Substrate processing method and substrate processing apparatus

Abstract

A substrate processing method includes a processing liquid supplying step of supplying a processing liquid having a solute and a solvent toward a surface of a substrate, a processing film forming step of curing or hardening the processing liquid supplied to the surface of the substrate, and a processing film forming step of forming a processing film on the surface of the substrate. A method for removing a substrate includes forming a treatment film on a surface of the substrate, the treatment film holding an object to be removed present on the surface of the substrate, and a peeling step of forming a peeling liquid by supplying a peeling liquid-forming liquid to the surface of the substrate and bringing the peeling liquid-forming liquid into contact with the treatment film to form the peeling liquid, and peeling the surface of the substrate by supplying the peeling liquid-forming liquid to the surface of the substrate. And a stripping step of stripping the processing film in a state in which the object to be removed is held from the surface of the substrate by the stripping liquid, and a removing step of continuously supplying the stripping liquid forming liquid after stripping the processing film, and removing the object to be removed by the stripping liquid forming liquid in a state in which the object to be removed is held by the processing film. The processing film is rinsed to remove the processing film from the surface of the substrate.

Description

[0001] This application is a divisional application of the application with the application date of December 16, 2019, application number 201911292029.0, and invention title "Substrate Processing Method and Substrate Processing Apparatus". Technical Field

[0002] The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. 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 discs, substrates for magnetic disks, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like. Background Art

[0003] In the manufacturing process of semiconductor devices, in order to remove various contaminants attached to the substrate, residues such as processing liquids and resists used in the previous process, and various particles, etc. (hereinafter, sometimes collectively referred to as "objects to be removed"), a cleaning process is implemented.

[0004] In the cleaning process, generally, a cleaning liquid such as deionized water (DIW: Deionized Water) is supplied to the substrate, and the objects to be removed are removed by the physical action of the cleaning liquid, or a chemical solution that chemically reacts with the objects to be removed is supplied to the substrate to chemically remove the objects to be removed.

[0005] However, the miniaturization and complication of the concavo-convex patterns formed on the substrate are developing. Therefore, it is becoming increasingly difficult to remove the objects to be removed by a cleaning liquid or a chemical solution while suppressing damage to the concavo-convex patterns.

[0006] Therefore, the following method has been proposed: a processing liquid including a solute and a volatile solvent is supplied to the upper surface of the substrate, and after forming a processing film obtained by solidifying or hardening the processing liquid, the processing film is dissolved to be removed (refer to U.S. Patent Application Publication No. 2014 / 041685 and U.S. Patent Application Publication No. 2015 / 128994).

[0007] In this method, when the processing liquid solidifies or hardens to form a processing film, the objects to be removed are separated from the substrate. Then, the separated objects to be removed are held in the processing film.

[0008] Next, a dissolving processing liquid is supplied to the upper surface of the substrate. As a result, the processing film is dissolved and removed on the substrate, and thus, the objects to be removed are removed from the upper surface of the substrate together with the dissolved matter of the processing film (refer to U.S. Patent Application Publication No. 2014 / 041685).

[0009] Alternatively, sometimes a stripping treatment liquid is supplied to the upper surface of the substrate. Thereby, the treatment film is stripped from the upper surface of the substrate. Then, by supplying a dissolution treatment liquid, the treatment film is dissolved on the substrate (refer to the specification of U.S. Patent Application Publication No. 2015 / 128994).

[0010] In the methods of the specification of U.S. Patent Application Publication No. 2014 / 041685 and the specification of U.S. Patent Application Publication No. 2015 / 128994, the treatment film is dissolved on the substrate. Therefore, the object to be removed on the substrate falls off from the treatment film, and the fallen object to be removed may adhere to the substrate again. Therefore, it may not be possible to efficiently remove the object to be removed from the substrate. Thus, there is a need for a method of removing the treatment film from the substrate while keeping the treatment film in a state of holding the object to be removed.

[0011] However, the stripping liquid that can strip and remove the treatment film from the surface of the substrate while keeping the treatment film in a state of holding the object to be removed is relatively expensive. When the stripping liquid is supplied to the upper surface of the substrate, since the stripping liquid is consumed in large quantities, the cost may increase. SUMMARY OF THE INVENTION

[0012] Accordingly, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can both suppress an increase in cost and efficiently remove an object to be removed existing on the surface of a substrate.

[0013] One embodiment of the present invention provides a substrate processing method, including: a treatment liquid supply step of supplying a treatment liquid having a solute and a solvent toward the surface of a substrate; a treatment film formation step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; a stripping step of forming a stripping liquid by bringing a stripping liquid forming liquid into contact with the treatment film by supplying the stripping liquid forming liquid to the surface of the substrate, and stripping the treatment film in a state of holding the object to be removed from the surface of the substrate by the stripping liquid; and a removal step of flushing away the treatment film and removing the treatment film from the surface of the substrate while the treatment film holds the object to be removed by continuing to supply the stripping liquid forming liquid after stripping the treatment film.

[0014] According to this method, by bringing the stripping liquid forming liquid supplied to the surface of the substrate into contact with the treatment film, a stripping liquid for stripping the treatment film from the surface of the substrate is formed on the substrate. The treatment film holding the object to be removed is stripped from the surface of the substrate by the stripping liquid spontaneously formed on the substrate. Then, by continuously supplying the stripping liquid forming liquid, the treatment film can be removed from the surface of the substrate while the treatment film holds the object to be removed. That is, by supplying only the stripping liquid forming liquid to the surface of the substrate without supplying the stripping liquid, the object to be removed can be removed from the surface of the substrate. That is, the object to be removed can be removed from the surface of the substrate without consuming a large amount of the relatively expensive stripping liquid. Therefore, both the increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0015] In one embodiment of the present invention, the solute has a stripping liquid forming substance. And, the treatment film forming step includes a step of forming the treatment film having the stripping liquid forming substance in a solid state. And, the stripping step includes a step of forming the stripping liquid by dissolving the stripping liquid forming substance in a solid state in the treatment film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0016] According to this method, the stripping liquid is formed by dissolving the stripping liquid forming substance in a solid state in the treatment film in the stripping liquid forming liquid. Therefore, the stripping liquid forming substance can be dissolved in the stripping liquid forming liquid near the treatment film, so that the stripping liquid can be formed near the treatment film. Therefore, the stripping liquid forming substance dissolved in the stripping liquid forming liquid can be uniformly diffused to the stripping liquid before the whole of the stripping liquid forming liquid, and the stripping liquid having a relatively high concentration of the stripping liquid forming substance acts on the treatment film. Thereby, the treatment film can be efficiently stripped, and thus the object to be removed existing on the surface of the substrate can be efficiently removed.

[0017] The stripping liquid forming substance required for the formation of the stripping liquid is also relatively expensive like the stripping liquid. And, the time required to supply the treatment liquid in an amount required for the formation of the treatment film to the substrate is shorter than the time required to strip the treatment film and remove it from the substrate. Therefore, in this method, the treatment liquid containing the stripping liquid forming substance is supplied to the substrate for forming the treatment film, and the stripping liquid forming liquid not containing the stripping liquid forming substance is supplied to the substrate for stripping and removing the treatment film. Therefore, compared with the method of supplying the treatment liquid not containing the stripping liquid forming substance to the substrate for forming the treatment film and supplying the stripping liquid (the stripping liquid forming liquid in which the stripping liquid forming substance is dissolved) to the substrate for stripping and removing the treatment film, the supply time (consumption amount) of the stripping liquid forming substance supplied to the substrate can be reduced. Therefore, the increase in cost can be suppressed.

[0018] As a result, both the increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0019] In one embodiment of the present invention, the stripping liquid is an alkaline liquid. The alkaline liquid can effectively strip the treatment film, but it is relatively expensive. Therefore, if a method of forming an alkaline liquid by bringing a stripping liquid forming liquid into contact with the treatment film is used, the alkaline liquid can be spontaneously generated on the substrate. Therefore, by supplying only the stripping liquid forming liquid to the surface of the substrate without supplying the alkaline liquid, the object to be removed can be removed from the surface of the substrate. That is, the object to be removed can be removed from the surface of the substrate without consuming a large amount of the relatively expensive alkaline liquid. Therefore, the consumption of the alkaline liquid can be reduced, and thus an increase in cost can be suppressed. As a result, both an increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0020] In one embodiment of the present invention, the stripping liquid forming liquid is pure water. Therefore, by using relatively inexpensive pure water as the stripping liquid forming liquid, the treatment film can be stripped and removed from the surface of the substrate. As a result, both an increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0021] In one embodiment of the present invention, the stripping process includes a through-hole forming process, in which by supplying the stripping liquid forming liquid to the surface of the substrate, the treatment film is partially dissolved to form through-holes in the treatment film.

[0022] According to this method, by supplying the stripping liquid forming liquid to the surface of the substrate, the treatment film is partially dissolved to form through-holes in the treatment film. By forming through-holes in the treatment film, the stripping liquid can easily reach the vicinity of the surface of the substrate. Therefore, the stripping liquid can act on the interface between the treatment film and the substrate, and thus the treatment film can be efficiently stripped from the surface of the substrate. On the other hand, although a part of the treatment film is dissolved to form through-holes, the remaining part remains in a solid state, that is, in the state of the object to be removed. As a result, the treatment film can be quickly stripped from the surface of the substrate, and the object to be removed can be efficiently removed from the surface of the substrate together with the treatment film.

[0023] In one embodiment of the present invention, the solute has a highly soluble substance and a low soluble substance whose solubility relative to the stripping liquid is lower than that of the highly soluble substance. And, the treatment film forming process includes a process of forming the treatment film having the highly soluble substance and the low soluble substance in a solid state. And, the through-hole forming process includes: a process of forming the through-holes in the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the stripping liquid formed on the substrate.

[0024] According to this method, highly soluble substances have higher solubility relative to the stripping liquid than poorly soluble substances. Therefore, by dissolving the highly soluble substances in the solid state in the treatment film in the stripping liquid, through-holes can be reliably formed in the treatment film. On the other hand, the poorly soluble substances in the treatment film are not dissolved and remain in the solid state. Therefore, while the object to be removed is held by the poorly soluble substances in the solid state, the stripping liquid can be allowed to act on the interface between the poorly soluble substances in the solid state and the substrate. As a result, the treatment film can be quickly peeled off from the surface of the substrate, and thus the object to be removed and the treatment film can be efficiently removed from the surface of the substrate.

[0025] In one embodiment of the present invention, the solubility of the poorly soluble substance relative to the stripping liquid forming liquid is lower than the solubility of the highly soluble substance relative to the stripping liquid forming liquid. And the through-hole forming step includes: a step of forming the through-hole in the treatment film by dissolving the highly soluble substance in the solid state in the treatment film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0026] According to this method, highly soluble substances have higher solubility relative to the stripping liquid forming liquid than poorly soluble substances. Therefore, by dissolving the highly soluble substances in the solid state in the treatment film in the stripping liquid forming liquid, through-holes can be reliably formed in the treatment film. On the other hand, the poorly soluble substances in the solid state in the treatment film are not dissolved and remain in the solid state. Therefore, while the object to be removed is held by the poorly soluble substances in the solid state, the stripping liquid can be allowed to act on the interface between the poorly soluble substances in the solid state and the substrate. As a result, the treatment film can be quickly peeled off from the surface of the substrate, and thus the object to be removed and the treatment film can be efficiently removed from the surface of the substrate.

[0027] In one embodiment of the present invention, the solute includes a highly soluble substance and a poorly soluble substance having lower solubility relative to the stripping liquid forming liquid than the highly soluble substance. And the treatment film forming step includes a step of forming the treatment film having the highly soluble substance and the poorly soluble substance in the solid state. And the through-hole forming step includes: a step of forming the through-hole in the treatment film by dissolving the highly soluble substance in the solid state in the treatment film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0028] According to this method, highly soluble substances have a higher solubility in the stripping liquid-forming liquid compared to low solubility substances. Therefore, by dissolving the highly soluble substances in the solid state in the treatment film in the stripping liquid-forming liquid, through holes can be reliably formed on the treatment film. On the other hand, the low solubility substances in the treatment film are not dissolved and remain in a solid state. Therefore, while using the low solubility substances in the solid state to hold the object to be removed, the stripping liquid can act on the interface between the solid state low solubility substances and the substrate. As a result, the treatment film can be quickly peeled off from the surface of the substrate, and thus the object to be removed can be efficiently removed from the surface of the substrate together with the treatment film.

[0029] One embodiment of the present invention provides a substrate processing method, including: a treatment liquid supply step of supplying a treatment liquid containing a solute containing an alkaline component and a solvent to the surface of the substrate; a treatment film formation step of forming a treatment film containing the alkaline component on the surface of the substrate by solidifying or hardening the treatment liquid supplied to the surface of the substrate, which holds the object to be removed present on the surface of the substrate; a stripping step of supplying pure water to the surface of the substrate to bring the pure water into contact with the treatment film, causing the alkaline component in the treatment film to dissolve into the pure water to form an alkaline aqueous solution, and peeling off the treatment film holding the object to be removed from the surface of the substrate through the alkaline aqueous solution; a removal step of continuing to supply the pure water after stripping the treatment film, and flushing away the treatment film while the treatment film holds the object to be removed to remove the treatment film from the surface of the substrate.

[0030] According to this method, by bringing the pure water supplied to the surface of the substrate into contact with the treatment film, the alkaline component in the treatment film dissolves into the pure water to form (prepare) an alkaline aqueous solution on the substrate. Through the alkaline aqueous solution spontaneously formed on the substrate, the treatment film holding the object to be removed is peeled off from the surface of the substrate. Then, by continuing to supply pure water, the treatment film can be removed from the surface of the substrate while the treatment film holds the object to be removed. That is, by supplying only pure water to the surface of the substrate without supplying an alkaline aqueous solution, the object to be removed can be removed from the surface of the substrate. That is, the object to be removed can be removed from the surface of the substrate without consuming a large amount of relatively expensive alkaline aqueous solution. Therefore, both the increase in cost can be suppressed, and the object to be removed present on the surface of the substrate can be efficiently removed.

[0031] Another embodiment of the present invention provides a substrate processing apparatus, including: a processing liquid supply unit configured to supply a processing liquid having a solute and a solvent to a surface of a substrate; a solid formation unit configured to solidify or harden the processing liquid; a stripping liquid forming liquid supply unit configured to supply a stripping liquid forming liquid to the surface of the substrate; and a controller configured to control the processing liquid supply unit, the solid formation unit, and the stripping liquid forming liquid supply unit.

