Substrate processing method and substrate processing device

Abstract

The present invention provides a substrate processing method and device, the substrate processing method comprising: a processing liquid supplying step, supplying a processing liquid having a solute and a solvent toward the surface of a substrate, a processing film forming step, solidifying or hardening the processing liquid supplied to the surface of the substrate, forming a processing film on the surface of the substrate that retains a removal object existing on the surface of the substrate, a stripping step, supplying a stripping liquid forming liquid to the surface of the substrate so that the stripping liquid forming liquid contacts the processing film to form a stripping liquid, and stripping the processing film that retains the removal object from the surface of the substrate by the stripping liquid, and a removal step, by continuously supplying the stripping liquid forming liquid after the processing film is stripped, rinsing the processing film in a state where the processing film retains the removal object, and removing the processing film from the surface of the substrate.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing device for processing substrates. The substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for FPD (Flat Panel Display: field emission display) such as organic EL (Electroluminescence) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like. Background Art

[0002] In the manufacturing process of semiconductor devices, a cleaning process is performed to remove various contaminants adhering to the substrate, processing liquid used in the previous process, resist residues, various particles, etc. (hereinafter sometimes collectively referred to as "removal objects").

[0003] In the cleaning process, generally, a cleaning liquid such as deionized water (DIW) is supplied to the substrate to remove the removal object by the physical action of the cleaning liquid, or a chemical solution that chemically reacts with the removal object is supplied to the substrate to chemically remove the removal object.

[0004] However, the concavo-convex patterns formed on substrates are becoming increasingly fine and complex, and therefore, it is becoming increasingly difficult to remove the object to be removed by a cleaning solution or a chemical solution while suppressing damage to the concavo-convex patterns.

[0005] Therefore, the following method is proposed: supplying a processing liquid including a solute and a volatile solvent to the upper surface of a substrate, and after forming a processing film by solidifying or hardening the processing liquid, dissolving the processing film to remove it (refer to U.S. Patent Application Publication No. 2014 / 041685 and U.S. Patent Application Publication No. 2015 / 128994).

[0006] In this method, when the processing liquid solidifies or hardens to form a processing film, the removal object is separated from the substrate. Then, the separated removal object is held in the processing film.

[0007] Next, a dissolving treatment liquid is supplied to the upper surface of the substrate, whereby the treatment film is dissolved and removed on the substrate, and thus the removal object is removed from the upper surface of the substrate together with the dissolved product of the treatment film (see US Patent Application Publication No. 2014 / 041685).

[0008] Alternatively, a stripping treatment liquid is sometimes supplied to the upper surface of the substrate. Thus, the treatment film is stripped from the upper surface of the substrate. Then, a dissolving treatment liquid is supplied to dissolve the treatment film on the substrate (see U.S. Patent Application Publication No. 2015 / 128994).

[0009] In the method of U.S. Patent Application Publication No. 2014 / 041685 and the method of U.S. Patent Application Publication No. 2015 / 128994, the processing film is dissolved on the substrate. Therefore, the removal object falls off from the processing film on the substrate, and the fallen removal object may be attached to the substrate again. Therefore, it may not be possible to efficiently remove the removal object from the substrate. Therefore, a method for removing the processing film from the substrate while keeping the removal object in the processing film is required.

[0010] However, the stripping liquid that can remove the processing film from the surface of the substrate while keeping the processing film as the removal object is relatively expensive. When the stripping liquid is supplied toward the upper surface of the substrate, a large amount of the stripping liquid is consumed, which may increase the cost. Summary of the invention

[0011] Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can efficiently remove a removal object existing on a surface of a substrate while suppressing an increase in cost.

[0012] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supplying step, supplying a processing liquid having a solute and a solvent toward the surface of a substrate, a processing film forming step, solidifying or hardening the processing liquid supplied to the surface of the substrate, and forming a processing film on the surface of the substrate that retains a removal object present on the surface of the substrate, a stripping step, supplying a stripping liquid forming liquid to the surface of the substrate so that the stripping liquid forming liquid contacts the processing film to form a stripping liquid, and stripping the processing film that retains the removal object from the surface of the substrate by the stripping liquid, and a removal step, by continuously supplying the stripping liquid forming liquid after the processing film is stripped, and washing away the processing film in a state where the processing film retains the removal object, thereby removing the processing film from the surface of the substrate.

[0013] According to this method, a stripping liquid forming liquid supplied to the surface of the substrate is brought into contact with the processing film, so that a stripping liquid that causes the processing film to be stripped from the surface of the substrate is formed on the substrate. The processing film that maintains a state of removing the object is stripped from the surface of the substrate by the stripping liquid that is spontaneously formed on the substrate. Then, by continuing to supply the stripping liquid forming liquid, the processing film can be removed from the surface of the substrate while the processing film maintains a state of removing the object. That is, the removal object can be removed from the surface of the substrate by supplying only the stripping liquid forming liquid without supplying the stripping liquid to 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, it is possible to suppress the increase in cost and efficiently remove the removal object present on the surface of the substrate.

[0014] In one embodiment of the present invention, the solute includes a stripping liquid forming substance. Furthermore, the process film forming step includes a step of forming the process film having the stripping liquid forming substance in a solid state. Furthermore, the stripping step includes a step of forming the stripping liquid by dissolving the solid stripping liquid forming substance in the process film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0015] According to this method, a stripping solution is formed by dissolving a solid stripping solution forming substance in the processing film into a stripping solution forming liquid. Therefore, the stripping solution forming substance can be dissolved in the stripping solution forming liquid near the processing film, so that the stripping solution can be formed near the processing film. Therefore, the stripping solution with a relatively high concentration of the stripping solution forming substance before the stripping solution forming substance dissolved in the stripping solution forming liquid is uniformly diffused to the entire stripping solution forming liquid can act on the processing film. Thus, the processing film can be efficiently stripped, so that the removal object existing on the surface of the substrate can be efficiently removed.

[0016] The stripping liquid forming substance required for the formation of the stripping liquid is also relatively expensive like the stripping liquid. In addition, the time required to supply the amount of processing liquid required for the formation of the processing film to the substrate is shorter than the time required to strip the processing film and remove it from the substrate. Therefore, in this method, a processing liquid containing a stripping liquid forming substance is supplied to the substrate in order to form the processing film, and a stripping liquid forming liquid that does not contain a stripping liquid forming substance is supplied to the substrate in order to strip and remove the processing film. Therefore, compared with a method in which a processing liquid that does not contain a stripping liquid forming substance is supplied to the substrate in order to form the processing film, and a stripping liquid (stripping liquid forming liquid in which the stripping liquid forming substance is dissolved) is supplied to the substrate in order to strip and remove the processing film, the supply time (consumption) of the stripping liquid forming substance to the substrate can be reduced. Therefore, the increase in cost can be suppressed.

[0017] As a result, it is possible to efficiently remove the removal object existing on the surface of the substrate while suppressing an increase in cost.

[0018] 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 the method of forming the alkaline liquid by the contact of the stripping liquid forming liquid with the treatment film, the alkaline liquid can be spontaneously generated on the substrate. Therefore, the alkaline liquid is not supplied to the surface of the substrate but only the stripping liquid forming liquid is supplied, and 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 liquid. Therefore, the consumption of the alkaline liquid can be reduced, and therefore, the increase in cost can be suppressed. Thus, the increase in cost can be suppressed, and the removal object present on the surface of the substrate can be efficiently removed.

[0019] In one embodiment of the present invention, the stripping liquid forming liquid is pure water. Therefore, by using relatively cheap pure water as the stripping liquid forming liquid, the treated film can be stripped and removed from the surface of the substrate. Thus, the increase in cost can be suppressed and the removal object existing on the surface of the substrate can be removed efficiently.

[0020] In one embodiment of the present invention, the stripping step includes a through-hole forming step of supplying the stripping liquid forming solution to the surface of the substrate to partially dissolve the processing film and form a through-hole in the processing film.

[0021] According to this method, by supplying a stripping liquid forming liquid to the surface of the substrate, the processing film is partially dissolved and a through hole is formed on the processing film. By forming a through hole on the processing film, the stripping liquid easily reaches the vicinity of the surface of the substrate. Therefore, the stripping liquid can act on the interface between the processing film and the substrate, so that the processing film can be efficiently stripped 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 maintains a solid state, that is, a state in which the object to be removed is maintained. As a result, the processing 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 processing film.

[0022] In one embodiment of the present invention, the solute includes a high-soluble substance and a low-soluble substance having a lower solubility with respect to the stripping solution than the high-soluble substance. Furthermore, the process film forming step includes a step of forming the process film having the high-soluble substance and the low-soluble substance in a solid state. Furthermore, the through-hole forming step includes a step of forming the through-hole in the process film by dissolving the high-soluble substance in a solid state in the process film in the stripping solution formed on the substrate.

[0023] According to this method, the high-solubility substance has a higher solubility in the stripping solution than the low-solubility substance. Therefore, by dissolving the high-solubility substance in the solid state in the processing film in the stripping solution, a through hole can be reliably formed on the processing film. On the other hand, the low-solubility substance in the processing film is not dissolved but maintained in a solid state. Therefore, it is possible to use the low-solubility substance in the solid state to maintain the removal object while allowing the stripping solution to act on the interface between the low-solubility substance in the solid state and the substrate. As a result, the processing film can be quickly stripped from the surface of the substrate, so that the removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0024] In one embodiment of the present invention, the solubility of the low-soluble substance in the stripping liquid forming liquid is lower than the solubility of the high-soluble substance in the stripping liquid forming liquid. Furthermore, the through-hole forming step includes a step of forming the through-hole in the processing film by dissolving the high-soluble substance in a solid state in the processing film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0025] According to this method, the high-solubility substance has a higher solubility in the stripping liquid forming liquid than the low-solubility substance. Therefore, by dissolving the high-solubility substance in the solid state in the processing film in the stripping liquid forming liquid, a through hole can be reliably formed on the processing film. On the other hand, the low-solubility substance in the solid state in the processing film is not dissolved but maintained in a solid state. Therefore, it is possible to use the low-solubility substance in the solid state to maintain the removal object while allowing the stripping liquid to act on the interface between the low-solubility substance in the solid state and the substrate. As a result, the processing film can be quickly stripped from the surface of the substrate, so that the removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0026] In one embodiment of the present invention, the solute includes a high-soluble substance and a low-soluble substance having a lower solubility than the high-soluble substance in the stripping liquid forming liquid. Furthermore, the process film forming step includes a step of forming the process film having the high-soluble substance and the low-soluble substance in a solid state. Furthermore, the through-hole forming step includes a step of forming the through-hole on the process film by dissolving the high-soluble substance in a solid state in the process film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0027] According to this method, the high-solubility substance has a higher solubility in the stripping liquid forming liquid than the low-solubility substance. Therefore, by dissolving the high-solubility substance in the solid state in the processing film in the stripping liquid forming liquid, a through hole can be reliably formed on the processing film. On the other hand, the low-solubility substance in the processing film is not dissolved but maintained in a solid state. Therefore, it is possible to use the low-solubility substance in the solid state to maintain the removal object while allowing the stripping liquid to act on the interface between the low-solubility substance in the solid state and the substrate. As a result, the processing film can be quickly stripped from the surface of the substrate, so that the removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0028] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supplying step, supplying a processing liquid having a solute containing an alkaline component and a solvent toward the surface of a substrate, a processing film forming step, solidifying or hardening the processing liquid supplied to the surface of the substrate, thereby forming a processing film on the surface of the substrate that retains a removal object present on the surface of the substrate and contains the alkaline component, a stripping step, supplying pure water to the surface of the substrate so that the pure water contacts the processing film, dissolves the alkaline component in the processing film into the pure water to form an alkaline aqueous solution, and stripping the processing film that retains the removal object from the surface of the substrate by the alkaline aqueous solution, and a removal step, by continuing to supply the pure water after the processing film is stripped, washing away the processing film in a state where the processing film retains the removal object, thereby removing the processing film from the surface of the substrate.

