dehydration unit 145 connected to the discharge port P via a fifth drainage pipe 60E (drainage pipe 60). A valve 142, a pump 143, and a filter 144 are provided in the fifth drainage pipe 60E.

[0182] The dehydration unit 145 includes a separation membrane 146 that separates water from IPA and a dehydration housing 147 that houses the separation membrane 146. The dehydration housing 147 includes a concentration chamber 148 and a permeation chamber 149 that are separated from each other by the separation membrane 146. The permeation chamber 149 is a chamber located downstream of the separation membrane 146 in the flow path and guides liquid that has permeated through the separation membrane 146 to a third drainage pipe 60C. On the other hand, the concentration chamber 148 is a chamber located upstream of the separation membrane 146 in the flow path and guides liquid that has not permeated through the separation membrane 146 to a fourth drainage pipe 60D. Specifically, the third drainage pipe 60C is connected to a first outlet port 145a that communicates with the permeation chamber 149, and the fourth drainage pipe 60D is connected to a second outlet port 145b that communicates with the concentration chamber 148. A vacuum pump 150 is provided in the third drainage pipe 60C to reduce the pressure in the permeation chamber 149.

[0183] The valve 142, the pump 143, the vacuum pump 150, etc. are controlled by a controller 3 (see FIG. 10).

[0184] When the pump 143 is operated with the valve 142 open, the liquid (a mixed liquid containing DIW and IPA) in the drain trap tank 111 is discharged from the discharge port P to the fifth drain pipe 60E. After foreign matter (particles, etc.) is removed by the filter 144, the liquid is introduced into the concentration chamber 148 from the inlet port 145c of the spin-drying unit 145. In the spin-drying unit 145, the DIW permeates the separation membrane 146 and is introduced into the permeation chamber 149 due to the pressure difference between the concentration chamber 148 and the permeation chamber 149. On the other hand, the IPA does not permeate the separation membrane 146 and remains in the concentration chamber 148. As a result, the DIW is introduced from the first outlet port 145a through the third drain pipe 60C to the first liquid storage mechanism 151, and the IPA is introduced from the second outlet port 145b through the fourth drain pipe 60D to the second liquid storage mechanism 152. In this way, the DIW and the IPA are separated (separation step 277 in FIG. 11), and can be accommodated in the first liquid containing mechanism 151 and the second liquid containing mechanism 152, respectively (accommodation step 278 in FIG. 11).

[0185] The DIW contained in the first liquid storage mechanism 151 contains dissolved matter of the treatment film 300, but there is no problem in reusing it as a residue removal liquid in the residue removal step 274 (see FIG. 12D). The IPA contained in the second liquid storage mechanism 152 is sufficiently dehydrated in the dehydration unit 145, so there is no problem in reusing it as a replacement liquid in the replacement step 275 (see FIG. 12E).

[0186] Therefore, a residue removing liquid pipe 255 is connected to the first tank 153 of the first liquid storage mechanism 151, and a pump 154 ​​and a filter 155 are interposed in the residue removing liquid pipe 255. When the pump 154 ​​is driven, the DIW stored in the first tank 153 is pumped out, and after foreign matter (particles) are removed by the filter 155, the DIW is supplied to the second moving nozzle 10 via a residue removing liquid valve 257 (also see FIG. 10 ).

[0187] Similarly, a substitute liquid pipe 256 is connected to the second tank 156 of the second liquid storage mechanism 152, and a pump 157 and a filter 158 are provided in the substitute liquid pipe 256. When the pump 157 is driven, the IPA stored in the second tank 156 is pumped out, and after foreign matter (particles) are removed by the filter 158, the IPA is supplied to the second moving nozzle 10 via the substitute liquid valve 258 (see also FIG. 10 ).

[0188] <Example of processing liquid> An example of each component in the treatment liquid used in the above-described embodiment will be described below.

[0189] In the following, "C x~y "," "C x~ C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1~6 Alkyl refers to alkyl chains having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0190] When a polymer has multiple types of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are represented by structural formulas, the n, m, etc. in parentheses indicate the number of repeating units.