[0032] The controller is programmed to perform: a processing liquid supply step of supplying the processing liquid from the processing liquid supply unit to the surface of the substrate; a processing film formation step of forming, by using the solid formation unit, a processing film that solidifies or hardens the processing liquid supplied to the surface of the substrate and holds a removal object present on the surface of the substrate; a stripping step of forming a stripping liquid by bringing the stripping liquid forming liquid supplied from the stripping liquid forming liquid supply unit into contact with the processing film, and stripping the processing film holding the removal object from the surface of the substrate by the stripping liquid; and a removal step of removing the processing film from the surface of the substrate while keeping the processing film holding the removal object by continuously supplying the stripping liquid forming liquid from the stripping liquid forming liquid supply unit after stripping the processing film.

[0033] According to this configuration, by bringing the stripping liquid forming liquid supplied to the surface of the substrate into contact with the processing film, a stripping liquid for stripping the processing film from the surface of the substrate is formed on the substrate. The processing film holding the removal object is stripped from the surface of the substrate by the stripping liquid spontaneously formed on the substrate. Then, by continuously supplying the stripping liquid forming liquid, the processing film can be removed from the surface of the substrate while the processing film holds the removal object. That is, by supplying only the stripping liquid forming liquid to the surface of the substrate without supplying the stripping liquid, the removal object can be removed from the surface of the substrate. That is, the removal object can be removed from the surface of the substrate without consuming a large amount of relatively expensive stripping liquid. Therefore, both an increase in cost can be suppressed and the removal object present on the surface of the substrate can be efficiently removed.

[0034] In another embodiment of the present invention, the solute includes a stripping liquid forming substance. And, in the processing film formation step, a processing film having the stripping liquid forming substance in a solid state is formed. And, in the stripping step, the stripping liquid is formed by dissolving the stripping liquid forming substance in a solid state in the processing film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0035] According to this structure, a stripping liquid is formed by dissolving a stripping liquid forming substance in a solid state in the treatment film into a stripping liquid forming solution. Therefore, the stripping liquid forming substance can be dissolved in the stripping liquid forming solution near the treatment film, and thus a stripping liquid can be formed near the treatment film. Therefore, the stripping liquid forming substance dissolved in the stripping liquid forming solution can be uniformly diffused to the whole of the stripping liquid forming solution, and the stripping liquid with a relatively high concentration of the stripping liquid forming substance before the diffusion can act on the treatment film. Thereby, the treatment film can be efficiently stripped, and thus the object to be removed existing on the surface of the substrate can be efficiently removed.

[0036] The stripping liquid forming substance required for the formation of the stripping liquid is also relatively expensive like the stripping liquid. Moreover, the time required to supply the amount of treatment liquid required for the formation of the treatment film to the substrate is shorter than the time required to strip the treatment film and remove it from the substrate. Therefore, in this structure, a treatment liquid containing a stripping liquid forming substance is supplied to the substrate for forming the treatment film, and a stripping liquid forming solution not containing a stripping liquid forming substance is supplied to the substrate for stripping and removing the treatment film. Therefore, compared with the structure in which a treatment liquid not containing a stripping liquid forming substance is supplied to the substrate for forming the treatment film, and a stripping liquid (a stripping liquid forming solution in which the stripping liquid forming substance is dissolved) is supplied to the substrate for stripping and removing the treatment film, the supply time (consumption amount) of the stripping liquid forming substance can be reduced. Therefore, an increase in cost can be suppressed.

[0037] As a result, both an increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0038] In another embodiment of the present invention, the stripping liquid is an alkaline liquid. The alkaline liquid can effectively strip the treatment film, but it is relatively expensive. If it is a structure in which an alkaline liquid is formed by the contact of the stripping liquid forming solution with the treatment film, the alkaline liquid can be spontaneously generated on the substrate. Therefore, by supplying only the stripping liquid forming solution to the surface of the substrate without supplying the alkaline liquid, the object to be removed can be removed from the surface of the substrate. That is, the object to be removed can be removed from the surface of the substrate without consuming a large amount of the relatively expensive alkaline liquid. Therefore, the consumption amount of the alkaline liquid can be reduced, and thus an increase in cost can be suppressed. Thereby, both an increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0039] In another embodiment of the present invention, the stripping liquid forming solution supply unit supplies pure water as the stripping liquid forming solution to the surface of the substrate. Therefore, relatively inexpensive pure water can be used as the stripping liquid forming solution, and the treatment film can be stripped and removed from the surface of the substrate. Thereby, both an increase in cost can be suppressed and the object to be removed existing on the surface of the substrate can be efficiently removed.

[0040] In another embodiment of the present invention, in the peeling step, by supplying the peeling liquid forming liquid to the surface of the substrate, the processing film is partially dissolved to form a through hole in the processing film.

[0041] According to this structure, by supplying the peeling liquid forming liquid to the surface of the substrate, the processing film is partially dissolved to form a through hole in the processing film. By forming a through hole in the processing film, the peeling liquid easily reaches the vicinity of the surface of the substrate. Therefore, the peeling liquid can act on the interface between the processing film and the substrate, so that the processing film can be efficiently peeled from the surface of the substrate. On the other hand, although a part of the processing film is dissolved to form a through hole, the remaining part remains in a solid state, that is, in a state of the object to be removed. As a result, the processing film can be quickly peeled from the surface of the substrate, and the object to be removed and the processing film can be efficiently removed from the surface of the substrate together.

[0042] In another embodiment of the present invention, the solute has a highly soluble substance and a low soluble substance whose solubility relative to the peeling liquid is lower than that of the highly soluble substance. And, in the processing film forming step, the processing film having the highly soluble substance and the low soluble substance in a solid state is formed. And, in the peeling step, the through hole is formed in the processing film by dissolving the highly soluble substance in a solid state in the processing film in the peeling liquid formed on the substrate.

[0043] According to this structure, the highly soluble substance has a higher solubility relative to the peeling liquid than the low soluble substance. Therefore, by dissolving the highly soluble substance in a solid state in the processing film in the peeling liquid, a through hole can be reliably formed in the processing film. On the other hand, the low soluble substance in the processing film is not dissolved and remains in a solid state. Therefore, while the object to be removed is held by the low soluble substance in a solid state, the peeling liquid can act on the interface between the low soluble substance in a solid state and the substrate. As a result, the processing film can be quickly peeled from the surface of the substrate, so that the object to be removed and the processing film can be efficiently removed from the surface of the substrate together.

[0044] In another embodiment of the present invention, the solubility of the low soluble substance relative to the peeling liquid forming liquid is lower than the solubility of the highly soluble substance relative to the peeling liquid forming liquid. And, in the processing film forming step, the through hole is formed in the processing film by dissolving the highly soluble substance in a solid state in the processing film in the peeling liquid forming liquid supplied to the surface of the substrate.

[0045] According to this structure, highly soluble substances have a higher solubility in the stripping liquid-forming liquid than low-soluble substances. Therefore, by dissolving the highly soluble substances in the solid state in the treatment film in the stripping liquid-forming liquid, through holes can be reliably formed in the treatment film. On the other hand, the low-soluble substances in the treatment film are not dissolved and remain in the solid state. Therefore, while the object to be removed is held by the low-soluble substances in the solid state, the stripping liquid can act on the interface between the low-soluble substances in the solid state and the substrate. As a result, the treatment film can be quickly stripped from the surface of the substrate, and thus the object to be removed and the treatment film can be efficiently removed from the surface of the substrate together.

[0046] In another embodiment of the present invention, the solute has a highly soluble substance and a low-soluble substance having a lower solubility in the stripping liquid-forming liquid than the highly soluble substance. And, in the treatment film forming step, a treatment film having the highly soluble substance and the low-soluble substance in the solid state is formed. And, in the stripping step, through holes are formed in the treatment film by dissolving the highly soluble substance in the solid state in the treatment film in the stripping liquid-forming liquid supplied to the surface of the substrate.

[0047] According to this structure, highly soluble substances have a higher solubility in the stripping liquid-forming liquid than low-soluble substances. Therefore, by dissolving the highly soluble substances in the solid state in the treatment film in the stripping liquid-forming liquid, through holes can be reliably formed in the treatment film. On the other hand, the low-soluble substances in the treatment film are not dissolved and remain in the solid state. Therefore, while the object to be removed is held by the low-soluble substances in the solid state, the stripping liquid can act on the interface between the low-soluble substances in the solid state and the substrate. As a result, the treatment film can be quickly stripped from the surface of the substrate, and thus the object to be removed and the treatment film can be efficiently removed from the surface of the substrate together.

[0048] Another embodiment of the present invention provides a substrate processing apparatus, a treatment liquid supply unit that supplies a treatment liquid containing a solute containing an alkaline component and a solvent to the surface of a substrate, a solid formation unit that solidifies or hardens the treatment liquid, a pure water supply unit that supplies pure water to the surface of the substrate, and a controller that controls the treatment liquid supply unit, the solid formation unit, and the pure water supply unit.

[0049] The controller is programmed to perform: a processing liquid supply step of supplying the processing liquid from the processing liquid supply unit to the surface of the substrate; a processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate by using the solid formation unit to form a processing film on the surface of the substrate that holds a removal object existing on the surface of the substrate and contains the alkaline component; a peeling step of bringing the pure water into contact with the processing film by supplying the pure water from the pure water supply unit to the surface of the substrate, dissolving the alkaline component in the processing film into the pure water to form an alkaline aqueous solution, and peeling the processing film holding the removal object from the surface of the substrate by means of the alkaline aqueous solution; and a removal step of continuing to supply the pure water from the pure water supply unit after peeling the processing film to remove the processing film from the surface of the substrate while the processing film holds the removal object.

[0050] According to this structure, by bringing the pure water supplied to the surface of the substrate into contact with the processing film, the alkaline component in the processing film is dissolved into the pure water to form (prepare) an alkaline aqueous solution on the substrate. By means of the alkaline aqueous solution spontaneously formed on the substrate, the processing film holding the removal object is peeled from the surface of the substrate. Then, by continuing to supply the pure water, the processing film can be removed from the surface of the substrate while the processing film holds the removal object. That is, by supplying only pure water to the surface of the substrate without supplying an alkaline aqueous solution, the removal object can be removed from the surface of the substrate. That is, the removal object can be removed from the surface of the substrate without consuming a large amount of relatively expensive alkaline aqueous solution. Therefore, both the increase in cost can be suppressed and the removal object existing on the surface of the substrate can be efficiently removed.

[0051] The above content or other objects, features, and effects of the present invention will become clearer by referring to the description of the following embodiments with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a schematic top view showing the internal configuration of a substrate processing apparatus according to a first embodiment of the present invention.

[0053] Figure 2 It is a schematic partial cross-sectional view showing the schematic structure of a processing unit included in the substrate processing apparatus.

[0054] Figure 3 It is a block diagram showing the electrical structure of the main part of the substrate processing apparatus.

[0055] Figure 4 It is a flowchart for explaining an example of the substrate processing performed by the substrate processing apparatus.

[0056] Figure 5A It is a schematic diagram for explaining the process liquid supply process (step S5) of the substrate processing.

[0057] Figure 5B It is a schematic diagram for explaining the thin film chemical process (step S6) of the substrate processing.

[0058] Figure 5C It is a schematic diagram for explaining the heating process (step S7) of the substrate processing.

[0059] Figure 5D It is a schematic diagram for explaining the stripping and removing process (step S8) of the substrate processing.

[0060] Figure 5E It is a schematic diagram for explaining the second rinsing process (step S9) of the substrate processing.

[0061] Figure 5F It is a schematic diagram for explaining the second organic solvent supply process (step S10) of the substrate processing.

[0062] Figure 5G It is a schematic diagram for explaining the spin drying process (step S11) of the substrate processing.

[0063] Figure 6A It is a schematic cross-sectional view for explaining the situation near the substrate surface after the heating process (step S7).

[0064] Figure 6B It is a schematic cross-sectional view for explaining the situation near the substrate surface during the execution of the stripping and removing process (step S8).

[0065] Figure 6C It is a schematic cross-sectional view for explaining the situation near the substrate surface during the execution of the stripping and removing process (step S8).

[0066] Figure 6D It is a schematic cross-sectional view for explaining the situation near the substrate surface during the execution of the stripping and removing process (step S8).

[0067] Figure 7 It is a schematic partial cross-sectional view showing the schematic structure of the processing unit included in the substrate processing apparatus according to the second embodiment. Detailed Embodiment

[0068] In this specification, unless otherwise specified, the singular forms include plural forms, and "a" and "the" mean "at least one". In this specification, unless otherwise specified, the elements of a concept can be manifested in various ways, and when the amount thereof (e.g., mass%, mole%) is described, the amount means the sum of these various amounts.

[0069] "And / or" includes all combinations of elements and also includes the use of monomers.

[0070] In this specification, when using "~" or "-" to represent a numerical range, unless otherwise specified, these numerical ranges include both endpoints and the units are common. For example, 5~25 mol% means 5 mol% or more and 25 mol% or less.

[0071] In this specification, "C x～y ", "C x ~C y ", and "C x " and other notations refer to the number of carbons in a molecule or substituent. For example, C 1～6 alkyl refers to an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0072] In this specification, when a polymer has multiple repeating units, these repeating units are copolymerized. As long as there is no special limitation, these copolymerizations can be any one of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or their mixtures. When representing a polymer or resin by a structural formula, n, m, etc. described in parentheses represent the number of repetitions.

[0073] <First Embodiment>

[0074] Figure 1 is a schematic top view showing the internal configuration of the substrate processing apparatus 1 according to the first embodiment of the present invention.

[0075] The substrate processing apparatus 1 is a single-sheet type apparatus that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a disk-shaped substrate.

[0076] The substrate processing apparatus 1 includes: a plurality of processing units 2 that process the substrate W using a fluid; a loading port LP on which a storage rack C for accommodating a plurality of substrates W processed by the processing units 2 is placed; transfer robots IR and CR that transfer the substrate W between the loading port LP and the processing units 2; and a controller 3 that controls the substrate processing apparatus 1.

[0077] Transfer robot IR transfers substrate W between storage rack C and transfer robot CR. Transfer robot CR transfers substrate W between transfer robot IR and processing unit 2. A plurality of processing units 2 have the same structure, for example. As will be described in detail later, the processing fluid supplied to substrate W in processing unit 2 includes chemical solution, rinse solution, processing solution, stripping solution forming solution, heat medium, inert gas, etc.

[0078] Each processing unit 2 has a chamber 4 and a processing cup 7 disposed in chamber 4, and the processing of substrate W is performed in processing cup 7. An entrance / exit (not shown) for loading or unloading substrate W by transfer robot CR is formed in chamber 4. A gate unit (not shown) for opening and closing the entrance / exit is provided on chamber 4.

[0079] Figure 2 It is a schematic diagram for explaining a structural example of processing unit 2. Processing unit 2 includes a rotating chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 8, a second moving nozzle 9, a third moving nozzle 10, a central nozzle 11, and a lower surface nozzle 12.