[0029] According to the method, by bringing the pure water supplied to the surface of the substrate into contact with the treatment film, the alkaline components in the treatment film are dissolved into the pure water to form (modulate) an alkaline aqueous solution on the substrate. The treatment film that maintains the state of removing the object is peeled off from the surface of the substrate by the alkaline aqueous solution formed spontaneously on 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 maintains the state of removing the object. That is, the alkaline aqueous solution is not supplied to the surface of the substrate but only pure water is supplied, so that 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, it is possible to suppress the increase in cost and efficiently remove the removal object present on the surface of the substrate.

[0030] Another embodiment of the present invention provides a substrate processing device, including: a processing liquid supply unit, which supplies a processing liquid having a solute and a solvent to the surface of a substrate, a solid forming unit, which solidifies or hardens the processing liquid, a stripping liquid forming liquid supply unit, which supplies a stripping liquid forming liquid to the surface of the substrate, and a controller, which controls the processing liquid supply unit, the solid forming unit and the stripping liquid forming liquid supply unit.

[0031] The controller is programmed to execute: a treatment liquid supplying step of supplying the treatment liquid from the treatment liquid supplying unit to the surface of the substrate; a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate by using the solid forming unit to form a treatment film on the surface of the substrate that holds a removal object present on the surface of the substrate; a stripping step of supplying the stripping liquid forming liquid from the stripping liquid forming liquid supplying unit to the surface of the substrate so that the stripping liquid forming liquid contacts the treatment film to form a stripping liquid, and stripping the treatment film that holds the removal object from the surface of the substrate by the stripping liquid; and a removal step of removing the treatment film from the surface of the substrate while the treatment film holds the removal object by continuing to supply the stripping liquid forming liquid from the stripping liquid forming liquid supplying unit after the treatment film is stripped.

[0032] According to this structure, a stripping liquid forming liquid supplied to the surface of the substrate is brought into contact with the processing film, so that a stripping liquid for stripping the processing film from the surface of the substrate is formed on the substrate. The processing film that maintains the state of removing the object is stripped from the surface of the substrate by the stripping liquid that is spontaneously formed on the substrate. Then, by continuing to supply the stripping liquid forming liquid, the processing film can be removed from the surface of the substrate while the processing film maintains the state of removing the object. That is, the removal object can be removed from the surface of the substrate by supplying only the stripping liquid forming liquid without supplying the stripping liquid to 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, it is possible to suppress the increase in cost and efficiently remove the removal object present on the surface of the substrate.

[0033] In another embodiment of the present invention, the solute includes a stripping liquid forming substance. Furthermore, in the process film forming step, the process film including the stripping liquid forming substance in a solid state is formed. Furthermore, in the stripping step, the stripping liquid is formed by dissolving the stripping liquid forming substance in a solid state in the process film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0034] According to this structure, the stripping liquid is formed by dissolving the solid stripping liquid forming substance in the processing film in the stripping liquid forming liquid. Therefore, the stripping liquid forming substance can be dissolved in the stripping liquid forming liquid near the processing film, so that the stripping liquid can be formed near the processing film. Therefore, the stripping liquid with a relatively high concentration of the stripping liquid forming substance before the stripping liquid forming substance dissolved in the stripping liquid forming liquid is uniformly diffused to the entire stripping liquid forming liquid can act on the processing film. Thus, the processing film can be efficiently stripped, and the removal object existing on the surface of the substrate can be efficiently removed.

[0035] The stripping liquid forming material required for the formation of the stripping liquid is also relatively expensive like the stripping liquid. In addition, the time required to supply the processing liquid required for the formation of the processing film to the substrate is shorter than the time required to strip the processing film and remove it from the substrate. Therefore, in this structure, the processing liquid containing the stripping liquid forming material is supplied to the substrate in order to form the processing film, and the stripping liquid forming liquid that does not contain the stripping liquid forming material is supplied to the substrate in order to strip and remove the processing film. Therefore, compared with the structure in which the processing liquid that does not contain the stripping liquid forming material is supplied to the substrate in order to form the processing film, and the stripping liquid (stripping liquid forming liquid in which the stripping liquid forming material is dissolved) is supplied to the substrate in order to strip and remove the processing film, the supply time (consumption) of the stripping liquid forming material can be reduced. Therefore, the increase in cost can be suppressed.

[0036] As a result, it is possible to efficiently remove the removal object existing on the surface of the substrate while suppressing an increase in cost.

[0037] 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 the structure of the alkaline liquid is formed by the contact between the stripping liquid forming liquid and the treatment film, the alkaline liquid can be spontaneously generated on the substrate. Therefore, the alkaline liquid is not supplied to the surface of the substrate but only the stripping liquid forming liquid is supplied, and 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 liquid. Therefore, the consumption of the alkaline liquid can be reduced, and therefore, the increase in cost can be suppressed. Thus, the increase in cost can be suppressed, and the removal object present on the surface of the substrate can be efficiently removed.

[0038] In another embodiment of the present invention, the stripping liquid forming liquid supply unit supplies pure water as the stripping liquid forming liquid to the surface of the substrate. Therefore, relatively cheap pure water can be used as the stripping liquid forming liquid, and the treated film can be stripped and removed from the surface of the substrate. Thus, the increase in cost can be suppressed, and the removal object existing on the surface of the substrate can be removed efficiently.

[0039] In another embodiment of the present invention, in the stripping step, the stripping solution forming liquid is supplied to the surface of the substrate, whereby the processing film is partially dissolved to form a through hole in the processing film.

[0040] According to this structure, by supplying the stripping liquid forming liquid to the surface of the substrate, the processing film is partially dissolved and a through hole is formed on the processing film. By forming the through hole on the processing film, the stripping liquid easily reaches the vicinity of the surface of the substrate. Therefore, the stripping liquid can act on the interface between the processing film and the substrate, so that the processing film can be efficiently stripped from the surface of the substrate. On the other hand, although a part of the processing film is dissolved to form the through hole, the remaining part maintains a solid state, that is, a state of keeping the object to be removed. As a result, the processing 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 processing film.

[0041] In another embodiment of the present invention, the solute includes a high-soluble substance and a low-soluble substance having a lower solubility than the high-soluble substance in the stripping solution. Furthermore, in the process film forming step, the process film including the high-soluble substance and the low-soluble substance in a solid state is formed. Furthermore, in the stripping step, the through hole is formed in the process film by dissolving the high-soluble substance in a solid state in the process film in the stripping solution formed on the substrate.

[0042] According to this structure, the high-solubility substance has a higher solubility in the stripping solution than the low-solubility substance. Therefore, by dissolving the high-solubility substance in the solid state in the processing film in the stripping solution, a through hole can be reliably formed on the processing film. On the other hand, the low-solubility substance in the processing film is not dissolved and remains in a solid state. Therefore, it is possible to use the low-solubility substance in the solid state to maintain the removal object while allowing the stripping solution to act on the interface between the low-solubility substance in the solid state and the substrate. As a result, the processing film can be quickly stripped from the surface of the substrate, so that the removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0043] In another embodiment of the present invention, the solubility of the low-soluble substance in the stripping liquid forming liquid is lower than the solubility of the high-soluble substance in the stripping liquid forming liquid. Furthermore, in the process film forming step, the through hole is formed in the process film by dissolving the high-soluble substance in a solid state in the process film in the stripping liquid forming liquid supplied to the surface of the substrate.

[0044] According to this structure, the high-solubility substance has a higher solubility in the stripping liquid forming liquid than the low-solubility substance. Therefore, by dissolving the high-solubility substance in the solid state in the processing film into the stripping liquid forming liquid, a through hole can be reliably formed on the processing film. On the other hand, the low-solubility substance in the solid state in the processing film is not dissolved but maintained in a solid state. Therefore, it is possible to use the low-solubility substance in the solid state to maintain the removal object while allowing the stripping liquid to act on the interface between the low-solubility substance in the solid state and the substrate. As a result, the processing film can be quickly stripped from the surface of the substrate, so that the removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0045] In another embodiment of the present invention, the solute includes a high-soluble substance and a low-soluble substance having a lower solubility than the high-soluble substance in the stripping solution forming liquid. Furthermore, in the process film forming step, the process film including the high-soluble substance and the low-soluble substance in a solid state is formed. Furthermore, in the stripping step, the through hole is formed in the process film by dissolving the high-soluble substance in a solid state in the process film in the stripping solution forming liquid supplied to the surface of the substrate.

[0046] According to this structure, the high-solubility substance has a higher solubility in the stripping liquid forming liquid than the low-solubility substance. Therefore, by dissolving the high-solubility substance in the solid state in the processing film into the stripping liquid forming liquid, a through hole can be reliably formed on the processing film. On the other hand, the low-solubility substance in the processing film is not dissolved but maintained in a solid state. Therefore, it is possible to use the low-solubility substance in the solid state to maintain the removal object while allowing the stripping liquid to act on the interface between the low-solubility substance in the solid state and the substrate. As a result, the processing film can be quickly stripped from the surface of the substrate, so that the removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0047] Another embodiment of the present invention provides a substrate processing device, a processing liquid supply unit, which supplies a processing liquid having a solute containing an alkaline component and a solvent to the surface of a substrate, a solid forming unit, which solidifies or hardens the processing liquid, a pure water supply unit, which supplies pure water to the surface of the substrate, and a controller, which controls the processing liquid supply unit, the solid forming unit and the pure water supply unit.

[0048] The controller is programmed to execute: a treatment liquid supplying process, supplying the treatment liquid from the treatment liquid supplying unit to the surface of the substrate, a treatment film forming process, solidifying or hardening the treatment liquid supplied to the surface of the substrate by using the solid forming unit, thereby forming a treatment film on the surface of the substrate that retains the removal object present on the surface of the substrate and contains the alkaline component, a stripping process, supplying the pure water from the pure water supplying unit to the surface of the substrate so that the pure water contacts the treatment film, dissolves the alkaline component in the treatment film into the pure water to form an alkaline aqueous solution, and stripping the treatment film that retains the removal object from the surface of the substrate by the alkaline aqueous solution, and a removal process, removing the treatment film from the surface of the substrate while the treatment film retains the removal object by continuing to supply the pure water from the pure water supplying unit after the treatment film is stripped.