[0191] <Low solubility component (second component)> The (A) low-solubility component includes at least one of novolak, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, the (A) low-solubility component may include at least one of novolak, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, the (A) low-solubility component may include at least one of novolak, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. The novolak may be a phenolic novolak.

[0192] The treatment liquid may contain one or a combination of two or more of the above preferred examples as the low-solubility component (A). For example, the low-solubility component (A) may contain both novolak and polyhydroxystyrene.

[0193] In a preferred embodiment, the low-solubility component (A) is dried to form a film, and the film is peeled off while retaining the object to be removed without being dissolved in the stripping solution for the most part. However, an embodiment in which only a small part of the low-solubility component (A) is dissolved in the stripping solution is acceptable.

[0194] Preferably, (A) the low-solubility component does not contain fluorine and / or silicon, more preferably does not contain both.

[0195] The copolymerization is preferably random copolymerization or block copolymerization.

[0196] Although there is no intention to limit the scope of the rights, specific examples of the low-solubility component (A) include the compounds shown in Chemical Formulas 1 to 7 below.

[0197] [ka]

[0198] [ka]

[0199] [ka] (An asterisk * indicates a bond to an adjacent building block.)

[0200] [ka] (R is C 1~4 (The asterisk * indicates a bond to an adjacent structural unit.)

[0201] [ka]

[0202] [ka]

[0203] [ka] (Me means a methyl group. An asterisk * indicates a bond to an adjacent structural unit.)

[0204] The weight average molecular weight (Mw) of the (A) low-solubility component is preferably 150 to 500,000, more preferably 300 to 300,000, even more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

[0205] (A) Low-solubility components can be obtained by synthesis. They can also be purchased. If purchased, examples of suppliers include the following. Suppliers can also synthesize (A) polymers. Novolac: Showa Kasei Co., Ltd., Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd. Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd. Polyacrylic acid derivative: Nippon Shokubai Co., Ltd. Polycarbonate: Sigma-Aldrich Polymethacrylic acid derivatives: Sigma-Aldrich

[0206] Compared to the total mass of the treatment liquid, the amount of the low-solubility component (A) is 0.1 to 50 mass%, preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, and even more preferably 1 to 10 mass%. In other words, the total mass of the treatment liquid is taken as 100 mass%, and the amount of the low-solubility component (A) is 0.1 to 50 mass% based on this. In other words, "compared to" can be rephrased as "based on." The same applies hereinafter unless otherwise specified.

[0207] <Highly soluble component (first component)> The (B) highly soluble component is the (B') crack-accelerating component. The (B') crack-accelerating component contains a hydrocarbon and further contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). When the (B') crack-accelerating component is a polymer, one of the constituent units contains a hydrocarbon on a unit-by-unit basis and further contains a hydroxyl group and / or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and enone, with carboxylic acid being preferred.

[0208] Without intending to limit the scope of the invention or being bound by theory, it is believed that when the treatment solution is dried to form a treatment film on the substrate and the stripper solution strips the treatment film, the (B) highly soluble component creates a portion that triggers the treatment film to peel off. For this reason, it is preferable that the (B) highly soluble component has a higher solubility in the stripper solution than the (A) low solubility component. Examples of embodiments of the (B') crack-promoting component that contain a ketone as a carbonyl group include cyclic hydrocarbons. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0209] In a more specific embodiment, the highly soluble component (B) is represented by at least one of the following (B-1), (B-2), and (B-3). (B-1) is a compound containing 1 to 6 (preferably 1 to 4) structural units of the following chemical formula 8, each of which is linked by a linking group (linker L1). Here, the linker L1 may be a single bond or a C 1~6 It may be alkylene. 1~6 The alkylene acts as a linker to connect the constituent units and is not limited to a divalent group. Preferably, it is a divalent to tetravalent group. 1~6 The alkylene may be either straight-chain or branched.

[0210] [ka]

[0211] Cy1 is C 5~30 Preferably, it is phenyl, cyclohexane, or naphthyl, more preferably phenyl. In a preferred embodiment, the linker L1 connects multiple Cy1s.

[0212] R1 is independently C 1~5 alkyl, preferably methyl, ethyl, propyl, or butyl. 1~5 The alkyl may be either straight-chain or branched.