[0080] Rotating chuck 5 holds substrate W horizontally and rotates substrate W about a vertical rotation axis A1 (vertical axis) passing through the central portion of substrate W. Rotating chuck 5 includes a plurality of chuck pins 20, a rotating base 21, a rotating shaft 22, and a rotating motor 23.

[0081] Rotating base 21 has a circular plate shape in the horizontal direction. A plurality of chuck pins 20 that hold the periphery of substrate W are arranged at intervals along the circumferential direction of rotating base 21 on the upper surface of rotating base 21. Rotating base 21 and the plurality of chuck pins 20 constitute a substrate holding unit that holds substrate W horizontally. The substrate holding unit is also referred to as a substrate holder.

[0082] Rotating shaft 22 extends in the vertical direction along rotation axis A1. The upper end portion of rotating shaft 22 is joined to the center of the lower surface of rotating base 21. Rotating motor 23 applies a rotational force to rotating shaft 22. By rotating rotating shaft 22 using rotating motor 23, rotating base 21 rotates. Thereby, substrate W rotates about rotation axis A1. Rotating motor 23 is an example of a substrate rotation unit that rotates substrate W about rotation axis A1.

[0083] Opposing member 6 faces substrate W held by rotating chuck 5 from above. Opposing member 6 is formed in a circular plate shape having a diameter substantially the same as or larger than that of substrate W. Opposing member 6 has an opposing surface 6a that faces the upper surface (upper side surface) of substrate W. Opposing surface 6a is disposed substantially in a horizontal plane above rotating chuck 5.

[0084] A hollow shaft 60 is fixed to the side of the opposing member 6 opposite to the opposing surface 6a. A communication hole 6b is formed in a portion of the opposing member 6 that overlaps with the rotation axis A1 in a plan view. The communication hole 6b penetrates the opposing member 6 vertically and communicates with the internal space 60a of the hollow shaft 60.

[0085] The opposing member 6 blocks the environmental gas in the space between the opposing surface 6a and the upper surface of the substrate W and the environmental gas outside the space. Therefore, the opposing member 6 is also referred to as a partition plate.

[0086] The processing unit 2 further includes an opposing member lifting unit 61 that drives the lifting of the opposing member 6. The opposing member lifting unit 61 can position the opposing member 6 at any position (height) from the lower position to the upper position. The lower position refers to the position where the opposing surface 6a is closest to the substrate W within the movable range of the opposing member 6. The upper position refers to the position where the opposing surface 6a is farthest from the substrate W within the movable range of the opposing member 6.

[0087] The opposing member lifting unit 61 includes, for example: a ball screw mechanism (not shown), which is coupled to a support member (not shown) that supports the hollow shaft 60; and an electric motor (not shown), which provides driving force to the ball screw mechanism. The opposing member lifting unit 61 is also referred to as an opposing member elevator (partition plate elevator).

[0088] The processing cup 7 includes: a plurality of baffles 71 that block the liquid flying outward from the substrate W held by the chuck 5; a plurality of cups 72 that catch the liquid guided downward by the plurality of baffles 71; and a cylindrical outer wall member 73 that surrounds the plurality of baffles 71 and the plurality of cups 72.

[0089] In this embodiment, an example is illustrated in which two baffles 71 (a first baffle 71A and a second baffle 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided.

[0090] The first cup 72A and the second cup 72B each have a shape of an upwardly open annular groove.

[0091] The first baffle 71A is arranged to surround the rotating base 21. The second baffle 71B is arranged to surround the rotating base 21 on the outer side in the radial direction of rotation of the substrate W compared to the first baffle 71A.

[0092] The first baffle 71A and the second baffle 71B each have a substantially cylindrical shape, and the upper end portions of the respective baffles (the first baffle 71A and the second baffle 71B) are inclined inwardly toward the rotating base 21.

[0093] The first cup 72A catches the liquid guided downward by the first baffle 71A. The second cup 72B is integrally formed with the first baffle 71A and catches the liquid guided downward by the second baffle 71B.

[0094] The processing unit 2 includes a baffle lifting unit 74 that lifts and lowers the first baffle 71A and the second baffle 71B respectively. The baffle lifting unit 74 lifts and lowers the first baffle 71A between the lower position and the upper position. The baffle lifting unit 74 lifts and lowers the second baffle 71B between the lower position and the upper position.

[0095] When both the first baffle 71A and the second baffle 71B are in the upper position, the liquid scattered from the substrate W is blocked by the first baffle 71A. When the first baffle 71A is in the lower position and the second baffle 71B is in the upper position, the liquid scattered from the substrate W is blocked by the second baffle 71B.

[0096] The baffle lifting unit 74 includes, for example: a first ball screw mechanism (not shown) coupled to the first baffle 71A, a first motor (not shown) that provides driving force to the first ball screw mechanism, a second ball screw mechanism (not shown) coupled to the second baffle 71B, and a second motor (not shown) that provides driving force to the second ball screw mechanism. The baffle lifting unit 74 is also referred to as a baffle elevator.

[0097] The first moving nozzle 8 is an example of a liquid medicine supply unit that supplies (ejects) liquid medicine onto the upper surface of the substrate W held by the rotary chuck 5.

[0098] The first moving nozzle 8 moves in the horizontal direction and the vertical direction by a first nozzle moving unit 36. The first moving nozzle 8 can move between the center position and the original position (retracted position) in the horizontal direction. When the first moving nozzle 8 is at the center position, it is opposite to the rotation center of the upper surface of the substrate W. The rotation center of the upper surface of the substrate W refers to the intersection position on the upper surface of the substrate W with the rotation axis A1. When the first moving nozzle 8 is at the original position, it is not opposite to the upper surface of the substrate W and is located outside the processing cup 7 in a top view. The first moving nozzle 8 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0099] The first nozzle moving unit 36 includes, for example: a rotation axis (not shown) in the vertical direction, an arm (not shown) coupled to the rotation axis and extending horizontally, and a rotation axis driving unit (not shown) that raises, lowers, or rotates the rotation axis.

[0100] The rotation axis driving unit swings the arm by rotating the rotation axis about a vertical rotation axis. Further, the rotation axis driving unit moves the arm up and down by raising and lowering the rotation axis in the vertical direction. The first moving nozzle 8 is fixed to the arm. According to the swing and lifting of the arm, the first moving nozzle 8 moves in the horizontal direction and the vertical direction.

[0101] The first moving nozzle 8 is connected to a chemical liquid pipe 40 that guides the chemical liquid. When the chemical liquid valve 50 installed in the chemical liquid pipe 40 is opened, the chemical liquid is continuously ejected downward from the first moving nozzle 8.

[0102] The chemical liquid ejected from the first moving nozzle 8 is a liquid including at least one of, for example, sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, hydrogen peroxide, organic acids (e.g., citric acid, oxalic acid, etc.), organic bases (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactants, and corrosion inhibitors. Examples of the chemical liquid in which these liquids are mixed include SPM liquid (sulfuric acid / hydrogen peroxide mixture) and SC1 liquid (ammonia-hydrogen peroxide mixture).

[0103] The second moving nozzle 9 is an example of a processing liquid supply unit that supplies (ejects) a processing liquid toward the upper surface of the substrate W held by the rotating chuck 5.

[0104] The second moving nozzle 9 is moved in the horizontal direction and the vertical direction by a second nozzle moving unit 37. The second moving nozzle 9 can move between a center position and an original position (retracted position) in the horizontal direction. When the second moving nozzle 9 is located at the center position, it is opposed to the rotation center of the upper surface of the substrate W. When the second moving nozzle 9 is located at the original position, it is not opposed to the upper surface of the substrate W and is located outside the processing cup 7 in a top view. The second moving nozzle 9 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0105] The second nozzle moving unit 37 has the same structure as the first nozzle moving unit 36. That is, the second nozzle moving unit 37 includes, for example, a rotating shaft (not shown) in the vertical direction, an arm (not shown) that is combined with the rotating shaft and the second moving nozzle 9 and extends horizontally, and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0106] The second moving nozzle 9 is connected to a processing liquid pipe 41 that guides the processing liquid. When the processing liquid valve 51 installed in the processing liquid pipe 41 is opened, the processing liquid is continuously ejected downward from the second moving nozzle 9.

[0107] The processing liquid ejected from the second moving nozzle 9 includes a solute and a solvent. The processing liquid is solidified or hardened by at least a part of the solvent volatilizing (evaporating). The processing liquid forms a processing film that holds removal objects such as particles existing on the substrate W by being solidified or hardened on the substrate W.

[0108] Here, "solidification" means that, for example, with the evaporation of the solvent, the solute hardens by means of forces acting between molecules or atoms, etc. "Hardening" means that, for example, through chemical changes such as polymerization or crosslinking, the solute hardens. Therefore, "solidification or hardening" means that the solute "hardens" due to various reasons.

[0109] The third moving nozzle 10 is an example of a stripping liquid forming liquid supply unit (pure water supply unit) that supplies (ejects) a stripping liquid forming liquid such as pure water onto the upper surface of the substrate W held by the rotating chuck 5 to form a liquid.

[0110] The third moving nozzle 10 moves in the horizontal direction and the vertical direction by a third nozzle moving unit 38. The third moving nozzle 10 can move between the center position and the original position (retracted position) in the horizontal direction. The third moving nozzle 10 is opposite to the rotation center of the upper surface of the substrate W when located at the center position. The third moving nozzle 10 is not opposite to the upper surface of the substrate W when located at the original position and is located outside the processing cup 7 in a top view. The third moving nozzle 10 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0111] The third nozzle moving unit 38 has the same structure as the first nozzle moving unit 36. That is, the third nozzle moving unit 38 includes, for example, a rotating shaft (not shown) in the vertical direction, an arm (not shown) that is combined with the rotating shaft and the third moving nozzle 10 and extends horizontally, and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0112] The third moving nozzle 10 is connected to an upper stripping liquid forming liquid pipe 42 that guides the stripping liquid forming liquid to the third moving nozzle 10. When the upper stripping liquid forming liquid valve 52 installed in the upper stripping liquid forming liquid pipe 42 is opened, the stripping liquid forming liquid is continuously ejected downward from the ejection port of the third moving nozzle 10.

[0113] The stripping liquid forming liquid is a liquid for forming the stripping liquid described later. The stripping liquid forming liquid is, for example, pure water, and DIW (deionized water) is particularly preferred. Liquids other than DIW can also be used as the stripping liquid forming liquid. Examples of liquids other than DIW used as the stripping liquid forming liquid include carbonated water and functional water such as ammonia water with a dilution concentration (for example, about 10 ppm to 100 ppm).

[0114] The solute in the processing liquid ejected from the second moving nozzle 9 contains low-solubility substances, high-solubility substances, and stripping liquid forming substances.

[0115] The stripping liquid forming substance is a substance that forms a stripping liquid for stripping the treatment film from the surface of the substrate W by dissolving in the stripping liquid forming liquid. The stripping liquid forming substance is, for example, a salt (basic component) that dissolves in the stripping liquid forming liquid and exhibits alkalinity (basicity). The stripping liquid forming substance is, for example, primary amine, secondary amine, tertiary amine, and quaternary ammonium salt, etc. The stripping liquid is an aqueous solution of primary amine, secondary amine, tertiary amine, and quaternary ammonium salt, etc., that is, a basic aqueous solution (basic liquid).

[0116] The low solubility substance and the high solubility substance can use substances with different solubilities relative to the stripping liquid forming liquid and the stripping liquid. Specifically, as the high solubility substance, a substance with a higher solubility than the substance used as the low solubility substance in at least any one of the stripping liquid forming liquid and the stripping liquid can be used.

[0117] Regarding the high solubility substance, if its solubility in one of the stripping liquid forming liquid and the stripping liquid is higher than that of the low solubility substance, its solubility in the other of the stripping liquid forming liquid and the stripping liquid can be as low as the same level as the low solubility substance, and it can be almost insoluble in the other of the stripping liquid forming liquid and the stripping liquid. On the contrary, even if the high solubility substance is a substance with a higher solubility than the low solubility substance in one of the stripping liquid forming liquid and the stripping liquid, a substance with a lower solubility than the low solubility substance in the other of the stripping liquid forming liquid and the stripping liquid cannot be used.

[0118] The low solubility substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, novolac, and the high solubility substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane.

[0119] The solvent contained in the treatment liquid ejected from the second moving nozzle 9 is a liquid that can dissolve the low solubility substance, the high solubility substance, and the stripping liquid forming substance. Preferably, the solvent contained in the treatment liquid is a liquid that is compatible (can be mixed) with the stripping liquid forming liquid. The details of the solvent, the low solubility substance, the high solubility substance, and the stripping liquid forming substance contained in the treatment liquid ejected from the second moving nozzle 9, together with the details of the stripping liquid forming liquid ejected from the third moving nozzle 10, will be described later.

[0120] The central nozzle 11 is accommodated in the internal space 60a of the hollow shaft 60 of the relative member 6. The ejection port 11a provided at the tip of the central nozzle 11 faces the central region of the upper surface of the substrate W from above. The central region of the upper surface of the substrate W is a region on the upper surface of the substrate W that includes the rotation center of the substrate W.

[0121] The central nozzle 11 includes a plurality of tubes (a first tube 31, a second tube 32, and a third tube 33) that eject fluid downward, and a cylindrical housing 30 that surrounds the plurality of tubes. The plurality of tubes and the housing 30 extend in the vertical direction along the rotation axis A1. The ejection port 11a of the central nozzle 11 may also be the ejection ports of the plurality of tubes.

[0122] The first tube 31 is an example of a rinse liquid supply unit that supplies a rinse liquid to the upper surface of the substrate W. The second tube 32 is an example of a gas supply unit that supplies gas between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6. The third tube 33 is an example of an organic solvent supply unit that supplies an organic solvent such as IPA to the upper surface of the substrate W.

[0123] The first tube 31 is connected to an upper-side rinse liquid pipe 44 that guides the rinse liquid to the first tube 31. When the upper-side rinse liquid valve 54 installed in the upper-side rinse liquid pipe 44 is opened, the rinse liquid is continuously ejected from the first tube 31 (central nozzle 11) toward the central region of the upper surface of the substrate W.

[0124] The second tube 32 is connected to a gas pipe 45 that guides gas to the second tube 32. When the gas valve 55 installed in the gas pipe 45 is opened, the gas is continuously ejected downward from the second tube 32 (central nozzle 11).

[0125] The gas ejected from the second tube 32 is, for example, an inert gas such as nitrogen (N 2 ). The gas ejected from the second tube 32 may also be air. The inert gas is not limited to nitrogen, and any gas that is inert with respect to the upper surface of the substrate W and the pattern formed on the upper surface of the substrate W is acceptable. Examples of inert gases other than nitrogen include noble gases such as argon.