[0049] According to this structure, by bringing the pure water supplied to the surface of the substrate into contact with the treatment film, the alkaline components in the treatment film are dissolved into the pure water to form (modulate) an alkaline aqueous solution on the substrate. The treatment film that maintains the state of removing the object is peeled off from the surface of the substrate by the alkaline aqueous solution spontaneously formed on 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 maintains the state of removing the object. That is, the removal object can be removed from the surface of the substrate by supplying only pure water without supplying the alkaline aqueous solution to 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, it is possible to suppress the increase in cost and efficiently remove the removal object present on the surface of the substrate.

[0050] The above and other objects, features and effects of the present invention will become more apparent from the following description of the embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 It is a schematic plan view showing the internal configuration of the substrate processing apparatus according to the first embodiment of the present invention.

[0052] Figure 2 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit included in the substrate processing apparatus.

[0053] Figure 3 This is a block diagram showing the electrical structure of the main parts of the substrate processing apparatus.

[0054] Figure 4 This is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus.

[0055] Figure 5A It is a schematic diagram for explaining the process of supplying the processing liquid (step S5) of the substrate processing.

[0056] Figure 5B It is a schematic diagram for explaining the thinning step (step S6) of the substrate processing.

[0057] Figure 5C It is a schematic diagram for explaining the heating process (step S7) of the substrate processing.

[0058] Figure 5D It is a schematic diagram for explaining the peeling and removing step (step S8) of the substrate processing.

[0059] Figure 5E It is a schematic diagram for explaining the second rinsing step (step S9) of the substrate processing.

[0060] Fig. 5F It is a schematic diagram for explaining the state of the second organic solvent supplying step (step S10) of the substrate treatment.

[0061] Figure 5G It is a schematic diagram for explaining the spin drying process (step S11) of the substrate processing.

[0062] Fig. 6A It is a schematic cross-sectional view for explaining the state near the surface of the substrate after the heating step (step S7).

[0063] Figure 6B It is a schematic cross-sectional view for explaining the state near the surface of the substrate during the execution of the above-mentioned peeling and removing step (step S8).

[0064] Figure 6C It is a schematic cross-sectional view for explaining the state near the surface of the substrate during the execution of the above-mentioned peeling and removing step (step S8).

[0065] Fig.6D It is a schematic cross-sectional view for explaining the state near the surface of the substrate during the execution of the above-mentioned peeling and removing step (step S8).

[0066] Figure 7 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit included in a substrate processing apparatus according to a second embodiment. DETAILED DESCRIPTION

[0067] In this specification, unless otherwise specified, the singular includes the plural, and "a", "the" means "at least one". In this specification, unless otherwise specified, some conceptual elements can be expressed in multiple ways, and when the amount (e.g., mass % or mole %) is recorded, the amount means the sum of these multiple ways.

[0068] “And / or” includes all combinations of elements and also includes the use of individual elements.

[0069] In this specification, when "to" or "-" is used to express a numerical range, unless otherwise specified, the numerical range includes both endpoints and the unit is common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0070] In this manual, “C x～y ”, “C x ~C y ” and “C x " refers to the number of carbon atoms in a molecule or a substituent. For example, C 1～6 The alkyl group refers to an alkyl chain having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0071] In this specification, when a polymer has multiple repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerizations, random copolymerizations, block copolymerizations, graft copolymerizations, or any of their mixtures. When a polymer or resin is represented by a structural formula, n or m, etc., recorded in brackets, represent the number of repetitions.

[0072] <First embodiment>

[0073] Figure 1 It is a schematic plan view showing the internal configuration of the substrate processing apparatus 1 according to the first embodiment of the present invention.

[0074] 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.

[0075] The substrate processing device 1 includes: a plurality of processing units 2 for processing substrates W using fluid; a loading port LP for carrying a receiving rack C for receiving a plurality of substrates W to be processed by the processing unit 2; transport robots IR and CR for transporting substrates W between the loading port LP and the processing unit 2; and a controller 3 for controlling the substrate processing device 1.

[0076] The transport robot IR transports the substrate W between the storage rack C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing unit 2. A plurality of processing units 2 have, for example, the same structure. Although described in detail later, the processing fluid supplied to the substrate W in the processing unit 2 includes a chemical solution, a rinse solution, a processing solution, a stripping solution forming solution, a heat medium, an inert gas, etc.

[0077] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and processes the substrate W in the processing cup 7. An entrance (not shown) is formed in the chamber 4 for carrying in or out the substrate W by the transport robot CR. The chamber 4 includes a gate unit (not shown) for opening and closing the entrance.

[0078] Figure 2 1 is a schematic diagram for explaining a configuration example of the processing unit 2. The processing unit 2 includes a spin 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.

[0079] The spin chuck 5 rotates the substrate W about a vertical rotation axis A1 (vertical axis) passing through the center of the substrate W while holding the substrate W horizontally. The spin chuck 5 includes a plurality of chuck pins 20 , a spin base 21 , a rotation shaft 22 , and a rotation motor 23 .

[0080] The rotating base 21 has a disk shape along the horizontal direction. A plurality of chuck pins 20 for holding the periphery of the substrate W are arranged on the upper surface of the rotating base 21 at intervals along the circumferential direction of the rotating base 21. The rotating base 21 and the plurality of chuck pins 20 constitute a substrate holding unit for holding the substrate W horizontally. The substrate holding unit is also called a substrate holder.

[0081] The rotating shaft 22 extends in the vertical direction along the rotating axis A1. The upper end of the rotating shaft 22 is connected to the center of the lower surface of the rotating base 21. The rotating motor 23 applies a rotating force to the rotating shaft 22. By rotating the rotating shaft 22 by the rotating motor 23, the rotating base 21 rotates. As a result, the substrate W rotates around the rotating axis A1. The rotating motor 23 is an example of a substrate rotating unit that rotates the substrate W around the rotating axis A1.

[0082] The opposing member 6 is opposed to the substrate W held by the spin chuck 5 from above. The opposing member 6 is formed in a disk shape having a diameter substantially the same as or larger than that of the substrate W. The opposing member 6 has an opposing surface 6a opposed to the upper surface (upper surface) of the substrate W. The opposing surface 6a is arranged substantially along a horizontal plane above the spin chuck 5.

[0083] A hollow shaft 60 is fixed to the opposite side of the opposing surface 6a of the opposing member 6. A communicating hole 6b is formed in a portion of the opposing member 6 overlapping the rotation axis A1 in a plan view. The communicating hole 6b vertically penetrates the opposing member 6 and communicates with the internal space 60a of the hollow shaft 60.

[0084] The opposing member 6 blocks the atmosphere in the space between the opposing surface 6 a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the opposing member 6 is also called a blocking plate.

[0085] The processing unit 2 further includes a relative member lifting unit 61 for driving the relative member 6 to rise and fall. The relative member lifting unit 61 can make the relative member 6 be located at any position (height) from a lower position to an upper position. The lower position refers to a position where the relative surface 6a is closest to the substrate W within the movable range of the relative member 6. The upper position refers to a position where the relative surface 6a is farthest from the substrate W within the movable range of the relative member 6.

[0086] The relative member lifting unit 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) supporting the hollow shaft 60, and an electric motor (not shown) providing a driving force to the ball screw mechanism. The relative member lifting unit 61 is also called a relative member lifter (blocking plate lifter).

[0087] The processing cup 7 includes: a plurality of baffles 71 for blocking liquid flying outward from the substrate W held by the chuck 5; a plurality of cups 72 for receiving the liquid guided downward by the plurality of baffles 71; and a cylindrical outer wall member 73 surrounding the plurality of baffles 71 and the plurality of cups 72.

[0088] 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.

[0089] The first cup 72A and the second cup 72B each have a shape of an annular groove that is open upward.

[0090] The first baffle plate 71A is disposed so as to surround the spin base 21. The second baffle plate 71B is disposed so as to surround the spin base 21 on the outer side in the rotation radial direction of the substrate W than the first baffle plate 71A.

[0091] The first baffle plate 71A and the second baffle plate 71B each have a substantially cylindrical shape, and the upper end of each baffle plate (the first baffle plate 71A and the second baffle plate 71B) is inclined inwardly toward the spin base 21 .

[0092] The first cup 72A receives the liquid guided downward by the first baffle plate 71A. The second cup 72B is formed integrally with the first baffle plate 71A and receives the liquid guided downward by the second baffle plate 71B.

[0093] The processing unit 2 includes a shutter lifting unit 74 for lifting the first shutter 71A and the second shutter 71B. The shutter lifting unit 74 lifts the first shutter 71A between a lower position and an upper position. The shutter lifting unit 74 lifts the second shutter 71B between a lower position and an upper position.

[0094] When the first baffle 71A and the second baffle 71B are both in the upper position, the liquid splashing 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 splashing from the substrate W is blocked by the second baffle 71B.

[0095] 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) for providing a 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) for providing a driving force to the second ball screw mechanism. The baffle lifting unit 74 is also referred to as a baffle lifter.

[0096] The first movable nozzle 8 is an example of a chemical liquid supply unit that supplies (discharges) the chemical liquid toward the upper surface of the substrate W held by the spin chuck 5 .

[0097] The first movable nozzle 8 is moved in the horizontal direction and the vertical direction by the first nozzle moving unit 36. The first movable nozzle 8 can move between the center position and the original position (retreat position) in the horizontal direction. When the first movable nozzle 8 is located 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 with the rotation axis A1 in the upper surface of the substrate W. When the first movable nozzle 8 is located at the original position, it is not opposite to the upper surface of the substrate W, and is located outside the processing cup 7 when viewed from above. The first movable nozzle 8 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0098] The first nozzle moving unit 36 ​​includes, for example, a rotation shaft (not shown) extending in the vertical direction, an arm (not shown) coupled to the rotation shaft and extending horizontally, and a rotation shaft driving unit (not shown) for lifting or rotating the rotation shaft.

[0099] The rotation axis driving unit causes the arm to swing by rotating the rotation axis about the vertical rotation axis. Furthermore, the rotation axis driving unit causes the arm to move up and down by raising and lowering the rotation axis in the vertical direction. The first movable nozzle 8 is fixed to the arm. According to the swinging and raising and lowering of the arm, the first movable nozzle 8 moves in the horizontal direction and the vertical direction.

[0100] The first moving nozzle 8 is connected to a chemical liquid pipe 40 that guides the chemical liquid. When a chemical liquid valve 50 attached to the chemical liquid pipe 40 is opened, the chemical liquid is continuously ejected downward from the first moving nozzle 8.