[0213] n b1 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. b1’ is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0214] The following chemical formula 9 is a chemical formula that uses a linker L9 to represent the structural unit described in chemical formula 8. The linker L9 is preferably a single bond, methylene, ethylene, or propylene.

[0215] [ka]

[0216] Although not intending to limit the scope of the invention, suitable examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These may be obtained by polymerization or condensation.

[0217] As an example, we will explain 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following chemical formula 10. In (B-1), this compound has three structural units of chemical formula 8, and the structural units are linked by a linker L1 (methylene). b1 =n b1’ =1 and R1 is methyl.

[0218] [ka]

[0219] (B-2) is represented by the following chemical formula 11.

[0220] [ka]

[0221] R 21 , R 22 , R 23 , and R 24 are each independently hydrogen or C 1~5 and is preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

[0222] Linker L 21 and linker L 22 are each independently, C 1~20 Alkylene, C 1~20 Cycloalkylene, C 2~4 Alkenylene, C 2~4 Alkynylene of C 6~20 These groups are arylenes of the formula C 1~5 The linker L may be substituted with an alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon group having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. 21 and linker L 22 is preferably C 2~4 alkylene, acetylene (C alkynylene) or phenylene, more preferably C 2~4 or acetylene, more preferably acetylene.

[0223] n b2 is 0, 1 or 2, preferably 0 or 1, more preferably 0.

[0224] Although not intending to limit the scope of the invention, suitable examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, suitable examples of (B-2) include 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol.

[0225] (B-3) is a polymer containing a constituent unit represented by the following chemical formula 12, and has a weight average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

[0226] [ka]

[0227] where R 25 is —H, —CH3, or —COOH, preferably —H or —COOH. It is also acceptable for one (B-3) polymer to contain two or more types of constitutional units each represented by Chemical Formula 12.

[0228] Although not intending to limit the scope of the invention, preferred examples of the (B-3) polymer include polymers of acrylic acid, maleic acid, or a combination thereof. More preferred examples include polyacrylic acid and maleic-acrylic acid copolymers.

[0229] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0230] As an example, the maleic acid acrylic acid copolymer shown in the following chemical formula 13 will be described. This copolymer is included in (B-3) and has two types of structural units shown in chemical formula 12, with R 25 is -H, and in another building block, R 25 is -COOH.

[0231] [ka]

[0232] Needless to say, the treatment solution may contain one or a combination of two or more of the above preferred examples as the highly soluble component (B). For example, the highly soluble component (B) may contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0233] The (B) highly soluble component may have a molecular weight of 80 to 10,000. The (B) highly soluble component preferably has a molecular weight of 90 to 5000, more preferably 100 to 3000. When the (B) highly soluble component is a resin, a polymer, or a polymer, the molecular weight is expressed as a weight average molecular weight (Mw).

[0234] (B) Highly soluble components can be synthesized or purchased from suppliers such as Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai.

[0235] In the treatment liquid, the amount of the highly soluble component (B) is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, relative to the mass of the low solubility component (A).In the treatment liquid, the amount of the highly soluble component (B) is further preferably 1 to 30% by mass, relative to the mass of the low solubility component (A).

[0236] <Solvent> The (C) solvent may be water (particularly in the case of the embodiment shown in FIG. 10, etc.), or may be primarily composed of an organic solvent. The (C) solvent may be volatile. Volatile means more volatile than water. For example, the boiling point of the (C) solvent at 1 atmosphere is preferably 50 to 250°C. The boiling point of the solvent at 1 atmosphere is more preferably 50 to 200°C, and even more preferably 60 to 170°C. The boiling point of the solvent at 1 atmosphere is even more preferably 70 to 150°C. When the (C) solvent is an organic solvent, it is acceptable for the solvent to contain a small amount of pure water. The amount of pure water contained in the (C) solvent is preferably 30% by mass or less relative to the total amount of the (C) solvent. The amount of pure water contained in the solvent is more preferably 20% by mass or less, and even more preferably 10% by mass or less. The amount of pure water contained in the solvent is even more preferably 5% by mass or less. A preferred embodiment is one in which the solvent does not contain pure water (0% by mass). The pure water is preferably DIW.