[0126] The third tube 33 is connected to an organic solvent pipe 46 that guides the organic solvent to the third tube 33. When the organic solvent valve 56 installed in the organic solvent pipe 46 is opened, the organic solvent is continuously ejected from the third tube 33 (central nozzle 11) toward the central region of the upper surface of the substrate W.

[0127] The organic solvent ejected from the third tube 33 is a residue removal liquid for removing residues remaining on the upper surface of the substrate W after the treatment film has been removed by the stripping liquid. Preferably, the organic solvent ejected from the third tube 33 is compatible with the treatment liquid and the rinse liquid.

[0128] Examples of the organic solvent ejected from the third tube 33 include liquids containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

[0129] In addition, the organic solvent ejected from the third tube 33 does not have to consist only of monomer components, and may also be a liquid mixed with other components. For example, it may be a mixture of IPA and DIW, or a mixture of IPA and HFE.

[0130] The lower surface nozzle 12 is inserted into a through hole 21a that opens at the center of the upper surface of the rotating base 21. The ejection port 12a of the lower surface nozzle 12 is exposed from the upper surface of the rotating base 21. The ejection port 12a of the lower surface nozzle 12 faces the central region of the lower surface (the lower side surface) of the substrate W from below. The central region of the lower surface of the substrate W is the region of the lower surface of the substrate W that includes the rotation center of the substrate W.

[0131] One end of a common pipe 80 that jointly guides the rinse liquid, the stripping liquid forming liquid, and the heat medium is connected to the lower surface nozzle 12. At the other end of the common pipe 80, a lower side rinse liquid pipe 81 that guides the rinse liquid to the common pipe 80, a lower side stripping liquid forming liquid pipe 82 that guides the stripping liquid forming liquid to the common pipe 80, and a heat medium pipe 83 that guides the heat medium to the common pipe 80 are connected.

[0132] When the lower side rinse liquid valve 86 installed in the lower side rinse liquid pipe 81 is opened, the rinse liquid is continuously ejected from the lower surface nozzle 12 toward the central region of the lower surface of the substrate W. When the lower side stripping liquid forming liquid valve 87 installed in the lower side stripping liquid forming liquid pipe 82 is opened, the stripping liquid forming liquid is continuously ejected from the lower surface nozzle 12 toward the central region of the lower surface of the substrate W. When the heat medium valve 88 installed in the heat medium pipe 83 is opened, the heat medium is continuously ejected from the lower surface nozzle 12 toward the central region of the lower surface of the substrate W.

[0133] The lower surface nozzle 12 is an example of a lower side rinse liquid supply unit that supplies the rinse liquid to the lower surface of the substrate W. In addition, the lower surface nozzle 12 is an example of a lower side stripping liquid forming liquid supply unit that supplies the stripping liquid forming liquid to the lower surface of the substrate W. In addition, the lower surface nozzle 12 is an example of a heat medium supply unit that supplies the heat medium for heating the substrate W to the substrate W. The lower surface nozzle 12 may also be a substrate heating unit that heats the substrate W.

[0134] The heat medium ejected from the lower surface nozzle 12 is, for example, high-temperature DIW at a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid. When the solvent contained in the processing liquid is IPA, for example, DIW at 60°C to 80°C is used as the heat medium. The heat medium ejected from the lower surface nozzle 12 is not limited to high-temperature DIW, and may also be a high-temperature gas such as high-temperature inert gas or high-temperature air at a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid.

[0135] Figure 3It is a block diagram showing the electrical structure of the main part of the substrate processing apparatus 1. The controller 3 has a microcomputer and controls the controlled objects of the substrate processing apparatus 1 according to a prescribed control program.

[0136] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B that stores the control program. The controller 3 is configured to execute various controls for substrate processing by the processor 3A executing the control program.

[0137] In particular, the controller 3 is programmed to control the transfer robots IR, CR, the rotation motor 23, the first nozzle moving unit 36, the second nozzle moving unit 37, the third nozzle moving unit 38, the relative member lifting unit 61, the baffle lifting unit 74, the chemical liquid valve 50, the processing liquid valve 51, the upper side stripping liquid forming liquid valve 52, the upper side rinsing liquid valve 54, the gas valve 55, the organic solvent valve 56, the lower side rinsing liquid valve 86, the lower side stripping liquid forming liquid valve 87, and the heat medium valve 88.

[0138] Figure 4 It is a flowchart for explaining an example of the substrate processing performed by the substrate processing apparatus 1. In Figure 4 mainly shows the processing implemented by the controller 3 executing the program. Figures 5A to 5G It is a schematic diagram for explaining the situations of the respective processes of the substrate processing.

[0139] In the substrate processing performed by the substrate processing apparatus 1, for example, as Figure 4 shown, the substrate loading process (step S1), the chemical liquid supply process (step S2), the first rinsing process (step S3), the first organic solvent supply process (step S4), the processing liquid supply process (step S5), the film forming process (step S6), the heating process (step S7), the stripping removal process (step S8), the second rinsing process (step S9), the second organic solvent supply process (step S10), the spin drying process (step S11), and the substrate unloading process (step S12) are sequentially executed.

[0140] First, the unprocessed substrate W is transferred from the storage rack C into the processing unit 2 by the transfer robots IR, CR (refer to Figure 1 ) and handed over to the rotary chuck 5 (step S1). Thereby, the substrate W is held horizontally by the rotary chuck 5 (substrate holding process). The holding of the substrate W by the rotary chuck 5 continues until the end of the spin drying process (step S11). When loading the substrate W, the relative member 6 retracts to the upper position.

[0141] Next, after the transfer robot CR retracts outside the processing unit 2, the liquid medicine supply process (step S2) is started. Specifically, the rotation motor 23 rotates the rotation base 21. Thereby, the substrate W held horizontally is rotated (substrate rotation process). The baffle lifting unit 74 moves the first baffle 71A and the second baffle 71B to the upward position.

[0142] The first nozzle moving unit 36 moves the first moving nozzle 8 to the processing position. The processing position of the first moving nozzle 8 is, for example, the central position. Then, the liquid medicine valve 50 is opened. Thereby, the liquid medicine is supplied (sprayed) from the first moving nozzle 8 toward the central region of the upper surface of the rotating substrate W. The liquid medicine supplied to the upper surface of the substrate W spreads radially under the action of centrifugal force and covers the entire upper surface of the substrate W. Thereby, the upper surface of the substrate W is processed by the liquid medicine. The spraying of the liquid medicine from the first moving nozzle 8 continues for a predetermined time, for example, 30 seconds. In the liquid medicine supply process, the substrate W rotates at a predetermined liquid medicine rotation speed, for example, 800 rpm.

[0143] Next, the first rinsing process (step S3) is started. In the first rinsing process, the liquid medicine on the substrate W is rinsed with the rinsing liquid.

[0144] Specifically, the liquid medicine valve 50 is closed. Thereby, the supply of the liquid medicine to the substrate W is stopped. Then, the first nozzle moving unit 36 moves the first moving nozzle 8 to the original position. Then, the relative member lifting unit 61 moves the relative member 6 to the processing position between the upward position and the downward position. When the relative member 6 is in the processing position, the distance between the upper surface of the substrate W and the opposing surface 6a is, for example, 30 mm. In the first rinsing process, the first baffle 71A and the second baffle 71B are maintained in the upward position.

[0145] Then, the upper side rinsing liquid valve 54 is opened. Thereby, the rinsing liquid is supplied (sprayed) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W. The rinsing liquid supplied from the central nozzle 11 to the upper surface of the substrate W spreads radially under the action of centrifugal force and covers the entire upper surface of the substrate W. Thereby, the liquid medicine on the upper surface of the substrate W is rinsed out of the substrate W. In the first rinsing process, the substrate W rotates at a predetermined first rinsing rotation speed, for example, 800 rpm.

[0146] In addition, open the lower cleaning liquid valve 86. Thereby, the cleaning liquid is supplied (sprayed) from the lower surface nozzle 12 toward the central region of the lower surface of the rotating substrate W. The cleaning liquid supplied from the lower surface nozzle 12 to the lower surface of the substrate W is radially expanded by the centrifugal force and spreads over the entire lower surface of the substrate W. Even when the chemical liquid dispersed from the substrate W adheres to the lower surface, the chemical liquid adhering to the lower surface can be washed by the cleaning liquid supplied from the lower surface nozzle 12. The spraying of the cleaning liquid from the central nozzle 11 and the lower surface nozzle 12 continues for a specified time, for example, 30 seconds.

[0147] Next, start the first organic solvent supply process (step S4). In the first organic solvent supply process, the cleaning liquid on the substrate W is replaced by the organic solvent.

[0148] Specifically, close the upper cleaning liquid valve 54 and the lower cleaning liquid valve 86. Thereby, the supply of the cleaning liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the baffle lifting unit 74 moves the first baffle 71A to the lower position while maintaining the second baffle 71B in the upper position. The relative member 6 is maintained at the processing position.

[0149] Then, open the organic solvent valve 56. Thereby, the organic solvent is supplied (sprayed) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W.

[0150] The organic solvent supplied from the central nozzle 11 to the upper surface of the substrate W is radially diffused by the centrifugal force and spreads over the entire upper surface of the substrate W. Thereby, the cleaning liquid on the substrate W is replaced by the organic solvent. The spraying of the organic solvent from the central nozzle 11 continues for a specified time, for example, 10 seconds.

[0151] In the first organic solvent supply process, the substrate W rotates at a specified first organic solvent rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not need to rotate at a constant rotation speed in the first organic solvent supply process. For example, the rotation motor 23 may rotate the substrate W at 300 rpm when starting to supply the organic solvent, and while supplying the organic solvent to the substrate W, accelerate the rotation of the substrate W until the rotation speed of the substrate W becomes 1500 rpm.

[0152] Next, start the processing liquid supply process (step S5). Specifically, close the organic solvent valve 56. Thereby, the supply of the organic solvent to the substrate W is stopped. Then, the relative member lifting unit 61 moves the relative member 6 to the upper position. Then, the baffle lifting unit 74 moves the first baffle 71A to the upper position. In the processing liquid supply process, the substrate W rotates at a specified processing liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0153] Then, asFigure 5A As shown, the second nozzle moving unit 37 moves the second moving nozzle 9 to the processing position. The processing position of the second moving nozzle 9 is, for example, the central position. Then, the processing liquid valve 51 is opened. Thereby, the processing liquid is supplied (sprayed) from the second moving nozzle 9 toward the central region of the upper surface of the rotating substrate W (processing liquid supply process, processing liquid spraying process). Thereby, the organic solvent on the substrate W is replaced by the processing liquid, and thus a liquid film 101 (processing liquid film) of the processing liquid is formed on the substrate W (processing liquid film forming process). The supply of the processing liquid from the second moving nozzle 9 continues for a predetermined time, for example, 2 seconds to 4 seconds.

[0154] Next, a processing film forming process (step S6 and step S7) is performed. In the processing film forming process, the processing liquid on the substrate W is solidified or hardened, so that a processing film 100 for holding the object to be removed existing on the substrate W is formed on the upper surface of the substrate W (refer to Figure 5C ).

[0155] In the processing film forming process, a thinning process (rotation stop process) (step S6) is performed. In the thinning process, first, the processing liquid valve 51 is closed. Thereby, the supply of the processing liquid to the substrate W is stopped. Then, the second nozzle moving unit 37 moves the second moving nozzle 9 to the original position.

[0156] As Figure 5B shown, in the thinning process, in a state where the supply of the processing liquid to the upper surface of the substrate W is stopped, a part of the processing liquid is discharged from the upper surface of the substrate W by centrifugal force so that the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness. In the thinning process, the opposing member 6, the first baffle 71A, and the second baffle 71B are maintained in the upper position.

[0157] In the thinning process, the rotation motor 23 changes the rotation speed of the substrate W to a predetermined thinning speed. The thinning speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W may also be kept constant within the range of 300 rpm to 1500 rpm, and may also be appropriately changed within the range of 300 rpm to 1500 rpm in the middle of the thinning process. The thinning process is performed for a predetermined time, for example, 30 seconds.

[0158] In the processing film forming process, after the thinning process, a heating process (step S7) for heating the substrate W is performed. In the heating process, in order to volatilize (evaporate) a part of the solvent of the processing liquid on the substrate W, the liquid film 101 on the substrate W (refer to Figure 5B ) is heated.

[0159] Specifically, as Figure 5CAs shown, the relative member lifting unit 61 moves the relative member 6 to a proximity position between the upper position and the lower position. The proximity position may also be the lower position. The proximity position is a position where the distance from the upper surface of the substrate W to the opposing surface 6a is, for example, 1 mm. In the heating process, the first baffle 71A and the second baffle 71B are maintained in the upper position.

[0160] Then, the gas valve 55 is opened. Thereby, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 101) and the opposing surface 6a of the relative member 6 (gas supply process).

[0161] By blowing gas onto the liquid film 101 on the substrate W, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (solvent evaporation process, solvent evaporation promotion process). Therefore, the time required for forming the processing film 100 can be shortened. The central nozzle 11 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0162] In addition, the heat medium valve 88 is opened. Thereby, the heat medium is supplied (sprayed) from the lower surface nozzle 12 toward the central region of the lower surface of the rotating substrate W (heat medium supply process, heat medium spraying process). The heat medium supplied from the lower surface nozzle 12 to the lower surface of the substrate W is radially expanded by the centrifugal force and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W continues for a predetermined time, for example, 60 seconds. In the heating process, the substrate W rotates at a predetermined heating rotation speed, for example, 1000 rpm.

[0163] By supplying the heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated via the substrate W. Thereby, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (solvent evaporation process, solvent evaporation promotion process). Therefore, the time required for forming the processing film 100 can be shortened. The lower surface nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0164] By performing the thin film process and the heating process, the processing liquid is solidified or hardened, thereby forming the processing film 100 on the substrate W. In this way, the substrate rotation unit (rotation motor 23), the central nozzle 11, and the lower surface nozzle 12 constitute a solid formation unit that solidifies or hardens the processing liquid to form a solid (processing film 100).

[0165] In the heating step, preferably, the substrate W is heated in such a manner that the temperature of the processing liquid on the substrate W is lower than the boiling point of the solvent. By heating the processing liquid to a temperature lower than the boiling point of the solvent, the solvent can be moderately retained in the processing film 100. As a result, compared with the case where no solvent remains in the processing film 100, in the subsequent peeling and removing step, due to the interaction between the solvent remaining in the processing film 100 and the peeling liquid forming liquid, the peeling liquid forming liquid can be easily fused with the processing film 100. Therefore, it is easy to form the peeling liquid.