[0101] The liquid sprayed from the first moving nozzle 8 is a liquid containing at least one of sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, hydrogen peroxide, organic acid (e.g., citric acid, oxalic acid, etc.), organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and anticorrosive agent. Examples of liquids mixed with these liquids include SPM liquid (sulfuric acid / hydrogen peroxide mixture: sulfuric acid hydrogen peroxide mixture), SC1 liquid (ammonia-hydrogen peroxide mixture: a mixture of ammonia water and hydrogen peroxide), etc.

[0102] The second movable nozzle 9 is an example of a processing liquid supply unit that supplies (discharges) the processing liquid toward the upper surface of the substrate W held by the spin chuck 5 .

[0103] The second movable nozzle 9 is moved in the horizontal direction and the vertical direction by the second nozzle moving unit 37. The second movable nozzle 9 can move between the center position and the home position (retreat position) in the horizontal direction. When the second movable nozzle 9 is located at the center position, it is opposite to the rotation center of the upper surface of the substrate W. When the second movable nozzle 9 is located at the home position, it is not opposite to the upper surface of the substrate W, and is located outside the processing cup 7 when viewed from above. The second movable nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0104] 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 rotation axis (not shown) extending in the vertical direction, an arm (not shown) connected to the rotation axis and the second moving nozzle 9 and extending horizontally, and a rotation axis driving unit (not shown) for lifting or rotating the rotation axis.

[0105] The second moving nozzle 9 is connected to a process liquid pipe 41 that guides the process liquid. When a process liquid valve 51 attached to the process liquid pipe 41 is opened, the process liquid is continuously ejected downward from the second moving nozzle 9.

[0106] The treatment liquid ejected from the second moving nozzle 9 includes a solute and a solvent. The treatment liquid solidifies or hardens by at least a portion of the solvent volatilizing (evaporating). The treatment liquid solidifies or hardens on the substrate W to form a treatment film that holds particles and other objects to be removed on the substrate W.

[0107] Here, "solidification" means that the solute becomes hard by the force acting between molecules or atoms, for example, accompanying the volatilization of the solvent. "Hardening" means that the solute becomes hard by chemical changes such as polymerization or cross-linking. Therefore, "solidification or hardening" means that the solute "hardens" due to various reasons.

[0108] The third moving nozzle 10 is an example of a stripping liquid forming liquid supply unit (pure water supply unit) that supplies (discharges) a stripping liquid forming liquid such as pure water toward the upper surface of the substrate W held by the spin chuck 5 .

[0109] The third movable nozzle 10 is moved in the horizontal direction and the vertical direction by the third nozzle moving unit 38. The third movable nozzle 10 can move between the center position and the home position (retreat position) in the horizontal direction. When the third movable nozzle 10 is located at the center position, it is opposite to the rotation center of the upper surface of the substrate W. When the third movable nozzle 10 is located at the home position, it is not opposite to the upper surface of the substrate W, and is located outside the processing cup 7 when viewed from above. The third movable nozzle 10 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0110] 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 rotation shaft (not shown) along the vertical direction, an arm (not shown) connected to the rotation shaft and the third moving nozzle 10 and extending horizontally, and a rotation shaft driving unit (not shown) for lifting or rotating the rotation shaft.

[0111] The third movable nozzle 10 is connected to an upper stripping liquid forming liquid pipe 42 that guides the stripping liquid forming liquid to the third movable 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 movable nozzle 10.

[0112] The stripping liquid forming liquid is a liquid used to form 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. Liquids other than DIW used as the stripping liquid forming liquid include functional water such as carbonated water and ammonia water with a diluted concentration (for example, about 10 ppm to 100 ppm).

[0113] The solute in the processing liquid ejected from the second moving nozzle 9 includes a low-soluble substance, a high-soluble substance, and a peeling liquid forming substance.

[0114] The stripping liquid forming substance is a substance that forms a stripping liquid for stripping the treated 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 (alkaline component) that is dissolved in the stripping liquid forming liquid and exhibits alkalinity (basicity). The stripping liquid forming substance is, for example, a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt. The stripping liquid is an aqueous solution of a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt, that is, an alkaline aqueous solution (alkaline liquid).

[0115] The low-soluble substance and the high-soluble substance can use substances with different solubility in the stripping solution forming liquid and the stripping solution. Specifically, the high-soluble substance can use a substance with higher solubility in at least one of the stripping solution forming liquid and the stripping solution than the substance used as the low-soluble substance.

[0116] If a highly soluble substance has a higher solubility in one of the stripping solution forming liquid and the stripping solution than a low soluble substance, then its solubility in the other of the stripping solution forming liquid and the stripping solution may be as low as that of the low soluble substance, and it may be almost insoluble in the other of the stripping solution forming liquid and the stripping solution. On the contrary, even if a highly soluble substance has a higher solubility in one of the stripping solution forming liquid and the stripping solution than a low soluble substance, it cannot have a lower solubility in the other of the stripping solution forming liquid and the stripping solution than a low soluble substance.

[0117] The low-soluble substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, novolac, and the high-soluble substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane.

[0118] The solvent contained in the processing liquid ejected from the second moving nozzle 9 may be a liquid that dissolves the low-soluble substance, the high-soluble substance, and the stripping liquid forming substance. Preferably, the solvent contained in the processing liquid is a liquid that is compatible (mixable) with the stripping liquid forming liquid. The details of the processing liquid solvent, the low-soluble substance, the high-soluble substance, and the stripping liquid forming substance ejected from the second moving nozzle 9 will be described later together with the details of the stripping liquid forming liquid ejected from the third moving nozzle 10.

[0119] The central nozzle 11 is accommodated in the internal space 60a of the hollow shaft 60 of the opposing member 6. The ejection port 11a provided at the top of the central nozzle 11 faces the central area of ​​the upper surface of the substrate W from above. The central area of ​​the upper surface of the substrate W is an area on the upper surface of the substrate W including the rotation center of the substrate W.

[0120] The central nozzle 11 includes a plurality of tubes (a first tube 31, a second tube 32, and a third tube 33) for ejecting fluid downward, and a cylindrical housing 30 surrounding 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 an ejection port of the plurality of tubes.

[0121] 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 a 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.

[0122] The first tube 31 is connected to an upper rinse liquid pipe 44 that guides the rinse liquid to the first tube 31. When the upper rinse liquid valve 54 installed on the upper rinse liquid pipe 44 is opened, the rinse liquid is continuously ejected from the first tube 31 (central nozzle 11) toward the central area of ​​the upper surface of the substrate W.

[0123] The second tube 32 is connected to a gas pipe 45 that guides gas to the second tube 32. When a gas valve 55 attached to the gas pipe 45 is opened, gas is continuously ejected downward from the second tube 32 (central nozzle 11).

[0124] The gas ejected from the second tube 32 is, for example, an inert gas such as nitrogen (N2). 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 to the upper surface of the substrate W and the pattern formed on the upper surface of the substrate W may be used. In addition to nitrogen, rare gases such as argon may be cited as examples of the inert gas.

[0125] The third tube 33 is connected to an organic solvent pipe 46 that guides the organic solvent to the third tube 33. When an organic solvent valve 56 attached to the organic solvent pipe 46 is opened, the organic solvent is continuously ejected from the third tube 33 (central nozzle 11) toward the central area of ​​the upper surface of the substrate W.

[0126] The organic solvent ejected from the third pipe 33 is a residue removing liquid for removing residues remaining on the upper surface of the substrate W after the process film is removed by the stripping liquid forming liquid. Preferably, the organic solvent ejected from the third pipe 33 is compatible with the process liquid and the rinse liquid.

[0127] Examples of the organic solvent ejected from the third pipe 33 include a liquid containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

[0128] The organic solvent ejected from the third pipe 33 does not need to be composed of only a monomer component, but may be a liquid mixed with other components. For example, it may be a mixed liquid of IPA and DIW, or a mixed liquid of IPA and HFE.

[0129] The lower surface nozzle 12 is inserted into a through hole 21a opened in 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 is opposite to the central area of ​​the lower surface (the lower surface) of the substrate W from below. The central area of ​​the lower surface of the substrate W is an area of ​​the lower surface of the substrate W that includes the rotation center of the substrate W.

[0130] One end of a common pipe 80 is connected to the lower surface nozzle 12, which guides the rinsing liquid, the stripping liquid forming liquid, and the heat medium together with the lower surface nozzle 12. The other end of the common pipe 80 is connected to: a lower side rinsing liquid pipe 81 for guiding the rinsing liquid to the common pipe 80, a lower side stripping liquid forming liquid pipe 82 for guiding the stripping liquid forming liquid to the common pipe 80, and a heat medium pipe 83 for guiding the heat medium to the common pipe 80.

[0131] When the lower rinse liquid valve 86 installed in the lower rinse liquid piping 81 is opened, the rinse liquid is continuously ejected from the lower surface nozzle 12 toward the central area of ​​the lower surface of the substrate W. When the lower stripping liquid forming liquid valve 87 installed in the lower stripping liquid forming liquid piping 82 is opened, the stripping liquid forming liquid is continuously ejected from the lower surface nozzle 12 toward the central area of ​​the lower surface of the substrate W. When the heat medium valve 88 installed in the heat medium piping 83 is opened, the heat medium is continuously ejected from the lower surface nozzle 12 toward the central area of ​​the lower surface of the substrate W.

[0132] The lower surface nozzle 12 is an example of a lower side rinsing liquid supply unit that supplies a rinsing 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 a 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 a 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.

[0133] The heat medium ejected from the lower surface nozzle 12 is, for example, high-temperature DIW having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the treatment liquid. When the solvent contained in the treatment liquid is IPA, 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, but may also be a high-temperature gas such as a high-temperature inert gas or high-temperature air having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the treatment liquid.

[0134] Figure 31 is a block diagram showing the electrical configuration of a main part of the substrate processing apparatus 1. The controller 3 includes a microcomputer and controls a control object of the substrate processing apparatus 1 according to a predetermined control program.

[0135] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B storing a control program. The controller 3 is configured to execute various controls for substrate processing by the processor 3A executing the control program.

[0136] In particular, the controller 3 is programmed to control the transport robots IR, CR, the rotary motor 23, the first nozzle moving unit 36, the second nozzle moving unit 37, the third nozzle moving unit 38, the relative component 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.

[0137] Figure 4 1 is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1. Figure 4 2 mainly shows the processing implemented by the controller 3 executing the program. Figure 5A to Figure 5G It is a schematic diagram for explaining the state of each process of the said substrate processing.

[0138] In the substrate processing performed by the substrate processing apparatus 1, for example, Figure 4 As shown, the substrate carrying-in process (step S1), the chemical solution supplying process (step S2), the first rinsing process (step S3), the first organic solvent supplying process (step S4), the processing liquid supplying process (step S5), the thin filming process (step S6), the heating process (step S7), the stripping and removal process (step S8), the second rinsing process (step S9), the second organic solvent supplying process (step S10), the spin drying process (step S11) and the substrate carrying-out process (step S12) are performed in sequence.