[0237] Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These organic solvents can be used alone or in combination.

[0238] In a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When two organic solvents are combined, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

[0239] The proportion of (C) solvent relative to the total mass of the treatment liquid is 0.1 to 99.9 mass%. The proportion of (C) solvent relative to the total mass of the treatment liquid is preferably 50 to 99.9 mass%, more preferably 75 to 99.5 mass%. The proportion of (C) solvent relative to the total mass of the treatment liquid is even more preferably 80 to 99 mass%, even more preferably 85 to 99 mass%.

[0240] <Other additives> The treatment solution may further contain (D) other additives. (D) Other additives include surfactants, acids, bases, antibacterial agents, bactericides, preservatives, or antifungal agents (preferably surfactants), and may also contain any combination thereof.

[0241] Compared to the mass of the (A) low-solubility component in the treatment liquid, the mass of (D) other additives (if multiple additives are present, their sum total) is 0 to 100 mass % (preferably 0 to 10 mass %, more preferably 0 to 5 mass %, even more preferably 0 to 3 mass %, and even more preferably 0 to 1 mass %). The treatment liquid may not contain (D) other additives (0 mass %).

[0242] <Corrosion prevention ingredients> (E) Examples of corrosion inhibitors include, in addition to BTA, uric acid, caffeine, buterin, adenine, glyoxylic acid, glucose, fructose, and mannose.

[0243] Although the embodiment of the present invention has been described above, the present invention can also be embodied in other forms.

[0244] For example, the processing liquid is not limited to those described above. For example, a resist film forming liquid or a reflective film forming liquid can be used as the processing liquid. In this case, a developer can be used as the stripping liquid.

[0245] It is also possible to use, as the treatment liquid, a liquid containing a water-soluble polymer that forms a water-soluble film by evaporating the solvent (particularly in the case of the embodiment shown in FIG. 10, etc.).

[0246] The water-soluble polymer may contain at least one of the following: a cellulose-based polymer such as hydroxypropyl methylcellulose phthalate, hydroxypropyl methylcellulose acetate phthalate, hydroxypropyl methylcellulose acetate succinate, hydroxypropyl methylcellulose hexahydrophthalate, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose acetate hexahydrophthalate, carboxymethylcellulose, ethyl cellulose, or methylcellulose; an acrylic polymer such as N,N-dimethylacrylamide, dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, N-methylacrylamide, diacetone acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, acryloylmorpholine, or acrylic acid; or a vinyl-based polymer such as polyvinyl alcohol or polyvinylpyrrolidone. These water-soluble polymers may be used alone or in combination of two or more.

[0247] Furthermore, in the above-described embodiment, an example was shown in which the "second liquid" was supplied to the substrate, but the "second liquid" may be led to the drainage pipe without being supplied to the substrate. For example, a dissolving liquid for dissolving the pieces of the treatment film in the drainage pipe 60 may be supplied to the drainage pipe 60 from the vicinity of the guard 71. Furthermore, a liquid for flowing and moving the pieces of the treatment film to a drainage trap tank or the like may be supplied, for example, from the vicinity of the guard 71.

[0248] Furthermore, in the above embodiment, an example of a single-substrate processing apparatus has been described, but the present invention is also applicable to a batch-type substrate processing apparatus that processes a plurality of substrates at once.

[0249] In this specification, when a numerical range is indicated using "~" or "-", it includes both endpoints and has the same units, unless otherwise specified.

[0250] In addition, various design modifications can be made within the scope of the claims. [Explanation of symbols]