[0166] The heat medium scattered outside the substrate W due to the centrifugal force is blocked by the first baffle 71A. The heat medium blocked by the first baffle 71A may splash from the first baffle 71A. However, since the opposing member 6 is close to the upper surface of the substrate W, the upper surface of the substrate W can be protected from the heat medium splashing from the first baffle 71A. Therefore, since the attachment of the heat medium to the upper surface of the processing film 100 can be suppressed, the generation of particles caused by the splashing of the heat medium from the first baffle 71A can be suppressed.

[0167] Moreover, by supplying gas from the central nozzle 11, an air flow F moving from the central region of the upper surface of the substrate W toward the periphery of the upper surface of the substrate W is formed in the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W. By forming the air flow F moving from the central region of the upper surface of the substrate W toward the periphery of the upper surface of the substrate W, the heat medium splashing from the first baffle 71A can be pushed back toward the first baffle 71A. Therefore, the attachment of the heat medium to the upper surface of the processing film 100 can be further suppressed.

[0168] Next, a peeling and removing step (step S8) of peeling and removing the processing film 100 from the upper surface of the substrate W is performed. Specifically, the heat medium valve 88 is closed. As a result, the supply of the heat medium to the lower surface of the substrate W is stopped. In addition, the gas valve 55 is closed. As a result, the supply of gas to the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is stopped.

[0169] Then, the opposing member lifting unit 61 moves the opposing member 6 to the upper position. Then, as Figure 5D shown, the third nozzle moving unit 38 moves the third moving nozzle 10 to the processing position. The processing position of the third moving nozzle 10 is, for example, the central position.

[0170] Then, the upper side peeling liquid forming liquid valve 52 is opened. As a result, the peeling liquid forming liquid (upper side peeling liquid forming liquid supply step, upper side peeling liquid forming liquid ejection step) is supplied (ejected) from the third moving nozzle 10 toward the central region of the upper surface of the rotating substrate W. The peeling liquid forming liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by the centrifugal force.

[0171] The supply of the stripping liquid forming liquid to the upper surface of the substrate W continues for a specified time, for example, 60 seconds. As described above, the supply time of the processing liquid to the upper surface of the substrate W in the processing liquid supply step is, for example, 2 to 4 seconds. Therefore, the supply time of the stripping liquid forming liquid to the upper surface of the substrate W in the stripping and removal step is longer than the supply time of the processing liquid to the upper surface of the substrate W in the processing liquid supply step.

[0172] In the stripping and removal step, the substrate W rotates at a specified stripping rotation speed, for example, 800 rpm.

[0173] In addition, the lower stripping liquid forming liquid valve 87 is opened. Thereby, the stripping liquid forming liquid (lower stripping liquid forming liquid supply step, lower stripping liquid forming liquid ejection step) is supplied (ejected) from the lower surface nozzle 12 toward the central region of the lower surface of the rotating substrate W. The stripping liquid forming liquid supplied to the lower surface of the substrate W diffuses to the entire lower surface of the substrate W by centrifugal force.

[0174] By supplying the stripping liquid forming liquid to the upper surface of the substrate W, the stripping liquid forming liquid contacts the processing film 100, thereby forming a stripping liquid. Then, the processing film 100 is stripped from the upper surface of the substrate W together with the object to be removed by the stripping action of the stripping liquid (stripping step). The processing film 100 splits into film pieces when being stripped from the upper surface of the substrate W. Then, after stripping the processing film 100, by continuously supplying the stripping liquid forming liquid to the upper surface of the substrate W, the film pieces of the split processing film 100 are discharged out of the substrate W together with the stripping liquid forming liquid. Thereby, the film pieces of the processing film 100 maintaining the state of the object to be removed are removed from the upper surface of the substrate W (removal step).

[0175] Here, in Figure 5A the processing liquid supplied to the upper surface of the substrate W in the shown processing liquid supply step (step S5) sometimes spreads along the periphery of the substrate W to the lower surface of the substrate W. In addition, the processing liquid dispersed from the substrate W sometimes splashes from the first baffle 71A and adheres to the lower surface of the substrate W. Even in such a case, as Figure 5C shown, in the heating step (step S7), the heat medium is supplied to the lower surface of the substrate W. Therefore, through the flow of this heat medium, the processing liquid can be removed from the lower surface of the substrate W.

[0176] Moreover, sometimes the processing liquid adhering to the lower surface of the substrate W due to the processing liquid supply step (step S5) solidifies or hardens to form a solid. Even in such a case, as Figure 5DAs shown, during the period when the stripping liquid forming liquid is supplied to the upper surface of the substrate W in the stripping and removing process (step S8), by supplying (spraying) the stripping liquid forming liquid from the lower surface nozzle 12 to the lower surface of the substrate W, the solid can be stripped and removed from the lower surface of the substrate W. Specifically, the stripping liquid is formed by the contact between the stripping liquid forming liquid and the solid, and the solid is stripped from the lower surface of the substrate W by the stripping action of the stripping liquid.

[0177] After the stripping and removing process (step S8), a second rinsing process (step S9) is performed. Specifically, the upper side stripping liquid forming liquid valve 52 and the lower side stripping liquid forming liquid valve 87 are closed. Thereby, the supply of the stripping liquid forming liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the third nozzle moving unit 38 moves the third moving nozzle 10 to the original position. Then, as Figure 5E shown, the relative member lifting unit 61 moves the relative member 6 to the processing position. In the second rinsing process, the substrate W rotates at a prescribed second rinsing rotation speed, for example, 800 rpm. The first baffle 71A and the second baffle 71B are maintained in the upper position.

[0178] Then, the upper side rinsing liquid valve 54 is opened. Thereby, rinsing liquid is supplied (sprayed) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W (second upper side rinsing liquid supply process, second upper side rinsing liquid spraying process). The rinsing liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, the stripping liquid forming liquid adhering to the upper surface of the substrate W is rinsed by the rinsing liquid.

[0179] In addition, the lower side rinsing liquid valve 86 is opened. Thereby, rinsing liquid is supplied (sprayed) from the lower surface nozzle 12 toward the central region of the lower surface of the rotating substrate W (second lower side rinsing liquid supply process, second lower side rinsing liquid spraying process). Thereby, the stripping liquid forming liquid adhering to the lower surface of the substrate W is rinsed by the rinsing liquid. The supply of the rinsing liquid to the upper surface and the lower surface of the substrate W continues for a prescribed time, for example, 35 seconds.

[0180] Next, a second organic solvent supply process (step S10) is performed. Specifically, the upper side rinsing liquid valve 54 and the lower side rinsing liquid valve 86 are closed. Thereby, the supply of the rinsing liquid to the upper surface and the lower surface of the substrate W is stopped. Then, as Figure 5F shown, the baffle lifting unit 74 moves the first baffle 71A to the lower position. Then, the relative member 6 is maintained in the processing position. In the second organic solvent supply process, the substrate W rotates at a prescribed second organic solvent rotation speed, for example, 300 rpm.

[0181] Then, open the organic solvent valve 56. Thereby, an organic solvent is supplied (sprayed) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W (second organic solvent supply process, second organic solvent spraying process, residue removal liquid supply process). The supply of the organic solvent to the upper surface of the substrate W continues for a specified time, for example, 30 seconds.

[0182] The organic solvent supplied to the upper surface of the substrate W is radially expanded by the centrifugal force and spreads over the entire upper surface of the substrate W. Thereby, the rinsing liquid on the upper surface of the substrate W is replaced by the organic solvent. After the organic solvent supplied to the upper surface of the substrate W dissolves the residue of the processing film 100 remaining on the upper surface of the substrate W, it is discharged from the periphery of the upper surface of the substrate W (residue removal process).

[0183] Next, a spin drying process (step S11) is performed. Specifically, close the organic solvent valve 56. Thereby, the supply of the organic solvent to the upper surface of the substrate W is stopped. Then, as Figure 5G shown, the relative member lifting unit 61 moves the relative member 6 to the drying position below the processing position. When the relative member 6 is in the drying position, the distance between the opposing surface 6a of the relative member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, open the gas valve 55. Thereby, gas is supplied to the space between the upper surface of the substrate W and the opposing surface 6a of the relative member 6.

[0184] Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed. The substrate W in the spin drying process rotates at a drying speed, for example, 1500 rpm. The spin drying process is performed for a specified time, for example, 30 seconds. Thereby, a large centrifugal force acts on the organic solvent on the substrate W, and the organic solvent on the substrate W is thrown to the periphery of the substrate W. In the spin drying process, by supplying gas to the space between the upper surface of the substrate W and the opposing surface 6a of the relative member 6, the evaporation of the organic solvent can be promoted.

[0185] Then, the rotation motor 23 stops the rotation of the substrate W. The baffle lifting unit 74 moves the first baffle 71A and the second baffle 71B to the lower position. Close the gas valve 55. Then, the relative member lifting unit 61 moves the relative member 6 to the upper position.

[0186] The transfer robot CR enters the processing unit 2 and picks up the processed substrate W from the chuck pin 20 of the rotary chuck 5, and carries it out of the processing unit 2 (step S12). This substrate W is transferred from the transfer robot CR to the transfer robot IR and is received by the transfer robot IR and housed in the storage rack C.

[0187] Next, refer to Figures 6A to 6D to describe the situation when the processing film 100 is peeled off from the substrate W. Figure 6AShows the situation near the upper surface of the substrate W after the heating process (step S7). Figures 6B to 6D Shows the situation near the upper surface of the substrate W during the execution of the peeling and removing process (step S8).

[0188] In the heating process carried out in the processing film formation process, as described above, the liquid film 101 on the substrate W is heated by the heat medium via the substrate W. Thus, as Figure 6A shown, a processing film 100 that holds removal objects 103 such as particles is formed. Specifically, by evaporating at least a part of the solvent, highly soluble substances contained in the solute of the processing liquid form highly soluble solids 110 (highly soluble substances in solid state). In addition, by evaporating at least a part of the solvent, poorly soluble substances contained in the solute of the processing liquid form poorly soluble solids 111 (poorly soluble substances in solid state), and stripping liquid forming substances contained in the solute of the processing liquid form stripping liquid forming solids 112 (stripping liquid forming substances in solid state).

[0189] The processing film 100 is divided into a part where highly soluble solids 110 are concentrated and a part where poorly soluble solids 111 are concentrated. The stripping liquid forming solids 112 are uniformly formed throughout the processing film 100.

[0190] Refer to Figure 6B , in the peeling and removing process, when the stripping liquid forming liquid is supplied to the upper surface of the substrate W, the stripping liquid forming solids 112 dissolve in the stripping liquid forming liquid. By the stripping liquid forming solids 112 dissolving in the stripping liquid forming liquid, a stripping liquid (alkaline liquid) is formed.

[0191] Refer to Figure 6C , the highly soluble solids 110 are dissolved due to the supply of the stripping liquid forming liquid. That is, the processing film 100 is partially dissolved. By dissolving the highly soluble solids 110, through holes 102 are formed in the part of the processing film 100 where the highly soluble solids 110 are concentrated (through hole forming process). The through holes 102 are particularly likely to be formed in the part where the highly soluble solids 110 extend in the thickness direction T of the substrate W (also the thickness direction of the processing film 100). When viewed from above, the diameter of the through holes 102 is, for example, on the order of several nm.

[0192] In the case where the highly soluble solids 110 have the property of dissolving in both the stripping liquid forming liquid and the stripping liquid, even if the stripping liquid forming substances do not sufficiently dissolve out into the stripping liquid forming liquid, through holes 102 start to be formed from the moment the stripping liquid forming liquid comes into contact with the processing film 100. Then, when the stripping liquid is formed, the formation of the through holes 102 is promoted. That is, the through holes 102 are formed by both the stripping liquid and the stripping liquid forming liquid.

[0193] When the highly soluble solid 110 has the property of being almost insoluble in the stripping solution forming liquid but soluble in the stripping solution, after the stripping solution forming substance is sufficiently dissolved in the stripping solution forming liquid, the through hole 102 is started to be formed. That is, the through hole 102 is formed by the stripping solution.

[0194] When the highly soluble solid 110 has the property of being almost insoluble in the stripping solution but soluble in the stripping solution forming liquid, the through hole 102 is formed before the stripping solution forming substance is dissolved in the stripping solution forming liquid. That is, the through hole 102 is formed by the stripping solution forming liquid.

[0195] Until the through hole 102 is formed, the stripping solution forming substance is eluted from the processing film 100 into the stripping solution forming liquid to form the stripping solution. The solubility of the low solubility substance with respect to the stripping solution is low, and the low solubility substance is hardly dissolved by the stripping solution. Therefore, only the surface vicinity of the low solubility solid 111 is slightly dissolved by the stripping solution. Therefore, the stripping solution reaching the vicinity of the upper surface of the substrate W via the through hole 102 slightly dissolves the portion of the low solubility solid 111 near the upper surface of the substrate W. Thus, as Figure 6C shown in the enlarged view, the stripping solution gradually dissolves the low solubility solid 111 near the upper surface of the substrate W while entering the gap G (stripping solution entering step) between the processing film 100 and the upper surface of the substrate W.

[0196] When the concentrated portion of the highly soluble solid 110 in the processing film 100 is dissolved, the stripping solution forming solid 112 present in this portion and the stripping solution forming solid 112 present in the portion surrounding the through hole 102 in the processing film 100 are dissolved by the stripping solution (stripping solution forming liquid). Similarly, by the stripping solution entering the gap G, the stripping solution forming solid 112 present in the portion near the upper surface of the substrate W in the processing film 100 is dissolved by the stripping solution. Thus, the concentration of the alkaline component in the stripping solution can be further increased (refer to Figure 6C the enlarged view). Therefore, the stripping of the low solubility solid 111 of the processing film 100 can be further promoted.

[0197] Then, for example, the processing film 100 splits starting from the periphery of the through hole 102 and becomes a film piece. As Figure 6D shown, the film piece of the processing film 100 is peeled off from the substrate W while holding the object to be removed 103 (processing film splitting step, peeling step). Then, by continuously supplying the stripping solution forming liquid, the processing film 100 that has become a film piece is washed away (pushed out of the substrate W) while holding the object to be removed 103 and is removed from the upper surface of the substrate W (removing step).

[0198] In addition, there is also a case where the stripping liquid hardly dissolves the low-solubility solid 111. Even in this case, the treatment film 100 is peeled off from the substrate W by entering the minute gap G between the treatment film 100 and the upper surface of the substrate W.

[0199] According to the first embodiment, by bringing the stripping liquid-forming liquid (pure water) supplied to the upper surface of the substrate W into contact with the treatment film 100, a stripping liquid (alkaline liquid) for peeling the treatment film 100 from the upper surface of the substrate W is formed. Specifically, the alkaline component in the treatment film 100 dissolves in pure water, thereby forming an alkaline liquid (alkaline aqueous solution). The stripping liquid-forming liquid is relatively inexpensive, and pure water in the liquid used as the stripping liquid-forming liquid is particularly inexpensive. The alkaline liquid used as the stripping liquid is relatively expensive.