[0139] First, an unprocessed substrate W passes through the transport robots IR and CR (see Figure 1 ) is carried into the processing unit 2 from the storage rack C and transferred to the spin chuck 5 (step S1). Thus, the substrate W is held horizontally by the spin chuck 5 (substrate holding step). The spin chuck 5 holds the substrate W until the spin drying step (step S11) is completed. When the substrate W is carried in, the relative member 6 retreats to the upper position.

[0140] Next, after the transport robot CR retreats outside the processing unit 2, the liquid medicine supply process is started (step S2). Specifically, the rotary motor 23 rotates the spin base 21. As a result, the substrate W held horizontally is rotated (substrate rotating process). The baffle lifting unit 74 moves the first baffle 71A and the second baffle 71B to the upper position.

[0141] The first nozzle moving unit 36 ​​moves the first movable nozzle 8 to the processing position. The processing position of the first movable nozzle 8 is, for example, the central position. Then, the liquid medicine valve 50 is opened. Thus, the liquid medicine is supplied (discharged) from the first movable nozzle 8 toward the central area of ​​the upper surface of the rotating substrate W. The liquid medicine 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. Thus, the upper surface of the substrate W is processed by the liquid medicine. The discharge of the liquid medicine from the first movable 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.

[0142] Next, the first rinsing process is started (step S3 ). In the first rinsing process, the chemical liquid on the substrate W is rinsed with the rinse liquid.

[0143] Specifically, the liquid medicine valve 50 is closed. Thus, the supply of liquid medicine to the substrate W is stopped. Then, the first nozzle moving unit 36 ​​moves the first movable nozzle 8 to the home position. Then, the relative member lifting unit 61 moves the relative member 6 to the processing position between the upper position and the lower position. When the relative member 6 is located at the processing position, the distance between the upper surface of the substrate W and the relative surface 6a is, for example, 30 mm. In the first rinsing step, the first baffle 71A and the second baffle 71B are maintained in the upper position.

[0144] Then, the upper rinse liquid valve 54 is opened. Thus, the rinse liquid is supplied (discharged) from the central nozzle 11 toward the central area of ​​the upper surface of the rotating substrate W. The rinse liquid supplied from the central nozzle 11 to the upper surface of the substrate W is radially spread by the centrifugal force and spreads over the entire upper surface of the substrate W. Thus, the liquid on the upper surface of the substrate W is rinsed out of the substrate W. In the first rinse step, the substrate W is rotated at a predetermined first rinse rotation speed, for example, 800 rpm.

[0145] In addition, the lower rinsing liquid valve 86 is opened. Thus, the rinsing liquid is supplied (discharged) from the lower surface nozzle 12 toward the central area of ​​the lower surface of the rotating substrate W. The rinsing 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 in the case where the chemical liquid dispersed from the substrate W in the chemical liquid supply process adheres to the lower surface, the chemical liquid attached to the lower surface can be rinsed by the rinsing liquid supplied from the lower surface nozzle 12. The spraying of the rinsing liquid from the central nozzle 11 and the lower surface nozzle 12 continues for a predetermined time, for example, 30 seconds.

[0146] Next, a first organic solvent supplying process is started (step S4 ). In the first organic solvent supplying process, the rinse liquid on the substrate W is replaced with the organic solvent.

[0147] Specifically, the upper rinse liquid valve 54 and the lower rinse liquid valve 86 are closed. Thus, the supply of the rinse liquid to the upper and lower surfaces of the substrate W is stopped. Then, the shutter lifting unit 74 moves the first shutter 71A to the lower position while maintaining the second shutter 71B in the upper position. The opposing member 6 is maintained in the processing position.

[0148] Then, the organic solvent valve 56 is opened, thereby supplying (discharging) the organic solvent from the central nozzle 11 toward the central area of ​​the upper surface of the substrate W in the rotating state.

[0149] The organic solvent supplied from the central nozzle 11 to the upper surface of the substrate W is radially diffused by centrifugal force and spreads over the entire upper surface of the substrate W. Thus, the rinse liquid on the substrate W is replaced with the organic solvent. The ejection of the organic solvent from the central nozzle 11 is continued for a predetermined time, for example, 10 seconds.

[0150] In the first organic solvent supplying step, the substrate W is rotated at a predetermined first organic solvent rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not need to be rotated at a constant rotation speed in the first organic solvent supplying step. For example, the rotary motor 23 may rotate the substrate W at 300 rpm when the organic solvent supplying starts, and accelerate the rotation of the substrate W while supplying the organic solvent to the substrate W until the rotation speed of the substrate W reaches 1500 rpm.

[0151] Next, the process liquid supply process is started (step S5). Specifically, the organic solvent valve 56 is closed. Thus, 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 process liquid supply process, the substrate W is rotated at a predetermined process liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0152] Then, if Figure 5A As shown, the second nozzle moving unit 37 moves the second movable nozzle 9 to the processing position. The processing position of the second movable nozzle 9 is, for example, the central position. Then, the processing liquid valve 51 is opened. As a result, the processing liquid is supplied (discharged) from the second movable nozzle 9 toward the central area of ​​the upper surface of the substrate W in a rotating state (processing liquid supply process, processing liquid discharge process). As a result, the organic solvent on the substrate W is replaced by the processing liquid, thereby forming a liquid film 101 (processing liquid film) of the processing liquid on the substrate W (processing liquid film formation process). The supply of the processing liquid from the second movable nozzle 9 continues for a specified time, for example, 2 seconds to 4 seconds.

[0153] Next, a process film forming step is performed (step S6 and step S7). In the process film forming step, the process liquid on the substrate W is solidified or hardened, thereby forming a process film 100 (see step S6 and step S7) on the upper surface of the substrate W to retain the removal object on the substrate W. Figure 5C ).

[0154] In the process film forming process, a thin film forming process (rotation stopping process) is performed (step S6). In the thin film forming process, first, the process liquid valve 51 is closed. Thus, the supply of the process liquid to the substrate W is stopped. Then, the second nozzle moving unit 37 moves the second movable nozzle 9 to the home position.

[0155] like Figure 5B As shown, in the thin film forming step, 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 thin film forming step, the opposing member 6, the first baffle plate 71A, and the second baffle plate 71B are maintained in the upper position.

[0156] In the thin filming process, the rotary motor 23 changes the rotation speed of the substrate W to a predetermined thin filming speed. The thin filming 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, or may be appropriately changed within the range of 300 rpm to 1500 rpm during the thin filming process. The thin filming process is performed for a predetermined time, for example, 30 seconds.

[0157] In the process film forming step, after the thin film forming step, a heating step (step S7) of heating the substrate W is performed. In the heating step, in order to volatilize (evaporate) a part of the solvent of the process liquid on the substrate W, the liquid film 101 (see Figure 5B ) for heating.

[0158] Specifically, if Figure 5CAs shown, the relative member lifting unit 61 moves the relative member 6 to a close position between the upper position and the lower position. The close position may also be the lower position. The close position is a position where the distance from the upper surface of the substrate W to the relative surface 6a is, for example, 1 mm. During the heating process, the first baffle 71A and the second baffle 71B are maintained in the upper position.

[0159] Then, the gas valve 55 is opened to thereby supply gas to the space between the upper surface of the substrate W (the upper surface of the liquid film 101 ) and the opposing surface 6 a of the opposing member 6 (gas supplying step).

[0160] By blowing gas onto the liquid film 101 on the substrate W, the evaporation (volatization) 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) that evaporates the solvent in the processing liquid.

[0161] In addition, the heat medium valve 88 is opened. Thus, the heat medium is supplied (ejected) from the lower surface nozzle 12 toward the central area of ​​the lower surface of the rotating substrate W (heat medium supply process, heat medium ejection 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 heat medium is supplied to the substrate W for a predetermined time, for example, 60 seconds. In the heating process, the substrate W is rotated at a predetermined heating rotation speed, for example, 1000 rpm.

[0162] By supplying a heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated via the substrate W. Thus, the evaporation (volatization) 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) that evaporates the solvent in the processing liquid.

[0163] By performing the thin-filming step and the heating step, the processing liquid is solidified or hardened, thereby forming the processing film 100 on the substrate W. In this way, the substrate rotating unit (rotation motor 23), the central nozzle 11 and the lower surface nozzle 12 constitute a solid forming unit that solidifies or hardens the processing liquid to form a solid (processing film 100).

[0164] In the heating step, the substrate W is preferably heated so 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 appropriately left in the processing film 100. Thus, in the subsequent stripping and removal step, the stripping liquid forming liquid can be easily fused with the processing film 100 due to the interaction between the solvent remaining in the processing film 100 and the stripping liquid forming liquid, compared with a case where no solvent remains in the processing film 100. Therefore, the stripping liquid is easily formed.

[0165] 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 sometimes splashes 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 splashed from the first baffle 71A. Therefore, since the heat medium can be suppressed from adhering to the upper surface of the processing film 100, the generation of particles caused by the splash of the heat medium from the first baffle 71A can be suppressed.

[0166] Furthermore, by supplying gas from the central nozzle 11, an airflow F is formed in the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W, which moves from the central area of ​​the upper surface of the substrate W toward the peripheral edge of the upper surface of the substrate W. By forming the airflow F that moves from the central area of ​​the upper surface of the substrate W toward the peripheral edge of the upper surface of the substrate W, the heat medium splashed from the first baffle plate 71A can be pushed back toward the first baffle plate 71A. Therefore, it is possible to further suppress the heat medium from adhering to the upper surface of the processing film 100.

[0167] Next, a stripping and removing process (step S8) is performed to strip and remove the processing film 100 from the upper surface of the substrate W. Specifically, the heat medium valve 88 is closed. Thus, the supply of heat medium to the lower surface of the substrate W is stopped. In addition, the gas valve 55 is closed. Thus, 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.

[0168] Then, the relative member lifting unit 61 moves the relative member 6 to the upper position. Figure 5D As shown, the third nozzle moving unit 38 moves the third nozzle 10 to the processing position. The processing position of the third nozzle 10 is, for example, the central position.

[0169] Then, the upper stripping liquid forming liquid valve 52 is opened. Thus, the stripping liquid forming liquid is supplied (discharged) from the third movable nozzle 10 toward the central area of ​​the upper surface of the rotating substrate W (upper stripping liquid forming liquid supplying step, upper stripping liquid forming liquid discharging step). The stripping liquid forming liquid supplied to the upper surface of the substrate W is spread to the entire upper surface of the substrate W by centrifugal force.

[0170] The supply of the stripping liquid forming liquid to the upper surface of the substrate W is continued for a predetermined 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 supplying 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 removing step is longer than the supply time of the processing liquid to the upper surface of the substrate W in the processing liquid supplying step.

[0171] In the lift-off and removal step, the substrate W is rotated at a predetermined lift-off rotation speed, for example, 800 rpm.