[0251] 1: Substrate processing equipment 2: Processing unit 3: Controller 5: Spin chuck 7: Processing cup 9: First moving nozzle 10: Second moving nozzle 23: Spin motor 25: Heater 40: Residue removal liquid piping 41: Processing liquid piping 42: Stripping liquid piping 43: Rinse liquid piping 50: Residue removal liquid valve 51: Processing liquid valve 52: Stripping liquid valve 53: Rinse liquid valve 60: Drainage pipe 60A: First drainage pipe 60B: Second drainage pipe 60C: Third drainage pipe 60D: 4th drainage pipe 60E: 5th drainage pipe 71: Guard 71A: First Guard 71B: Second guard 72: Cup 72A: 1st Cup 72B: 2nd cup 74: Guard lifting unit 83: Heat medium piping 88: Heat transfer valve 91: Processing liquid 93: Stripping solution 94:Residue removal solution 95: Rinse 96: Processing liquid 97:Residue removal solution 98: Substitution liquid 100: Treated membrane 110: Separation mechanism 111: Drainage trap tank 112: Valve mechanism 113: Floating body 114:Fulcrum 115: Lever 116A: 1st valve member 116B:Second valve member 120: Interface 121: 1st liquid layer 122:Second liquid layer 124: Guide rail 125: Lifting member 126A: 1st valve member 126B:Second valve member 131: Cooling unit 132: Heating unit 133: Suction unit 134: Suction piping 135: Suction head 136: Head lift mechanism 140: Ion exchange resin unit 141: Ion exchange resin column 145: Dehydration unit 146: Separation membrane 151: First liquid containing mechanism 152: Second liquid containing mechanism 171: Processing liquid supply process 172: Treatment film formation process 173: Peeling process 174: Exclusion process 175:Residue removal process 176: Rinse process 177:Drying process 178: Separation process 179: Storage process 200: Drainage system 250: Stripping gas nozzle 252: Stripping gas piping 255: Residue removal liquid piping 256: Replacement liquid piping 257: Residue removal liquid valve 258: Replacement fluid valve 271: Processing liquid supply process 272: Treatment film formation process 273: Peeling process 274:Residue removal process 275: Substitution process 276:Drying process 277: Separation process 278: Storage process 300: Treated membrane 301: Treatment liquid membrane PA: First discharge port PB: Second discharge port VA: First valve VB: Second valve W: Substrate

Claims

1. a substrate processing unit that processes substrates; a processing liquid nozzle for supplying a processing liquid containing a solute and a solvent to the surface of the substrate in the substrate processing section; a treatment film forming section in the substrate processing section that solidifies or hardens the treatment liquid to form a treatment film on the surface of the substrate; a peeling unit in the substrate processing unit that peels the processing film from the surface of the substrate; a drainage pipe for discharging wastewater from the substrate processing unit; a film piece discharge unit that guides film pieces of the treatment film peeled from the surface of the substrate by the peeling unit from the substrate processing unit to the drainage pipe using a first liquid; a second liquid supply unit that supplies a second liquid different from the first liquid to the drainage pipe; a separation mechanism provided in the drainage pipe for separating the first liquid and the second liquid; a first liquid containing mechanism that receives the first liquid separated by the separation mechanism; a second liquid containing mechanism that receives the second liquid separated by the separation mechanism, The substrate processing apparatus, wherein the processing film is soluble in one of the first liquid and the second liquid, and is insoluble or hardly soluble in the other of the first liquid and the second liquid.

2. The substrate processing apparatus according to claim 1 , wherein the second liquid supply unit supplies the second liquid to the substrate in the substrate processing unit.

3. the treatment film is insoluble or poorly soluble in the first liquid and soluble in the second liquid; the peeling unit peels the processing film from the surface of the substrate by supplying the first liquid as a peeling liquid to the surface of the substrate in the substrate processing unit; The substrate processing apparatus according to claim 1 , wherein the film fragment discharge unit guides the stripping liquid discharged from the surface of the substrate together with the film fragments of the processing film to the drainage pipe.

4. the second liquid supply unit includes a residue removal processing unit in the substrate processing unit that supplies the second liquid to the surface of the substrate as a residue removal liquid and dissolves and removes residue of the processing film remaining on the surface of the substrate from which the processing film has been peeled by the peeling unit, The substrate processing apparatus according to claim 3 , wherein the residue removing liquid discharged from the surface of the substrate is guided to the drainage pipe.