[0200] The treatment film 100 holding the object to be removed 103 is peeled off from the upper surface of the substrate W by the stripping liquid spontaneously formed on the substrate W. Then, by continuously supplying the stripping liquid-forming liquid, the treatment film 100 can be rinsed and removed from the upper surface of the substrate W while the treatment film 100 holds the object to be removed 103. That is, by supplying only the stripping liquid-forming liquid to the upper surface of the substrate W without supplying the stripping liquid, the object to be removed 103 can be removed from the upper surface of the substrate W. That is, the relatively expensive stripping liquid is not consumed in large quantities, and thus the object to be removed 103 can be removed from the upper surface of the substrate W. Therefore, both the increase in cost can be suppressed and the object to be removed 103 present on the upper surface of the substrate W can be efficiently removed.

[0201] In addition, according to this embodiment, by dissolving the stripping liquid-forming solid 112 in the treatment film 100 in the stripping liquid-forming liquid, a stripping liquid is formed. Therefore, the stripping liquid-forming substance can be dissolved in the stripping liquid-forming liquid near the treatment film 100, and thus a stripping liquid can be formed near the treatment film 100. Therefore, the stripping liquid-forming substance can be uniformly diffused to the stripping liquid having a high concentration of the stripping liquid-forming substance before the whole of the stripping liquid-forming liquid, and the stripping liquid acts on the treatment film 100. Thereby, the treatment film 100 can be efficiently peeled off. Thereby, the object to be removed 103 and the treatment film 100 are efficiently removed together from the upper surface of the substrate W.

[0202] The stripping liquid forming substance required for the formation of the stripping liquid is as expensive as the stripping liquid. Moreover, the time required to supply the processing liquid in an amount necessary for the formation of the processing film 100 to the substrate W (for example, 2 seconds to 4 seconds) is shorter than the time required to remove the processing film 100 from the substrate for stripping (for example, 60 seconds). Therefore, in this embodiment, in order to form the processing film 100, a processing liquid containing a stripping liquid forming substance is supplied to the substrate W, and in order to strip and remove the processing film 100, a stripping liquid forming liquid that does not contain a stripping liquid forming substance is supplied to the substrate W. Therefore, compared with the method of supplying a processing liquid that does not contain a stripping liquid forming substance to the substrate W to form the processing film 100 and supplying a stripping liquid (a stripping liquid forming liquid in which the stripping liquid forming substance is dissolved) to the substrate for stripping and removing the processing film 100, the supply time (consumption amount) of the stripping liquid forming substance supplied to the substrate W can be reduced. Therefore, an increase in cost can be suppressed.

[0203] In addition, when a large amount of a stripping liquid such as an alkaline liquid is supplied to the upper surface of the substrate W, it may cause damage to the substrate W and the components of the substrate processing apparatus 1. Therefore, it is necessary to use a substrate W and components having stripping liquid resistance (alkali resistance), and thus the cost may increase.

[0204] In this embodiment, by bringing a stripping liquid forming liquid such as pure water that hardly causes damage to the upper surface of the substrate W into contact with the processing film 100, the stripping liquid can be spontaneously generated. Therefore, by supplying only the stripping liquid forming liquid to the upper surface of the substrate W without supplying the stripping liquid, the object to be removed 103 can be removed from the upper surface of the substrate W. That is, the object to be removed 103 can be removed from the upper surface of the substrate W without supplying a large amount of the stripping liquid that is likely to cause damage to the substrate W and the components of the substrate processing apparatus 1. Therefore, damage to the substrate W and the components of the substrate processing apparatus 1 can be suppressed. Moreover, since it is not necessary to improve the stripping liquid resistance of the substrate W and the components of the substrate processing apparatus 1, an increase in cost can be suppressed.

[0205] In addition, in this embodiment, by supplying a stripping liquid forming liquid to the upper surface of the substrate W, the processing film 100 is partially dissolved to form through holes 102 in the processing film 100. By forming through holes 102 in the processing film 100, the stripping liquid can easily reach the vicinity of the upper surface of the substrate W. Therefore, the stripping liquid can act on the interface between the processing film 100 and the substrate W, and thus the processing film 100 can be efficiently stripped from the upper surface of the substrate W. On the other hand, although a part of the processing film 100 is dissolved to form through holes 102, the remaining part remains in a solid state, that is, in the state of holding the object to be removed 103. As a result, the object to be removed 103 and the processing film 100 can be efficiently removed from the upper surface of the substrate W together.

[0206] According to this embodiment, the solubility of highly soluble substances in at least one of the stripping liquid forming liquid and the stripping liquid is higher than that of low solubility substances. Therefore, by dissolving the highly soluble solid 110 in the treatment film 100 in the stripping liquid forming liquid or the stripping liquid, through holes 102 can be reliably formed in the treatment film 100. On the other hand, the low solubility solid 111 in the treatment film 100 is not dissolved and remains in a solid state. Therefore, while the object to be removed 103 is held by the low solubility solid 111, the stripping liquid can act on the interface between the solid state low solubility solid 111 and the substrate W. As a result, the treatment film 100 can be quickly peeled off from the upper surface of the substrate W, and the object to be removed 103 can be efficiently removed from the upper surface of the substrate W together with the treatment film 100.

[0207] <Second Embodiment>

[0208] Figure 7 It is a schematic partial cross-sectional view showing the schematic structure of the processing unit 2P included in the substrate processing apparatus 1P of the second embodiment. Refer to Figure 7 , the main difference between the processing unit 2P of the second embodiment and the processing unit 2 of the first embodiment (refer to Figure 2 ) is that the processing unit 2P of the second embodiment includes a fourth moving nozzle 14 in place of the opposing member 6 and the central nozzle 11.

[0209] The fourth moving nozzle 14 is an example of an organic solvent supply unit that supplies an organic solvent to the upper surface of the substrate W. In addition, the fourth moving nozzle 14 may also be an example of a gas supply unit that supplies a gas such as nitrogen to the upper surface of the substrate W.

[0210] The fourth moving nozzle 14 moves in the horizontal direction and the vertical direction by a fourth nozzle moving unit 35. The fourth moving nozzle 14 can move between the center position and the original position (retracted position) in the horizontal direction.

[0211] When the fourth moving nozzle 14 is located at the center position, it faces the rotation center of the upper surface of the substrate W. When the fourth moving nozzle 14 is located at the original position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a top view. The fourth moving nozzle 14 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W along the vertical direction.

[0212] The fourth nozzle moving unit 35 has the same structure as the first nozzle moving unit 36. That is, the fourth nozzle moving unit 35 includes, for example, a rotation axis in the vertical direction (not shown), an arm (not shown) that is combined with the rotation axis and the fourth moving nozzle 14 and extends horizontally, and a rotation axis drive unit (not shown) that raises or rotates the rotation axis.

[0213] An organic solvent pipe 90 for guiding an organic solvent to the fourth moving nozzle 14 is connected to the fourth moving nozzle 14. When an organic solvent valve 95 installed in the organic solvent pipe 90 is opened, the organic solvent is continuously ejected from the fourth moving nozzle 14 toward the central region of the upper surface of the substrate W.

[0214] A plurality of gas pipes (a first gas pipe 91, a second gas pipe 92, and a third gas pipe 93) for guiding gas to the fourth moving nozzle 14 are connected to the fourth moving nozzle 14. Gas valves (a first gas valve 96A, a second gas valve 97A, and a third gas valve 98A) for opening and closing their flow paths are respectively installed on the plurality of gas pipes (the first gas pipe 91, the second gas pipe 92, and the third gas pipe 93).

[0215] The fourth moving nozzle 14 has a central ejection port 14a for ejecting the organic solvent guided from the organic solvent pipe 90 in the vertical direction. The fourth moving nozzle 14 has a linear flow ejection port 14b for ejecting the gas supplied from the first gas pipe 91 linearly in the vertical direction. Further, the fourth moving nozzle 14 has a horizontal flow ejection port 14c for ejecting the gas supplied from the second gas pipe 92 radially around the fourth moving nozzle 14 in the horizontal direction. In addition, the fourth moving nozzle 14 has an inclined flow ejection port 14d for ejecting the gas supplied from the third gas pipe 93 radially around the fourth moving nozzle 14 in the obliquely downward direction.

[0216] A mass flow controller 96B for accurately adjusting the flow rate of the gas flowing in the first gas pipe 91 is installed on the first gas pipe 91. The mass flow controller 96B has a flow control valve. Further, a flow rate variable valve 97B for adjusting the flow rate of the gas flowing in the second gas pipe 92 is installed on the second gas pipe 92. In addition, a flow rate variable valve 98B for adjusting the flow rate of the gas flowing in the third gas pipe 93 is installed on the third gas pipe 93. Moreover, filters 96C, 97C, and 98C for removing foreign matters are respectively installed on the first gas pipe 91, the second gas pipe 92, and the third gas pipe 93.

[0217] Examples of the organic solvent ejected from the fourth moving nozzle 14 include the same organic solvent as that ejected from the third pipe 33 of the first embodiment (see Figure 2 ). Examples of the gas ejected from the fourth moving nozzle 14 include the same gas as that ejected from the second pipe 32 of the first embodiment (see Figure 2 ).

[0218] In addition, in the processing unit 2P of the second embodiment, an upper cleaning liquid pipe 43 for guiding the cleaning liquid is connected to the third moving nozzle 10. When the upper cleaning liquid valve 53 installed in the upper cleaning liquid pipe 43 is opened, the cleaning liquid is continuously ejected downward from the ejection port of the third moving nozzle 10.

[0219] The upper cleaning liquid valve 53, the first gas valve 96A, the second gas valve 97A, the third gas valve 98A, the mass flow controller 96B, the flow variable valve 97B, the flow variable valve 98B, and the fourth nozzle moving unit 35 are controlled by the controller 3 (see Figure 3 ).

[0220] By using the substrate processing apparatus 1P of the second embodiment, the same substrate processing as that of the substrate processing apparatus 1 of the first embodiment can be performed. However, in the first cleaning step (step S3) and the second cleaning step (step S9), the cleaning liquid is supplied from the third moving nozzle 10 to the upper surface of the substrate W.

[0221] Hereinafter, the details of (A) low-solubility substances, (B) stripping liquid forming substances, (C) solvents, (D) highly soluble substances in the processing liquid, and (F) details of the stripping liquid forming liquid will be described.

[0222] <Processing Liquid>

[0223] As described above, by drying the processing liquid on the substrate W, the (C) solvent is removed and the (A) low-solubility substances are formed into a film. That is, the processing film 100 is formed. The (B) stripping liquid forming substances and / or the (D) highly soluble substances are not removed together with the (C) solvent and remain in the processing film 100. "Curing" and "hardening" are a form of "film formation". In addition, the processing film 100 obtained from the processing liquid only needs to have a hardness sufficient to hold the particles (objects to be removed 103), and it is not necessary to completely remove the (C) solvent (for example, by vaporization). The processing liquid gradually shrinks and becomes a processing film as the (C) solvent volatilizes. "Not removed together with the (C) solvent" means that a very small amount is allowed to be removed (for example, by evaporation, volatilization) compared to the whole. For example, 0 to 10 mass% removal compared to the initial amount is allowed.

[0224] As described above, the processing film 100 holds the particles 103 on the substrate W and removes them by liquid stripping formed by the (F) stripping liquid. When the (B) stripping liquid forming substance remains in the processing film 100, the (B) stripping liquid forming substance dissolves in the (F) stripping liquid forming liquid by supplying the (F) stripping liquid forming liquid to the substrate W. Thus, it is considered that the pH of the (F) stripping liquid forming liquid rises to form (prepare) the stripping liquid. Therefore, it is considered that the (F) stripping liquid forming liquid does not need to be an alkaline solution such as ammonia water. In addition, when the (B) stripping liquid forming substance and / or the (D) highly soluble substance remain in the film, a portion that becomes the start of the stripping of the processing film 100 is generated.

[0225] <Low solubility substance>

[0226] (A) The low solubility substance includes at least one of novolac, polyhydroxystyrene, polystyrene, polyacrylate derivatives, polymaleate derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylate derivatives, and copolymers of their combinations. Preferably, (A) the low solubility substance includes at least one of novolac, polyhydroxystyrene, polyacrylate derivatives, polycarbonate, polymethacrylate derivatives, and copolymers of their combinations. More preferably, (A) the low solubility substance includes at least one of novolac, polyhydroxystyrene, polycarbonate, and copolymers of their combinations. The novolac may also be phenol novolac.

[0227] Of course, the processing liquid of the present invention may also include a combination of 1 or more of the above preferred examples as the (A) low solubility substance. For example, the (A) low solubility substance may also include both novolac and polyhydroxystyrene.

[0228] It is a preferred mode that by drying the (A) low solubility substance to form a film, most of the film will not dissolve in the (F) stripping liquid forming liquid (including the dissolved (B) stripping liquid forming substance) described later and will be stripped while holding the particles. In addition, a mode that allows a small portion of the (A) low solubility substance to be dissolved by the (F) stripping liquid forming liquid is also possible.

[0229] Preferably, the (A) low solubility substance does not contain fluorine and / or silicon, and more preferably, does not contain both.

[0230] The copolymerization is preferably random copolymerization or block copolymerization.

[0231] Although not intended to limit the present invention, specific examples of the (A) low solubility substance include the substances shown in the following Chemical Formulas 1 to 7.

[0232] [Chemical Formula 1]

[0233]

[0234] [Chemical Formula 2]

[0235]

[0236] [Chemical Formula 3]

[0237]

[0238] [Chemical Formula 4]

[0239]

[0240] (R represents a substituent such as C 1－4 alkyl)

[0241] [Chemical Formula 5]

[0242]

[0243] [Chemical Formula 6]

[0244]

[0245] [Chemical Formula 7]

[0246]

[0247] (A) The weight average molecular weight (Mw) of the poorly soluble substance is preferably 150 to 500,000.

[0248] (A) The poorly soluble substance can be obtained by synthesis. In addition, it can also be purchased. In the case of purchasing, as an example, the suppliers are as follows. In order to exert the effects of the present invention, the suppliers can also synthesize (A) the poorly soluble substance.

[0249] Novolac: Showa Denko K.K., Asahi Organic Chemicals Co., Ltd., Gun Ei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0250] Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.

[0251] Polyacrylic acid derivative: Nippon Shokubai Co., Ltd.