[0172] In addition, the lower stripping liquid forming liquid valve 87 is opened. As a result, the stripping liquid forming liquid is supplied (ejected) from the lower surface nozzle 12 toward the central area of ​​the lower surface of the rotating substrate W (lower stripping liquid forming liquid supplying step, lower stripping liquid forming liquid ejecting step). The stripping liquid forming liquid supplied to the lower surface of the substrate W is diffused to the entire lower surface of the substrate W by centrifugal force.

[0173] By supplying a 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 removal object by the stripping action of the stripping liquid (stripping process). The processing film 100 is split into film pieces when being stripped from the upper surface of the substrate W. Then, after the processing film 100 is stripped, by continuously supplying the stripping liquid forming liquid to the upper surface of the substrate W, the split film pieces of the processing film 100 are discharged to the outside of the substrate W together with the stripping liquid forming liquid. Thus, the film pieces of the processing film 100 that maintain the state of removing the object are removed from the upper surface of the substrate W (removal process).

[0174] Here, in Figure 5A In the process liquid supplying step (step S5) shown in FIG. 1 , the process liquid supplied to the upper surface of the substrate W may spread along the periphery of the substrate W to the lower surface of the substrate W. In addition, the process liquid dispersed from the substrate W may splash from the first baffle 71A and adhere to the lower surface of the substrate W. Even in such a case, Figure 5C As shown, in the heating process (step S7 ), the heat medium is supplied to the lower surface of the substrate W, and therefore, the processing liquid can be removed from the lower surface of the substrate W by the flow of the heat medium.

[0175] Furthermore, the processing liquid attached to the lower surface of the substrate W may solidify or harden to form a solid due to the processing liquid supply process (step S5). Figure 5DAs shown, during the supply of the stripping liquid forming liquid to the upper surface of the substrate W in the stripping and removal process (step S8), the stripping liquid forming liquid is supplied (ejected) from the lower surface nozzle 12 to the lower surface of the substrate W, so that 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.

[0176] After the stripping and removing process (step S8), the second rinsing process (step S9) is performed. Specifically, the upper stripping liquid forming liquid valve 52 and the lower stripping liquid forming liquid valve 87 are closed. Thus, 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 movable nozzle 10 to the original position. Then, as shown in FIG. Figure 5E As shown, the opposing member lifting unit 61 moves the opposing member 6 to the processing position. In the second rinsing step, the substrate W is rotated at a predetermined second rinsing rotation speed, for example, 800 rpm. The first shutter plate 71A and the second shutter plate 71B are maintained at the upper position.

[0177] Then, the upper rinse liquid valve 54 is opened. Thus, the rinse liquid is supplied (discharged) from the central nozzle 11 toward the central area of ​​the upper surface of the rotating substrate W (second upper rinse liquid supplying step, second upper rinse liquid discharging step). The rinse liquid supplied to the upper surface of the substrate W is spread to the entire upper surface of the substrate W by centrifugal force. Thus, the stripping liquid forming liquid attached to the upper surface of the substrate W is rinsed by the rinse liquid.

[0178] In addition, the lower rinse liquid valve 86 is opened. Thus, the rinse liquid is supplied (discharged) from the lower surface nozzle 12 toward the central area of ​​the lower surface of the rotating substrate W (second lower rinse liquid supplying step, second lower rinse liquid discharging step). Thus, the stripping liquid forming liquid attached to the lower surface of the substrate W is rinsed by the rinse liquid. The rinse liquid is supplied to the upper surface and the lower surface of the substrate W for a predetermined time, for example, 35 seconds.

[0179] Next, the second organic solvent supply process is performed (step S10). Specifically, the upper rinse liquid valve 54 and the lower rinse liquid valve 86 are closed. Thus, the supply of the rinse liquid to the upper surface and the lower surface of the substrate W is stopped. Fig. 5F As shown, the shutter lifting unit 74 moves the first shutter 71A to the lower position. Then, the opposing member 6 is maintained at the processing position. In the second organic solvent supplying step, the substrate W is rotated at a predetermined second organic solvent rotation speed, for example, 300 rpm.

[0180] Then, the organic solvent valve 56 is opened. Thus, the organic solvent is supplied (ejected) from the central nozzle 11 toward the central area of ​​the upper surface of the rotating substrate W (second organic solvent supplying step, second organic solvent ejecting step, residue removing liquid supplying step). The organic solvent is supplied to the upper surface of the substrate W for a predetermined time, for example, 30 seconds.

[0181] The organic solvent supplied to the upper surface of the substrate W is radially spread by the centrifugal force and spreads to the entire upper surface of the substrate W. As a result, the rinse liquid on the upper surface of the substrate W is replaced by the organic solvent. 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 and is then discharged from the periphery of the upper surface of the substrate W (residue removal step).

[0182] Next, a spin drying process is performed (step S11). Specifically, the organic solvent valve 56 is closed. Thus, the supply of the organic solvent to the upper surface of the substrate W is stopped. Figure 5G As shown in FIG. 1 , 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 located at the drying position, the distance between the relative surface 6a of the relative member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 55 is opened. Thus, gas is supplied to the space between the upper surface of the substrate W and the relative surface 6a of the relative member 6.

[0183] Then, the rotary motor 23 accelerates the rotation of the substrate W, so that the substrate W rotates 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 predetermined time, for example, 30 seconds. As a result, 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 opposing member 6, the evaporation of the organic solvent can be promoted.

[0184] Then, the rotary motor 23 stops the rotation of the substrate W. The shutter plate lifting unit 74 moves the first shutter plate 71A and the second shutter plate 71B to the lower position. The gas valve 55 is closed. Then, the opposing member lifting unit 61 moves the opposing member 6 to the upper position.

[0185] The transport robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S12). The substrate W is transferred from the transport robot CR to the transport robot IR, and is stored in the storage rack C by the transport robot IR.

[0186] Next, refer to Figure 6A to Figure 6D A situation in which the processing film 100 is peeled off from the substrate W will be described. Fig. 6AThe state near the upper surface of the substrate W after the heating step (step S7) is shown. Figure 6B to Figure 6D The vicinity of the upper surface of the substrate W is shown during the peeling and removing step (step S8 ).

[0187] In the heating process performed in the process film forming process, as described above, the liquid film 101 on the substrate W is heated by the heat medium via the substrate W. Fig. 6A As shown, a treatment film 100 is formed to hold a removal object 103 such as particles. Specifically, by evaporating at least a portion of the solvent, a highly soluble substance contained in the solute of the treatment liquid forms a highly soluble solid 110 (a highly soluble substance in a solid state). In addition, by evaporating at least a portion of the solvent, a low soluble substance contained in the solute of the treatment liquid forms a low soluble solid 111 (a low soluble substance in a solid state), and a stripping liquid forming substance contained in the solute of the treatment liquid forms a stripping liquid forming solid 112 (a stripping liquid forming substance in a solid state).

[0188] The treated film 100 is divided into a portion where the high-soluble solid 110 is concentrated and a portion where the low-soluble solid 111 is concentrated. The stripping liquid-formed solid 112 is uniformly formed on the entire treated film 100 .

[0189] Reference Figure 6B In the stripping and removing step, the stripping liquid forming solid 112 is dissolved in the stripping liquid forming liquid when the stripping liquid forming liquid is supplied to the upper surface of the substrate W. The stripping liquid forming solid 112 is dissolved in the stripping liquid forming liquid to form a stripping liquid (alkaline liquid).

[0190] Reference Figure 6C , the highly soluble solid 110 is dissolved by supplying the stripping liquid forming liquid. That is, the processing film 100 is partially dissolved. By dissolving the highly soluble solid 110, a through hole 102 is formed in a portion where the highly soluble solid 110 is concentrated in the processing film 100 (through hole forming step). The through hole 102 is particularly likely to be formed in a portion where the highly soluble solid 110 extends 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 hole 102 is, for example, a few nanometers.

[0191] In the case where the highly soluble solid 110 has the property of being soluble in both the stripping solution forming liquid and the stripping solution, even if the stripping solution forming substance is not sufficiently eluted into the stripping solution forming liquid, the through hole 102 starts to be formed from the moment the stripping solution forming liquid contacts the processing film 100. Then, when the stripping solution is formed, the formation of the through hole 102 is promoted. That is, the through hole 102 is formed by both the stripping solution and the stripping solution forming liquid.

[0192] When the highly soluble solid 110 is hardly soluble in the stripping solution forming liquid but soluble in the stripping solution, the through hole 102 starts to be formed after the stripping solution forming substance is sufficiently dissolved in the stripping solution forming liquid. That is, the through hole 102 is formed by the stripping solution.

[0193] When the highly soluble solid 110 is hardly soluble in the stripping solution but soluble in the stripping solution forming solution, the through hole 102 is formed before the stripping solution forming substance is dissolved in the stripping solution forming solution. That is, the through hole 102 is formed by the stripping solution forming solution.

[0194] Until the through hole 102 is formed, the stripping liquid forming substance is dissolved from the processing film 100 into the stripping liquid forming liquid to form the stripping liquid. The solubility of the low-soluble substance in the stripping liquid is low, and the low-soluble substance is hardly dissolved by the stripping liquid. Therefore, the low-soluble solid 111 is only slightly dissolved near the surface by the stripping liquid. Therefore, the stripping liquid that reaches the upper surface of the substrate W through the through hole 102 slightly dissolves the portion of the low-soluble solid 111 near the upper surface of the substrate W. As a result, Figure 6C As shown in the enlarged view of , the stripping liquid gradually dissolves the low-soluble solid 111 near the upper surface of the substrate W while entering the gap G between the processing film 100 and the upper surface of the substrate W (stripping liquid entering step).

[0195] When the concentrated area of ​​the highly soluble solid 110 in the processing film 100 is dissolved, the stripping liquid forming solid 112 existing in the area and the stripping liquid forming solid 112 existing in the portion surrounding the through hole 102 in the processing film 100 are dissolved by the stripping liquid (stripping liquid forming liquid). Similarly, as the stripping liquid enters the gap G, the stripping liquid forming solid 112 existing in the portion near the upper surface of the substrate W in the processing film 100 is dissolved by the stripping liquid. As a result, the concentration of the alkaline component in the stripping liquid can be further increased (see Figure 6C Therefore, the peeling of the low-soluble solid 111 of the treatment film 100 can be further promoted.

[0196] Then, for example, the processing film 100 is split with the periphery of the through hole 102 as the starting point to become a film sheet, such as Fig.6D As shown, the film piece of the processing film 100 is peeled off from the substrate W while the removal object 103 is retained (processing film splitting step, peeling step). Then, by continuously supplying the stripping liquid forming liquid, the processing film 100 that has become a film piece is washed away (pushed out of the substrate W) while the removal object 103 is retained and removed from the upper surface of the substrate W (removal step).

[0197] In addition, the stripping liquid may hardly dissolve the low-soluble solid 111. Even in this case, the stripping liquid enters the minute gap G between the stripping film 100 and the upper surface of the substrate W, so that the stripping film 100 is stripped from the substrate W.