5. the treatment film is soluble in the first liquid and insoluble or poorly soluble in the second liquid; the film piece discharge unit includes a residue removal processing unit in the substrate processing unit that supplies the first liquid as a residue removal liquid to the surface of the substrate and dissolves residues of the processing film remaining on the surface of the substrate from which the processing film has been peeled by the peeling unit, and guides the residue removal liquid discharged from the surface of the substrate together with the film pieces of the processing film to the drainage pipe; 2. The substrate processing apparatus according to claim 1, wherein the second liquid supply unit includes a replacement processing unit in the substrate processing unit that supplies the second liquid to the surface of the substrate and replaces the residue removal liquid remaining on the surface of the substrate with the second liquid, and the second liquid discharged from the surface of the substrate is guided to the drainage piping.

6. The substrate processing apparatus according to claim 5 , wherein the removing section removes the processing film from the surface of the substrate by blowing gas toward the surface of the substrate in the substrate processing section.

7. the first liquid and the second liquid are incompatible with each other and have different densities; The separation mechanism includes: a waste liquid trap tank for storing the first liquid and the second liquid and dissolving membrane fragments of the treatment membrane; a first drain port for draining the first liquid from the drain trap tank; a second drain port for draining the second liquid from the drain trap tank; a valve mechanism having a float that moves up and down following the interface between the first liquid and the second liquid in the drain trap tank, and that opens one of the first discharge port and the second discharge port and closes the other of the first discharge port and the second discharge port by the up and down movement of the float; The substrate processing apparatus of claim 1 , comprising:

8. the first liquid and the second liquid are incompatible with each other, have different densities, and have different melting points; The separation mechanism includes: a waste liquid trap tank for storing the first liquid and the second liquid and dissolving membrane fragments of the treatment membrane; a cooling unit that freezes one of a first liquid layer and a second liquid layer formed by the first liquid and the second liquid being separated into upper and lower layers in the drain trap tank, causing the first liquid layer and the second liquid layer to transition to a solid phase, and maintains the other of the first liquid layer and the second liquid layer in a liquid phase; a discharge unit that discharges the other of the first and second liquid layers, which is maintained in a liquid phase, from the drain trap tank while one of the first and second liquid layers is in a solid phase; The substrate processing apparatus of claim 1 , comprising:

9. 2 . The substrate processing apparatus according to claim 1 , wherein the separation mechanism includes an ion exchange resin unit that selectively extracts the first liquid or the second liquid from the mixed liquid of the first liquid and the second liquid.

10. one of the first liquid and the second liquid contains water, The substrate processing apparatus according to claim 1 , wherein the separation mechanism includes a dehydration unit that extracts water from the mixture of the first liquid and the second liquid.

11. 11. The substrate processing apparatus according to claim 9, further comprising a waste liquid trap tank provided in the waste liquid piping, which stores the first liquid and the second liquid and dissolves pieces of the processing film, and a mixture of the first liquid and the second liquid is supplied from the waste liquid trap tank to the separation mechanism.

12. a processing liquid supplying step of supplying a processing liquid containing a solute and a solvent onto the surface of the substrate in the substrate processing section; a treatment film forming step of solidifying or curing the treatment liquid in the substrate processing unit to form a treatment film on the surface of the substrate; a peeling step of peeling the processing film from the surface of the substrate in the substrate processing section; a film fragment discharge step of guiding the film fragments of the treatment film peeled off from the surface of the substrate by the peeling step from the substrate processing unit to a drainage pipe using a first liquid; a second liquid supplying step of supplying a second liquid different from the first liquid to the drainage pipe; a separation step of separating the first liquid and the second liquid by a separation mechanism provided in the drainage pipe; a storing step of storing the first liquid and the second liquid separated by the separation mechanism in a first liquid storing mechanism and a second liquid storing mechanism, respectively; The substrate processing method, wherein the processing film is soluble in one of the first liquid and the second liquid, and is insoluble or hardly soluble in the other of the first liquid and the second liquid.

13. the treatment film is insoluble or poorly soluble in the first liquid and soluble in the second liquid; the removing step includes, in the substrate processing unit, supplying the first liquid as a remover to the surface of the substrate, thereby removing the treatment film from the surface of the substrate; The substrate processing method according to claim 12 , wherein the film fragment discharging step includes guiding the stripping liquid discharged from the surface of the substrate together with the film fragments of the processing film to the drain pipe.