[0252] Polycarbonate: Sigma-Aldrich

[0253] Polymethacrylic acid derivative: Sigma-Aldrich

[0254] As one aspect of the present invention, the content of (A) low solubility substance is 0.1 to 50% by mass relative to the total mass of the treatment liquid. In other words, based on the total mass of the treatment liquid being 100% by mass, the content of (A) low solubility substance is 0.1 to 50% by mass. That is, "relative to..." can be paraphrased as "based on...". The same applies throughout this specification unless otherwise stated.

[0255] <Stripping liquid forming substance>

[0256] (B) The stripping liquid forming substance contains at least one of primary amine, secondary amine, tertiary amine, and quaternary ammonium salt (preferably primary amine, secondary amine, and tertiary amine), and (B) the stripping liquid forming substance contains a hydrocarbon. As a preferred aspect, (B) the stripping liquid forming substance remains in the treatment film 100 formed from the treatment liquid, and when the stripping liquid strips the treatment film 100, (B) the stripping liquid forming substance dissolves into (F) the stripping liquid forming solution. For this reason, the boiling point of the basic component of (B) at one atmosphere is preferably 20 to 400 °C.

[0257] The types of the stripping liquid forming substance are not intended to be limited, but as preferred examples of (B), N-benzylethanolamine, diethanolamine, monoethanolamine, 2-(2-aminoethylamino)ethanol, 4,4'-diaminodiphenylmethane, 2-(butylamino)ethanol, 2-anilinoethanol, triethanolamine, ethylenediamine, diethylenetriamine, tris(2-aminoethyl)amine, tris[2-(dimethylamino)ethyl]amine can be mentioned.

[0258] The types of the stripping liquid forming substance are not intended to be limited, but as preferred examples of (B), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetraethylethylenediamine can be mentioned.

[0259] The types of the stripping liquid forming substance are not intended to be limited, but as specific examples of (B) having a cage-like three-dimensional structure, 1,4-diazabicyclo[2.2.2]octane, hexamethylenetetramine can be mentioned. The present invention is not intended to be limited, but as preferred examples of (B) having a planar ring structure, 1,4,7,10-tetraazacyclododecane, 1,4,7,10,13,16-hexaazacyclooctadecane can be mentioned.

[0260] Of course, for the treatment liquid of the present invention, as (B) the stripping liquid forming substance, it may also include a combination of one or more of the above-mentioned preferred examples. For example, (B) the stripping liquid forming substance may include both N-benzylethanolamine and diethanolamine. In addition, (B) the stripping liquid forming substance may include both N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and 1,4-diazabicyclo[2.2.2]octane.

[0261] The molecular weight of (B) the stripping liquid forming substance is preferably 50 to 500.

[0262] (B) The stripping liquid forming substance can be obtained by synthesis or purchased. Suppliers include Sigma-Aldrich and Tokyo Chemical Industry Co., Ltd.

[0263] As one aspect of the present invention, compared with the mass of (A) low-solubility substance in the treatment liquid, (B) the stripping liquid forming substance is preferably 1 to 100% by mass.

[0264] <Solvent>

[0265] Preferably, (C) the solvent contains an organic solvent. (C) The solvent is volatile. Being volatile means having a higher volatility than water. Preferably, the boiling point of (C) the solvent at one atmosphere is 50 to 200 °C. It is also allowed that (C) the solvent contains a small amount of pure water. The pure water contained in (C) the solvent is preferably 30% by mass or less compared to the whole of (C) the solvent. A preferred mode is also not containing pure water (0% by mass). The pure water is preferably DIW.

[0266] As a preferred aspect of the present invention, the components (including additives) contained in the treatment liquid are dissolved in (C) the solvent. It is considered that the embedding performance of the treatment liquid in this way will have good film uniformity.

[0267] Examples of the organic solvent contained in (C) include alcohols such as isopropyl alcohol (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, lactate 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-dimethylacetamide and N-methylpyrrolidone, lactones such as γ-butyrolactone, etc. These organic solvents can be used alone or in combination of two or more.

[0268] As a preferred aspect, the organic solvent containing (C) the solvent is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. In the case of a combination of two organic solvents, the volume ratio is 20:80 to 80:20.

[0269] Compared with the total mass of the treatment liquid, (C) the solvent is 0.1 to 99.9% by mass.

[0270] <High-solubility substance>

[0271] (D) The highly soluble substances include hydrocarbons, and also include hydroxyl groups (-OH) and / or carbonyl groups (-C(=O)-). (D) In the case where the highly soluble substance is a polymer, each unit of one type of constituent unit contains a hydrocarbon, and also contains a hydroxyl group and / or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and ketene, and carboxylic acid is preferred.

[0272] As described above, (D) highly soluble substances remain on the treatment film formed on the substrate by drying the treatment liquid. When the (F) stripping liquid forms a liquid to strip the treatment film, (D) highly soluble substances generate a part that becomes the start of the stripping of the treatment film. For this reason, as the (D) highly soluble substance, it is preferable to use a substance with a solubility in the (F) stripping liquid forming liquid higher than that of the (A) low-soluble substance.

[0273] As a mode in which the (D) highly soluble substance contains a ketone as the carbonyl group, cyclic hydrocarbons can be cited. As a specific example, 1,2-cyclohexanedione or 1,3-cyclohexanedione can be cited.

[0274] It is not intended to limit the scope of the claims, but as a preferred example of (D), 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, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane can be cited. These can be obtained by polymerization or condensation.

[0275] It is not intended to limit the scope of the claims. As a preferred example of (D), 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol can be cited. As another mode, 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol are also preferred examples of (D).

[0276] It is not intended to limit the scope of the claims. As a preferred example of the (D) polymer, polymers of acrylic acid, maleic acid, or a combination thereof can be cited. Polyacrylic acid and maleic acid-acrylic acid copolymer are more preferred examples.

[0277] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0278] Of course, as for the treatment liquid, as the (D) highly soluble substance, a combination of one or two or more of the above preferred examples can also be included. For example, the (D) highly soluble substance can also include both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0279] (D) The molecular weight of the highly soluble substance is, for example, 80 to 10,000. When the (D) highly soluble substance is a resin, polymer, or copolymer, the molecular weight is expressed as the weight average molecular weight (Mw).

[0280] (D) The highly soluble substance can be obtained by synthesis or purchased. Examples of suppliers include Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai Co., Ltd.

[0281] As one aspect of the present invention, the (D) highly soluble substance is preferably 1 to 100% by mass relative to the mass of the (A) low-soluble substance in the treatment liquid.

[0282] <Other additives>

[0283] The treatment liquid of the present invention may further contain (E) other additives. The (E) other additives may include surfactants, antibacterial agents, fungicides, preservatives, antifungal agents, or alkalis (preferably surfactants), and may also include any combination thereof.

[0284] The (E) other additives (when there are multiple types, their sum) are preferably 0 to 10% by mass relative to the mass of the (A) low-soluble substance in the treatment liquid. The treatment liquid may not contain the (E) other additives (0% by mass).

[0285] <Stripping liquid forming liquid>

[0286] As described above, by drying the treatment liquid supplied to the substrate W, the (C) solvent is removed and the (A) low-soluble substance is formed into a film. That is, a treatment film is formed. The (B) stripping liquid forming substance and / or the (D) highly soluble substance are not removed together with the (C) solvent and remain in the treatment film. The treatment film can hold the particles present on the substrate and be removed by the (F) stripping liquid forming liquid in the held state.

[0287] Here, the (F) stripping liquid forming liquid is preferably neutral or weakly acidic. The pH of the (F) stripping liquid forming liquid is preferably 4 to 7, more preferably 5 to 7, and further preferably 6 to 7. Preferably, the pH measurement is preferably performed after degassing to avoid the influence caused by the dissolution of carbon dioxide in the air.

[0288] Preferably, the (F) stripping liquid forming liquid contains pure water. As described above, the treatment liquid of the present invention contains the (B) stripping liquid forming substance. Therefore, when dissolved in the (F) stripping liquid forming liquid, by increasing the pH of the (F) stripping liquid forming liquid, a (prepared) stripping liquid is formed. Therefore, most of the (F) stripping liquid forming liquid can be pure water. Compared with the total mass of the (F) stripping liquid forming liquid, the pure water contained in (F) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, further preferably 95 to 100% by mass, and still further preferably 99 to 100% by mass. It is also preferred that the (F) stripping liquid forming liquid consists only of pure water (100% by mass).

[0289] In the case where the treatment liquid is composed of the (A) poorly soluble substance, the (B) stripping liquid forming substance, and the (C) solvent, the formation of the treatment film and the stripping of the treatment film from the substrate can also be explained as follows.

[0290] By dropping the treatment liquid onto the substrate W to which particles are attached and drying it, the poorly soluble substance (polymer) is formed into a film. By forming the poorly soluble substance into a film, a treatment film is formed. The stripping liquid forming substance (alkaline component) remains in the treatment film. Then, the stripping liquid forming liquid is supplied to the treatment film, and the alkaline component is dissolved in the stripping liquid forming liquid. By the dissolution of the alkaline component, the pH of the stripping liquid forming liquid near the treatment film rises, thereby forming (preparing) a stripping liquid for stripping the treatment film from the substrate W. By the dissolution of the alkaline component, traces (voids) of the dissolution of the alkaline component are generated on the treatment film. By the dissolution of the alkaline component, the pH of the stripping liquid near the treatment film rises, and the effect of stripping the treatment film from the substrate can be improved. Moreover, the traces formed by the dissolution of the alkaline component become the starting point of the stripping of the treatment film, and starting from this point, the cracks expand. The treatment film separated by the expansion of the cracks is removed from the substrate while holding the particles.

[0291] In the case where the treatment liquid is composed of the (A) poorly soluble substance, the (B) stripping liquid forming substance, the (C) solvent, and the (D) highly soluble substance, the formation of the treatment film and the stripping of the treatment film from the substrate can also be explained as follows.

[0292] A low-solubility substance (polymer) is formed into a film by dropping a treatment liquid onto a substrate W to which particles are attached and drying the liquid. By forming the low-solubility substance into a film, a treatment film is formed. A stripping liquid forming substance (alkaline component) remains in the treatment film. Then, a stripping liquid forming liquid is supplied to the treatment film, and the alkaline component dissolves into the stripping liquid forming liquid. By the dissolution of the alkaline component, the pH of the stripping liquid forming liquid near the treatment film rises, thereby forming (preparing) a stripping liquid for peeling the treatment film from the substrate W. In addition, a highly soluble substance (crack promoting component) remains in the treatment film. The crack promoting component dissolves into the stripping liquid forming liquid / stripping liquid, and traces (voids) in which the crack promoting component is dissolved are formed on the treatment film. The traces formed by the dissolution of the crack promoting component become the starting point for the peeling of the treatment film, and starting from this point, the cracks expand. The treatment film that has been segmented by the expansion of the cracks is removed from the substrate W while holding the particles.

[0293] It is considered that when the (F) stripping liquid forming liquid removes (peels) the treatment film (particle holding layer), the (B) stripping liquid forming substance and / or the (D) highly soluble substance remaining in the treatment film generate a portion that becomes the starting point for film peeling. Therefore, preferably, the solubility of the (B) stripping liquid forming substance and the (D) highly soluble substance in the (F) stripping liquid forming liquid is higher than that of the (A) low-solubility substance. Solubility can be evaluated by known methods. For example, under the condition of 20 to 35 °C (more preferably 25 ± 2 °C), the (A) or (B) is added to pure water in a flask, the lid is covered, and the mixture is shaken with an oscillator for 3 hours, whereby it can be determined whether the (A) or (B) dissolves. In order to evaluate solubility, the pure water can also be changed to an alkaline liquid (for example, 5.0 mass% ammonia water).

[0294] It is a preferred mode of the present invention that the treatment film is not completely dissolved by the (F) stripping liquid forming liquid and is removed from the substrate while holding the particles. For example, the treatment film becomes a state in which it is finely cut by the "portion that becomes the starting point for peeling" and is removed.

[0295] The present invention is described below by various examples. In addition, the treatment liquid and the stripping liquid forming liquid are not limited to these examples.

[0296] Preparation of pattern substrate

[0297] A KrF resist composition (AZ DX-6270P, Merck Performance Materials Plasma Co., Ltd., hereinafter referred to as MPM) is dropped onto an 8-inch Si substrate and spin-coated onto the substrate at 1500 rpm. The substrate is soft-baked at 120 °C for 90 seconds. Using a KrF stepper (FPA-3000EX5, Canon), at 20 mJ / cm 2Exposure was carried out, and PEB (post-exposure bake) was performed at 130 °C for 90 seconds, followed by development using a developer (AZ MIF-300, MPM Co., Ltd.). As a result, a resist pattern with a line-and-space having a pitch of 360 nm and a duty ratio of 1:1 was obtained. Using this resist pattern as an etching mask, the substrate was etched using a dry etching apparatus (NE-5000N, ULVAC). Then, the substrate was cleaned using a stripper (AZ400T, MPM Co., Ltd.) to remove the resist pattern and resist residues. Thus, a pattern substrate with a pitch of 360 nm, a duty ratio of 1:1, and a line height of 150 nm was fabricated.

[0298] Preparation of bare substrate

[0299] An 8-inch Si substrate was used.

[0300] Preparation of evaluation substrate

[0301] Particles were attached to the above-mentioned pattern substrate and the bare substrate.

[0302] As the particles for the experiment, ultra-high purity colloidal silica (PL-10H, Fuso Chemical Industry Co., Ltd., average primary particle size of 90 nm) was used. By dropping 50 mL of the silica microparticle composition and rotating it at 500 rpm for 5 seconds, coating was performed. Then, by rotating it at 1000 rpm for 30 seconds, the solvent of the silica microparticle composition was spin-dried. Thus, an evaluation substrate was obtained.

[0303] Comparative test of presence or absence of each component in treatment liquid

[0304] 5 g of novolac (Mw of about 5,000 (A) low-solubility substance) was added to 95 g of isopropyl alcohol ((C) solvent). It was stirred for 1 hour using a stirrer to obtain a liquid with a (A) low-solubility substance concentration of 5 mass%. 2.5 g each of diethanolamine ((B) stripping solution-forming substance) and 3,6-dimethyl-4-octyne-3,6-diol (Tokyo Chemical Industry Co., Ltd., hereinafter referred to as TCI Co., Ltd., (D) high-solubility substance) were added to the above liquid. It was stirred for 1 hour using a stirrer. The liquid was filtered using Optimizer UPE (Nippon Seiko Co., Ltd.). Thus, a treatment liquid containing (A), (B), and (D) was obtained.

[0305] A treatment liquid containing (A) and (B) was obtained in the same manner except that the (D) component was not added.

[0306] A treatment liquid containing (A) and (D) was obtained in the same manner except that the (B) component was not added.

[0307] A treatment liquid containing (B) and (D) was obtained in the same manner except that the (A) component was not added.