[0198] According to the first embodiment, a stripping liquid forming liquid (pure water) supplied to the upper surface of the substrate W is brought into contact with the processing film 100 to form a stripping liquid (alkaline liquid) for stripping the processing film 100 from the upper surface of the substrate W. Specifically, the alkaline component in the processing film 100 is dissolved in pure water to form an alkaline liquid (alkaline aqueous solution). The stripping liquid forming liquid is relatively cheap, and pure water among the liquids used as the stripping liquid forming liquid is particularly cheap. The alkaline liquid used as the stripping liquid is relatively expensive.

[0199] The processing film 100 that maintains the state of the removal object 103 is peeled off from the upper surface of the substrate W by the stripping liquid that is spontaneously formed on the substrate W. Then, by continuously supplying the stripping liquid forming liquid, the processing film 100 can be rinsed and removed from the upper surface of the substrate W while the processing film 100 maintains the state of the removal object 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 removal object 103 can be removed from the upper surface of the substrate W. That is, the removal object 103 can be removed from the upper surface of the substrate W without consuming a large amount of relatively expensive stripping liquid. Therefore, the increase in cost can be suppressed, and the removal object 103 existing on the upper surface of the substrate W can be removed efficiently.

[0200] In addition, according to this embodiment, the stripping liquid forming solid 112 in the processing film 100 is dissolved in the stripping liquid forming liquid to form the stripping liquid. Therefore, the stripping liquid forming substance can be dissolved in the stripping liquid forming liquid near the processing film 100, so that the stripping liquid can be formed near the processing film 100. Therefore, the stripping liquid with a high concentration of the stripping liquid forming substance before the stripping liquid forming substance is uniformly diffused throughout the stripping liquid forming liquid can act on the processing film 100. Thus, the processing film 100 can be efficiently stripped. Thus, the removal object 103 is efficiently removed from the upper surface of the substrate W together with the processing film 100.

[0201] The stripping liquid forming substance required for the formation of the stripping liquid is relatively expensive, just like the stripping liquid. Furthermore, the time required to supply the processing liquid required for the formation of the processing film 100 to the substrate W (for example, 2 to 4 seconds) is shorter than the time required to remove the processing film 100 from the substrate (for example, 60 seconds). Therefore, in this embodiment, in order to form the processing film 100, the processing liquid containing the stripping liquid forming substance is supplied to the substrate W, and in order to strip and remove the processing film 100, the stripping liquid forming liquid that does not contain the stripping liquid forming substance is supplied to the substrate W. Therefore, compared with the method of supplying the processing liquid that does not contain the stripping liquid forming substance to the substrate W in order to form the processing film 100, and supplying the stripping liquid (stripping liquid forming liquid in which the stripping liquid forming substance is dissolved) to the substrate in order to strip and remove the processing film 100, the supply time (consumption) of the stripping liquid forming substance to the substrate W can be reduced. Therefore, the increase in cost can be suppressed.

[0202] Furthermore, when a large amount of stripping liquid such as an alkaline liquid is supplied toward the upper surface of the substrate W, the substrate W and various components of the substrate processing apparatus 1 may be damaged. Therefore, it is necessary to use a substrate W and components that are resistant to the stripping liquid (alkali resistance), which may increase the cost.

[0203] In the present embodiment, the stripping liquid can be spontaneously generated by contacting the processing film 100 with a stripping liquid forming liquid such as pure water that hardly causes damage to the upper surface of the substrate W. Therefore, by supplying only the stripping liquid forming liquid to the upper surface of the substrate W without supplying the stripping liquid, the removal object 103 can be removed from the upper surface of the substrate W. That is, the removal object 103 can be removed from the upper surface of the substrate W without supplying a large amount of stripping liquid to the substrate W that can easily cause damage to the substrate W and the components of the substrate processing device 1. Therefore, damage to the substrate W and the components of the substrate processing device 1 can be suppressed. In addition, since it is not necessary to increase the stripping liquid resistance of the substrate W and the components of the substrate processing device 1, an increase in cost can be suppressed.

[0204] 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 a through hole 102 in the processing film 100. By forming the through hole 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, so that 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 the through hole 102, the remaining part maintains a solid state, that is, maintains a state of the removal object 103. As a result, the removal object 103 can be efficiently removed from the upper surface of the substrate W together with the processing film 100.

[0205] According to this embodiment, the high-soluble substance has a higher solubility in at least one of the stripping liquid forming liquid and the stripping liquid than the low-soluble substance. Therefore, by dissolving the high-soluble solid 110 in the processing film 100 in the stripping liquid forming liquid or the stripping liquid, the through hole 102 can be reliably formed in the processing film 100. On the other hand, the low-soluble solid 111 in the processing film 100 is not dissolved and remains in a solid state. Therefore, while the low-soluble solid 111 is used to hold the removal object 103, the stripping liquid can be made to act on the interface between the low-soluble solid 111 in a solid state and the substrate W. As a result, the processing film 100 can be quickly stripped from the upper surface of the substrate W, and the removal object 103 can be efficiently removed from the upper surface of the substrate W together with the processing film 100.

[0206] <Second embodiment>

[0207] Figure 7 1 is a schematic partial cross-sectional view showing a schematic structure of a processing unit 2P included in a substrate processing apparatus 1P according to the second embodiment. Figure 7 The processing unit 2P of the second embodiment is different from the processing unit 2 of the first embodiment (see Figure 2 ) is that the processing unit 2P of the second embodiment includes a fourth movable nozzle 14 to replace the relative member 6 and the central nozzle 11.

[0208] The fourth movable nozzle 14 is an example of an organic solvent supply unit that supplies an organic solvent to the upper surface of the substrate W. Alternatively, the fourth movable nozzle 14 may be an example of a gas supply unit that supplies a gas such as nitrogen to the upper surface of the substrate W.

[0209] The fourth movable nozzle 14 is moved in the horizontal direction and the vertical direction by the fourth nozzle moving unit 35. The fourth movable nozzle 14 is movable between a center position and a home position (retracted position) in the horizontal direction.

[0210] When the fourth movable nozzle 14 is located at the center position, it is opposite to the rotation center of the upper surface of the substrate W. When the fourth movable nozzle 14 is located at the home position, it is not opposite to the upper surface of the substrate W, and is located outside the processing cup 7 in a plan view. The fourth movable nozzle 14 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W in the vertical direction.

[0211] 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 shaft (not shown) along the vertical direction, an arm (not shown) connected to the rotation shaft and the fourth moving nozzle 14 and extending horizontally, and a rotation shaft driving unit (not shown) for lifting or rotating the rotation shaft.

[0212] The fourth moving nozzle 14 is connected to an organic solvent pipe 90 that guides the organic solvent to the fourth moving nozzle 14. When an organic solvent valve 95 attached to the organic solvent pipe 90 is opened, the organic solvent is continuously ejected from the fourth moving nozzle 14 toward the center area of ​​the upper surface of the substrate W.

[0213] The fourth moving nozzle 14 is connected to 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. Gas valves (a first gas valve 96A, a second gas valve 97A, and a third gas valve 98A) for opening and closing the flow paths of the plurality of gas pipes (the first gas pipe 91, the second gas pipe 92, and the third gas pipe 93) are respectively installed.

[0214] The fourth movable 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 movable nozzle 14 has a linear flow ejection port 14b for ejecting the gas supplied from the first gas pipe 91 in a straight line in the vertical direction. Moreover, the fourth movable nozzle 14 has a horizontal flow ejection port 14c for ejecting the gas supplied from the second gas pipe 92 radially in the horizontal direction toward the periphery of the fourth movable nozzle 14. In addition, the fourth movable nozzle 14 has an inclined flow ejection port 14d for ejecting the gas supplied from the third gas pipe 93 radially in the oblique downward direction toward the periphery of the fourth movable nozzle 14.

[0215] 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. In addition, a flow 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 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. In addition, filters 96C, 97C, and 98C for removing foreign matter are installed on the first gas pipe 91, the second gas pipe 92, and the third gas pipe 93, respectively.

[0216] Examples of the organic solvent ejected from the fourth moving nozzle 14 include the organic solvent ejected from the third pipe 33 (see FIG. 1 ) of the first embodiment. Figure 2 ) is the same organic solvent as the organic solvent ejected from the fourth moving nozzle 14. The gas ejected from the second tube 32 of the first embodiment (see Figure 2 ) is the same gas as the gas ejected.

[0217] In the processing unit 2P of the second embodiment, an upper rinse liquid pipe 43 for guiding rinse liquid is connected to the third moving nozzle 10. When the upper rinse liquid valve 53 attached to the upper rinse liquid pipe 43 is opened, the rinse liquid is continuously ejected downward from the ejection port of the third moving nozzle 10.

[0218] The upper rinse liquid valve 53, the first gas valve 96A, the second gas valve 97A and the third gas valve 98A, the mass flow controller 96B, the variable flow valve 97B, the variable flow valve 98B, and the fourth nozzle moving unit 35 are controlled by the controller 3 (see Figure 3 ).

[0219] By using the substrate processing apparatus 1P of the second embodiment, the same substrate processing as the substrate processing apparatus 1 of the first embodiment can be performed. However, in the first rinsing step (step S3) and the second rinsing step (step S9), the rinsing liquid is supplied to the upper surface of the substrate W from the third movable nozzle 10.

[0220] The following describes in detail the (A) low-soluble substance, (B) stripping solution-forming substance, (C) solvent, (D) high-soluble substance, and (F) stripping solution-forming liquid in the treatment liquid.

[0221] <Treatment fluid>

[0222] As described above, by drying the processing liquid on the substrate W to remove the (C) solvent, (A) the low-soluble substance is formed into a film. That is, the processing film 100 is formed. The (B) stripping liquid forming substance and / or the (D) high-soluble substance are not removed together with the (C) solvent and remain in the processing film 100. "Curing" and "hardening" are one form of "filming". In addition, the processing film 100 obtained from the processing liquid only needs to have a hardness that can retain the particles (removal object 103), and there is no need to completely remove (for example, based on gasification) the (C) solvent. The processing liquid gradually shrinks and becomes a processing film as the (C) solvent evaporates. "Not removed together with the (C) solvent" means that a very small amount compared to the whole is allowed to be removed (for example, evaporated, volatilized). For example, 0 to 10% by mass is allowed to be removed compared to the initial amount.

[0223] As described above, the processing film 100 holds the particles 103 on the substrate W, and removes them by stripping with the (F) stripping liquid forming liquid. In the case where the (B) stripping liquid forming substance remains on the processing film 100, the (B) stripping liquid forming substance is dissolved in the (F) stripping liquid forming liquid by supplying the (F) stripping liquid forming liquid to the substrate W. As a result, it is considered that the pH of the (F) stripping liquid forming liquid rises to form (modulate) 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, in the case where the (B) stripping liquid forming substance and / or the (D) highly soluble substance remain on the film, a portion that becomes the beginning of the stripping of the processing film 100 is generated.