14. 14. The substrate processing method according to claim 13, wherein the second liquid supplying step includes a residue removing step in which the second liquid is supplied to the surface of the substrate as a residue removing liquid in the substrate processing unit to dissolve and remove residue of the processing film remaining on the surface of the substrate from which the processing film has been peeled by the peeling step, and the residue removing liquid discharged from the surface of the substrate is led to the drainage pipe.

15. the treatment film is soluble in the first liquid and insoluble or poorly soluble in the second liquid; the film fragment discharge step includes a residue removal step in which the first liquid is supplied to the surface of the substrate as a residue removal liquid in the substrate processing unit to dissolve residues of the treatment film remaining on the surface of the substrate from which the treatment film has been peeled in the peeling step, and the residue removal liquid discharged from the surface of the substrate together with the film fragments of the treatment film is guided to the drainage pipe; 13. The substrate processing method according to claim 12, wherein the second liquid supplying step includes a replacement step in the substrate processing unit of supplying the second liquid to the surface of the substrate and replacing the residue removing liquid remaining on the surface of the substrate with the second liquid, and the second liquid discharged from the surface of the substrate is led to the drainage pipe.

16. 16. The substrate processing method according to claim 15, wherein the removing step includes a gas removing step of removing the processing film from the surface of the substrate by blowing a gas toward the surface of the substrate in the substrate processing section.

17. the first liquid and the second liquid are incompatible with each other and have different densities; The separation mechanism includes: a waste liquid trap tank for storing the first liquid and the second liquid and dissolving membrane fragments of the treatment membrane; a first drain port for draining the first liquid from the drain trap tank; a second drain port for draining the second liquid from the drain trap tank; a valve mechanism having a float that moves up and down following the interface between the first liquid and the second liquid in the drain trap tank, and that opens one of the first discharge port and the second discharge port and closes the other of the first discharge port and the second discharge port by the up and down movement of the float; Including, The separation step comprises: a membrane fragment dissolving step of dissolving membrane fragments of the treatment membrane in the wastewater trap tank; a first discharge step of opening the first discharge port by the valve mechanism to discharge the first liquid from the drain trap tank; 13. The substrate processing method according to claim 12, further comprising: a second draining step of opening the second drain port by the valve mechanism to drain the second liquid from the drain trap tank.

18. the first liquid and the second liquid are incompatible with each other, have different densities, and have different melting points; the separation mechanism includes a waste liquid trap tank that stores the first liquid and the second liquid and dissolves membrane fragments of the treatment membrane, and a cooling unit that freezes one of a first liquid layer and a second liquid layer that are formed by the first liquid and the second liquid separating into upper and lower layers in the waste liquid trap tank, causing the first liquid layer and the second liquid layer to transition to a solid phase, and maintains the other of the first liquid layer and the second liquid layer in a liquid phase; The separation step comprises: a membrane fragment dissolving step of dissolving membrane fragments of the treatment membrane in the wastewater trap tank; a freezing step in which one of the first liquid layer and the second liquid layer is frozen by the cooling unit to transition to a solid phase, and the other of the first liquid layer and the second liquid layer is maintained in a liquid phase; a first discharge step of discharging the other of the first and second liquid layers, which is maintained in a liquid phase, from the drain trap tank while one of the first and second liquid layers is in a solid phase; a melting step of melting one of the first liquid layer and the second liquid layer to transition to a liquid phase after the first discharging step; a second discharge step of discharging one of the first liquid layer and the second liquid layer that has transitioned to a liquid phase from the drain trap tank after the melting step; The method of claim 12 , comprising:

19. The substrate processing method according to claim 12 , wherein the separation mechanism includes an ion exchange resin unit that selectively extracts the first liquid or the second liquid from the mixed liquid of the first liquid and the second liquid.

20. one of the first liquid and the second liquid contains water, The substrate processing method according to claim 12 , wherein the separation mechanism includes a dehydration unit that extracts water from the mixture of the first liquid and the second liquid.

21. 21. The substrate processing method of claim 19, further comprising a film fragment dissolving step of storing the first liquid and the second liquid in a waste liquid trap tank provided in the waste liquid piping to dissolve film fragments of the processing film, and a mixed liquid of the first liquid and the second liquid is supplied from the waste liquid trap tank to the separation mechanism.

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