[0308] Using a coater-developer RF3 (manufactured by SOKUDO Co., Ltd.), 10 cc of each treatment liquid was dropped onto each evaluation substrate, and the substrate was rotated at 1500 rpm for 60 seconds to perform coating and drying. While rotating the substrate at 100 rpm, DIW was dropped for 10 seconds, the entire substrate was covered with DIW, and this state was maintained for 20 seconds. By rotating the substrate at 1500 rpm, the substrate was dried. Through this rotation, in the presence of a film, the film was peeled off and removed.

[0309] The residual amount of particles on these substrates was compared. For the evaluation of the patterned substrate, a bright-field defect inspection device (UVision4, manufactured by AMAT) was used, and for the evaluation of the bare substrate, a dark-field defect inspection device (LS-9110, manufactured by Hitachi High-Technologies Corporation) was used.

[0310] Modulation example 1 of treatment liquid 1

[0311] 5 g of novolac (Mw of about 5,000 (A) low-solubility substance) was added to 95 g of isopropyl alcohol ((C) solvent). It was stirred with a stirrer for 1 hour to obtain a liquid with a concentration of 5 mass% of the (A) low-solubility substance. 2.5 g each of N-benzylethanolamine (manufactured by TCI Co., Ltd., (B) stripping liquid-forming substance) and 2,2-bis(4-hydroxyphenyl)propane (manufactured by TCI Co., Ltd., (D) high-solubility substance) were added to the above liquid. It was stirred with a stirrer for 1 hour. The liquid was filtered using Optimizer UPE (manufactured by Nippon Integration Co., Ltd.). Thus, treatment liquid 1 was obtained. The results are shown in Table 1.

[0312] In Tables 1 to 3 below, the above novolac is abbreviated as A1, N-benzylethanolamine is abbreviated as B1, isopropyl alcohol is abbreviated as IPA, and 2,2-bis(4-hydroxyphenyl)propane is abbreviated as D1. In addition, the numbers in parentheses in the (A) column refer to the concentration (mass%) when the (A) low-solubility substance is added to the (C) solvent. The numbers in parentheses in the (B) column refer to the concentration (mass%) compared to the (A) low-solubility substance when the (B) stripping liquid-forming substance is added to the liquid. The numbers in parentheses in the (D) column refer to the concentration (mass%) compared to the (A) low-solubility substance when the (D) high-solubility substance is added to the liquid.

[0313] Table 1

[0314]

[0315] Table 2

[0316]

[0317] Table 3

[0318]

[0319] In the above Tables 1 to 3,

[0320] Phenol novolac varnish (Mw about 10,000) is abbreviated as A2,

[0321] Phenol novolac varnish (Mw about 100,000) is abbreviated as A3,

[0322] Polyhydroxystyrene (Mw about 1,000) is abbreviated as A4,

[0323] Polyhydroxystyrene (Mw about 10,000) is abbreviated as A5,

[0324] Polyhydroxystyrene (Mw about 100,000) is abbreviated as A6,

[0325] The polyacrylic acid derivative (Mw about 1,000) composed of the structure shown by the following Chemical Formula 8 is abbreviated as A7,

[0326]

Chemical Formula 8

[0327]

[0328] The polyacrylic acid derivative (Mw about 10,000) composed of the above repeating units is abbreviated as A8,

[0329] The polyacrylic acid derivative (Mw about 100,000) composed of the above repeating units is abbreviated as A9,

[0330] Polymethyl methacrylate (Mw about 5,000) is abbreviated as A10,

[0331] Diethanolamine is abbreviated as B2,

[0332] Monoethanolamine is abbreviated as B3,

[0333] 2-(2-Aminoethylamino)ethanol is abbreviated as B4,

[0334] 4,4'-Diaminodiphenylmethane is abbreviated as B5,

[0335] 1,4-Diazabicyclo[2.2.2]octane is abbreviated as B6,

[0336] Hexamethylenetetramine is abbreviated as B7,

[0337] 2-(Butylamino)ethanol is abbreviated as B8,

[0338] 3,6-Dimethyl-4-octyne-3,6-diol is abbreviated as D2,

[0339] Polyacrylic acid (Mw about 1,000) is abbreviated as D3,

[0340] The polyacrylic acid (Mw of about 10,000) is abbreviated as D4.

[0341] The maleic acid - acrylic acid copolymer (Mw of about 3,000) composed of the following Chemical Formula 9 is abbreviated as D5.

[0342]

Chemical Formula 9

[0343]

[0344] Modulation examples 1 to 27 of treatment liquids 1 to 27

[0345] As the (A) low - solubility substance, (B) stripping - liquid - forming substance, (C) solvent, and (D) high - solubility substance, the substances described in Tables 1 to 3 are used. Except for being prepared in such a way that the concentrations are those described in Tables 1 to 3, the treatment liquids 2 to 27 are prepared in the same manner as in Preparation Example 1.

[0346] Evaluation of residual particle amount of treatment liquids 1 to 27

[0347] The evaluation substrates prepared as described in the preparation of the above - mentioned evaluation substrates are used.

[0348] Using a coater - developer RF3 (manufactured by SOKUDO Co., Ltd.), 10 cc of each treatment liquid is dropped onto each evaluation substrate, and it is rotated at 1500 rpm for 60 seconds to perform coating and drying. While rotating the substrate at 100 rpm, DIW is dropped for 10 seconds, and the entire substrate is covered with DIW and maintained in this state for 20 seconds. By rotating the substrate at 1500 rpm, the substrate is dried. Through this rotation, in the presence of a film, the film is peeled off and removed.

[0349] Compare the remaining amount of particles on these substrates. For the evaluation of the patterned substrates, a bright - field defect inspection device (UVision4, manufactured by AMAT) is used, and for the evaluation of the bare substrates, a dark - field defect inspection device (LS - 9110, manufactured by Hitachi High - Technologies Corporation) is used.

[0350] Confirm the coating condition and the film removal condition, count the remaining number of particles, and evaluate according to the following criteria. The evaluation results are recorded in Tables 1 to 3.

[0351] AA: ≤ 10

[0352] A: > 10, ≤ 100

[0353] B: > 100, ≤ 1000

[0354] C: > 1000

[0355] D: The film is not uniformly coated or the film is not removed.

[0356] Other modification examples

[0357] The present invention is not limited to the embodiments described above and can also be implemented in other ways.

[0358] For example, different from the substrate processing in the above-described embodiments, the chemical liquid supply step (step S2), the first rinsing step (step S3), and the first organic solvent supply step (step S4) may be omitted.

[0359] In addition, in the substrate processing in the above-described embodiments, in the processing film formation steps (steps S6 and S7), the solvent of the processing liquid is evaporated by heating the substrate W with a heat medium. However, the supply of the heat medium is not limited. For example, the substrate W can also be heated by heaters (not shown) built in the rotary base 21 and the opposing member 6. In this case, the heater functions as a substrate heating unit and an evaporation unit (evaporation promotion unit).

[0360] In addition, in the substrate processing in the above-described embodiments, after the peeling and removing step (step S8), the second rinsing step (step S9) is performed. However, the second rinsing step can also be omitted.

[0361] Specifically, in the peeling and removing step, pure water is used as the peeling liquid forming liquid. When the processing film 100 is discharged to the outside of the substrate W by the pure water as the peeling liquid forming liquid, there is no need to wash away the peeling liquid forming liquid, so the second rinsing step can be omitted. In addition, when the peeling liquid forming liquid supplied to the substrate W in the peeling and removing step and the organic solvent (residue removing liquid) supplied to the substrate W in the second organic solvent supply step (step S10) performed after the second rinsing step are compatible, the second rinsing step does not need to be performed either.

[0362] In addition, in the formation of the processing film 100, heating of the substrate W is not necessarily required. That is, in the thin film forming step (step S6), when the solvent volatilizes sufficiently, the subsequent heating step (step S7) may not be performed. In particular, when the solvent can remain inside the processing film 100, even without heating the substrate W, it is easy to evaporate the solvent to the required degree.

[0363] The embodiments of the present invention have been described in detail, but these are only specific examples used to clarify the technical content of the present invention and should not be construed as the present invention being limited to these specific examples. The scope of the present invention is only defined by the appended claims.

[0364] This application claims priority based on Japanese Patent Application No. 2018-234733 filed on December 14, 2018, and the entire content of this application is incorporated herein by reference.

Claims

1. A substrate processing method, comprising: a treatment liquid supply step of supplying a treatment liquid having a solute and a solvent onto the surface of a substrate, a treatment film formation step of curing or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that holds an object to be removed present on the surface of the substrate, a peeling step of forming a peeling liquid by bringing the peeling liquid formation liquid supplied to the surface of the substrate into contact with the treatment film, and peeling the treatment film holding the object to be removed from the surface of the substrate by the peeling liquid, a removal step of continuously supplying the peeling liquid formation liquid after peeling the treatment film, and flushing away the treatment film while keeping the treatment film in a state of holding the object to be removed to remove the treatment film from the surface of the substrate, the peeling step includes: a through-hole formation step of forming a through-hole in the treatment film by partially dissolving the treatment film by supplying the peeling liquid formation liquid to the surface of the substrate, the solute has a highly soluble substance and a low-soluble substance having a lower solubility relative to the peeling liquid than the highly soluble substance, the treatment film formation step includes a step of forming the treatment film having the highly soluble substance and the low-soluble substance in a solid state, the through-hole formation step includes: a step of forming the through-hole in the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the peeling liquid formed on the substrate.

2. The substrate processing method according to claim 1, wherein, the solubility of the low-soluble substance relative to the peeling liquid formation liquid is lower than the solubility of the highly soluble substance relative to the peeling liquid formation liquid, the through-hole formation step includes: a step of forming the through-hole in the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the peeling liquid formation liquid supplied to the surface of the substrate.

3. A substrate processing method, comprising: a treatment liquid supply step of supplying a treatment liquid having a solute and a solvent onto the surface of a substrate, a treatment film formation step of curing or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that holds an object to be removed present on the surface of the substrate, a peeling step of forming a peeling liquid by bringing the peeling liquid formation liquid supplied to the surface of the substrate into contact with the treatment film, and peeling the treatment film holding the object to be removed from the surface of the substrate by the peeling liquid, a removal step of continuously supplying the peeling liquid formation liquid after peeling the treatment film, and flushing away the treatment film while keeping the treatment film in a state of holding the object to be removed to remove the treatment film from the surface of the substrate, the peeling step includes: a through-hole formation step of forming a through-hole in the treatment film by partially dissolving the treatment film by supplying the peeling liquid formation liquid to the surface of the substrate, The solute includes a highly soluble substance and a lowly soluble substance having a lower solubility relative to the stripping liquid forming liquid than the highly soluble substance, The treatment film forming step includes a step of forming the treatment film having the highly soluble substance and the lowly soluble substance in a solid state, The through hole forming step includes: a step of forming the through hole on the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the stripping liquid forming liquid supplied to the surface of the substrate.

4. A substrate processing apparatus, comprising: A treatment liquid supply unit that supplies a treatment liquid having a solute and a solvent to the surface of the substrate, A solid forming unit that solidifies or hardens the treatment liquid, A stripping liquid forming liquid supply unit that supplies a stripping liquid forming liquid to the surface of the substrate, A controller that controls the treatment liquid supply unit, the solid forming unit, and the stripping liquid forming liquid supply unit, The controller is configured to execute: A treatment liquid supply step of supplying the treatment liquid from the treatment liquid supply unit to the surface of the substrate, A treatment film forming step of forming a treatment film that holds an object to be removed present on the surface of the substrate on the surface of the substrate by solidifying or hardening the treatment liquid supplied to the surface of the substrate using the solid forming unit, A stripping step of supplying the stripping liquid forming liquid from the stripping liquid forming liquid supply unit to the surface of the substrate, bringing the stripping liquid forming liquid into contact with the treatment film to form a stripping liquid, and stripping the treatment film holding the object to be removed from the surface of the substrate by the stripping liquid, A removal step of continuing to supply the stripping liquid forming liquid from the stripping liquid forming liquid supply unit after stripping the treatment film, and removing the treatment film from the surface of the substrate while keeping the treatment film in a state of holding the object to be removed, In the stripping step, by supplying the stripping liquid forming liquid to the surface of the substrate, the treatment film is partially dissolved to form a through hole in the treatment film, The solute includes a highly soluble substance and a lowly soluble substance having a lower solubility relative to the stripping liquid than the highly soluble substance, In the treatment film forming step, the treatment film having the highly soluble substance and the lowly soluble substance in a solid state is formed, In the stripping step, the through hole is formed in the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the stripping liquid formed on the substrate.

5. The substrate processing apparatus according to claim 4, wherein, The solubility of the lowly soluble substance relative to the stripping liquid forming liquid is lower than the solubility of the highly soluble substance relative to the stripping liquid forming liquid, In the treatment film forming step, the through hole is formed in the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the stripping liquid forming liquid supplied to the surface of the substrate.

6. A substrate processing apparatus, comprising: A treatment liquid supply unit that supplies a treatment liquid having a solute and a solvent to the surface of the substrate, Solid formation unit that solidifies or hardens the treatment liquid, Stripping liquid forming liquid supply unit that supplies a stripping liquid forming liquid to the surface of the substrate, Controller that controls the treatment liquid supply unit, the solid formation unit, and the stripping liquid forming liquid supply unit, The controller is configured to perform: Treatment liquid supply process of supplying the treatment liquid from the treatment liquid supply unit to the surface of the substrate, Treatment film formation process of forming, on the surface of the substrate, a treatment film that holds a removal object present on the surface of the substrate by solidifying or hardening the treatment liquid supplied to the surface of the substrate using the solid formation unit, Stripping process of forming a stripping liquid by bringing the stripping liquid forming liquid into contact with the treatment film by supplying the stripping liquid forming liquid from the stripping liquid forming liquid supply unit to the surface of the substrate, and stripping the treatment film that holds the removal object from the surface of the substrate with the stripping liquid, Removal process of removing the treatment film from the surface of the substrate while keeping the treatment film in a state of holding the removal object by continuously supplying the stripping liquid forming liquid from the stripping liquid forming liquid supply unit after stripping the treatment film, In the stripping process, by supplying the stripping liquid forming liquid to the surface of the substrate, the treatment film is partially dissolved to form through holes in the treatment film, The solute has a highly soluble substance and a low soluble substance whose solubility relative to the stripping liquid forming liquid is lower than that of the highly soluble substance, In the treatment film formation process, a treatment film having the highly soluble substance and the low soluble substance in a solid state is formed, In the stripping process, the through holes are formed in the treatment film by dissolving the highly soluble substance in a solid state in the treatment film in the stripping liquid forming liquid supplied to the surface of the substrate.

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