[0224] <Low soluble substances>

[0225] (A) The low solubility substance includes at least one of novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, (A) the low solubility substance includes at least one of novolac, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and copolymers of combinations thereof. Also preferably, (A) the low solubility substance includes at least one of novolac, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. Novolac may also be phenol novolac.

[0226] Of course, the treatment liquid of the present invention may include one or a combination of two or more of the above-mentioned preferred examples as (A) the low-soluble substance. For example, (A) the low-soluble substance may include both novolac and polyhydroxystyrene.

[0227] A preferred method is to dry the (A) low-solubility substance to form a film, and most of the film will not dissolve in the (F) stripping solution forming solution (containing the dissolved (B) stripping solution forming substance) described later, but will be stripped in the form of particles. In addition, a method in which a small part of the (A) low-solubility substance is dissolved by the (F) stripping solution forming solution is allowed.

[0228] Preferably, the (A) low-soluble substance does not contain fluorine and / or silicon, and more preferably does not contain both.

[0229] The copolymerization is preferably random copolymerization or block copolymerization.

[0230] Although not intended to limit the present invention, specific examples of the (A) low-solubility substance include substances represented by the following chemical formulas 1 to 7.

[0231]

Chemical formula 1

[0232]

[0233]

Chemical formula 2

[0234]

[0235]

Chemical formula 3

[0236]

[0237]

Chemical formula 4

[0238]

[0239] (R refers to C 1－4 Alkyl group and other substituents) [Chemical Formula 5]

[0240]

[0241]

Chemical formula 6

[0242]

[0243]

Chemical formula 7

[0244]

[0245] The weight average molecular weight (Mw) of the (A) low-solubility substance is preferably 150 to 500,000.

[0246] (A) The low-solubility substance can be obtained by synthesis. Alternatively, it can be purchased. In the case of purchase, the suppliers are listed below as examples. In order to exert the effect of the present invention, the supplier can also synthesize (A) the low-solubility substance.

[0247] Phenolic varnish: Showa Kasei Co., Ltd., Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0248] Polyhydroxystyrene: Japan Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.

[0249] Polyacrylic acid derivatives: Nippon Shokubai Co., Ltd.

[0250] Polycarbonate: Sigma-Aldrich

[0251] Polymethacrylic acid derivatives: Sigma-Aldrich

[0252] As one embodiment of the present invention, the low-soluble substance (A) is 0.1 to 50% by mass compared to the total mass of the treatment liquid. In other words, the total mass of the treatment liquid is 100% by mass, and the low-soluble substance (A) is 0.1 to 50% by mass based on this. That is, "compared to..." can be replaced by "based on...". Unless otherwise specified, the same applies in this specification.

[0253] <Substances that form peeling fluid>

[0254] The (B) stripping liquid forming substance includes at least one of a primary amine, a secondary amine, a tertiary amine and a quaternary ammonium salt (preferably a primary amine, a secondary amine and a tertiary amine), and the (B) stripping liquid forming substance includes a hydrocarbon. As a preferred embodiment, the (B) stripping liquid forming substance remains in the treatment film 100 formed by the treatment liquid, and when the stripping liquid strips the treatment film 100, the (B) stripping liquid forming substance dissolves into the (F) stripping liquid forming liquid. For this reason, the boiling point of the alkaline component of (B) at one atmosphere of pressure is preferably 20 to 400°C.

[0255] It is not intended to limit the type of stripping liquid forming material, but preferred examples of (B) include N-benzylethanolamine, diethanolamine, monoethanolamine, 2-(2-aminoethylamino)ethanol, 4,4'-diaminodiphenylmethane, 2-(butylamino)ethanol, 2-anilinoethanol, triethanolamine, ethylenediamine, diethylenetriamine, tris(2-aminoethyl)amine, and tris[2-(dimethylamino)ethyl]amine.

[0256] The type of the stripping solution-forming substance is not intended to be limited, but preferred examples of (B) include N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and N,N,N',N'-tetraethylethylenediamine.

[0257] Although the type of the stripping liquid forming substance is not intended to be limited, specific examples of (B) having a cage-type three-dimensional structure include 1,4-diazabicyclo[2.2.2]octane and hexamethylenetetramine. Although the present invention is not intended to be limited, preferred examples of (B) having a planar ring structure include 1,4,7,10-tetraazacyclododecane and 1,4,7,10,13,16-hexaazacyclooctadecane.

[0258] Of course, in the treatment liquid of the present invention, the stripping liquid forming material (B) may include a combination of one or more of the above-mentioned preferred examples. For example, the stripping liquid forming material (B) may include both N-benzylethanolamine and diethanolamine. In addition, the stripping liquid forming material (B) may include both N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and 1,4-diazabicyclo[2.2.2]octane.

[0259] The molecular weight of the stripping solution-forming substance (B) is preferably 50 to 500.

[0260] (B) The stripping solution-forming material can be obtained by synthesis or purchased. Examples of suppliers include Sigma-Aldrich and Tokyo Chemical Industry Co., Ltd.

[0261] As one embodiment of the present invention, the amount of the (B) stripping solution-forming substance is preferably 1 to 100% by mass relative to the mass of the (A) low-soluble substance in the treatment liquid.

[0262] <Solvent>

[0263] Preferably, the (C) solvent contains an organic solvent. The (C) solvent is volatile. Volatile means that the volatility is higher than that of water. Preferably, the boiling point of the (C) solvent at one atmosphere of pressure is 50 to 200° C. It is also allowed that the (C) solvent contains a small amount of pure water. The pure water contained in the (C) solvent is preferably 30% by mass or less compared to the (C) solvent as a whole. Not containing pure water (0% by mass) is also a preferred embodiment. Pure water is preferably DIW.

[0264] As a preferred embodiment of the present invention, the components (including additives) contained in the treatment liquid are dissolved in the (C) solvent. It is believed that the embedding performance of the treatment liquid in this embodiment will improve the uniformity of the film.

[0265] Examples of the organic solvent included 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, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N-dimethylacetamide and N-methylpyrrolidone, lactones such as γ-butyrolactone, etc. These organic solvents may be used alone or in combination of two or more.

[0266] As a preferred embodiment, the organic solvent containing the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When the organic solvent is a combination of two, the volume ratio thereof is 20:80 to 80:20.

[0267] The (C) solvent is contained in an amount of 0.1 to 99.9% by mass based on the total mass of the treatment liquid.

[0268] <Highly soluble substances>

[0269] (D) The highly soluble substance includes hydrocarbons and also includes hydroxyl groups (-OH) and / or carbonyl groups (-C(=O)-). (D) When the highly soluble substance is a polymer, one of the constituent units contains hydrocarbons per unit and also contains hydroxyl groups and / or carbonyl groups. Examples of the carbonyl group include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, and carboxylic acids are preferred.

[0270] As described above, the (D) highly soluble substance remains on the treatment film formed on the substrate by drying the treatment liquid. When the (F) stripping liquid forming liquid strips the treatment film, the (D) highly soluble substance forms a portion that becomes the start of the stripping of the treatment film. For this reason, as the (D) highly soluble substance, a substance having a higher solubility than the (A) low soluble substance relative to the (F) stripping liquid forming liquid is preferably used.

[0271] Examples of the embodiment in which the (D) highly soluble substance contains a ketone as a carbonyl group include cyclic hydrocarbons, and specific examples thereof include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0272] Although not intended to limit the scope of the invention, preferred examples of (D) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalene diol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These can be obtained by polymerization or condensation.

[0273] Although not intended to limit the scope of the invention, preferred examples of (D) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, 3-hexyne-2,5-diol, 1,4-butyne diol, 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).

[0274] Although not intended to limit the scope of the invention, preferred examples of the polymer (D) include polymers of acrylic acid, maleic acid, or a combination thereof, and more preferred examples include polyacrylic acid and maleic acid acrylic acid copolymers.

[0275] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0276] Of course, the treatment liquid may include a combination of one or more of the above-mentioned preferred examples as (D) highly soluble substances. For example, (D) highly soluble substances may include both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0277] The molecular weight of the highly soluble substance (D) is, for example, 80 to 10,000. When the highly soluble substance (D) is a resin, a polymer or a polymer, the molecular weight is expressed as a weight average molecular weight (Mw).

[0278] (D) Highly soluble substances can be obtained by synthesis or purchased. Examples of suppliers include Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai Co., Ltd.

[0279] As one embodiment of the present invention, the content of 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.

[0280] <Other additives>

[0281] The treatment liquid of the present invention may further include (E) other additives. (E) Other additives may include surfactants, antimicrobial agents, bactericides, preservatives, antifungal agents or alkalis (preferably surfactants), or any combination thereof.

[0282] The amount of (E) other additives (or the sum of the additives when there are two or more additives) is preferably 0 to 10% by mass compared to the mass of the (A) low-soluble substance in the treatment liquid. The treatment liquid may not contain (E) other additives (0% by mass).

[0283] <Stripping liquid forming liquid>

[0284] As described above, by drying the processing liquid supplied to the substrate W and removing the (C) solvent, the (A) low-solubility substance is formed into a film. That is, a processing film is formed. The (B) stripping liquid forming substance and / or the (D) high-solubility substance are not removed together with the (C) solvent and remain in the processing film. The processing film can hold the particles existing on the substrate and is removed by the (F) stripping liquid forming liquid while being held.

[0285] Here, the stripping solution forming liquid (F) is preferably neutral or weakly acidic. The pH of the stripping solution forming liquid (F) is preferably 4 to 7, more preferably 5 to 7, and further preferably 6 to 7. Preferably, the pH is measured by degassing to avoid the influence of dissolved carbon dioxide in the air.

[0286] Preferably, the (F) stripping solution forming liquid contains pure water. As described above, the treatment liquid of the present invention contains the (B) stripping solution forming substance, and therefore, it is eluted into the (F) stripping solution forming liquid, and the pH of the (F) stripping solution forming liquid is increased to form (modulate) the stripping solution. Therefore, most of the (F) stripping solution forming liquid can be pure water. Compared with the total mass of the (F) stripping solution forming liquid, the pure water contained in (F) is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, further preferably 95 to 100 mass%, and further preferably 99 to 100 mass%. It is also preferred that the (F) stripping solution forming liquid consists only of pure water (100 mass%).

[0287] When the treatment liquid is composed of (A) a low-soluble substance, (B) a stripping liquid-forming substance, and (C) a solvent, the formation of the treatment film and the stripping of the treatment film from the substrate can also be described as follows.

[0288] By dripping a treatment liquid onto the substrate W to which particles are attached and drying it, a low-soluble substance (polymer) is formed into a film. By forming a film of a low-soluble substance, a treatment film is formed. A stripping liquid forming substance (alkaline component) remains on the treatment film. Then, a stripping liquid forming liquid is supplied to the treatment film, and the alkaline component is dissolved into the stripping liquid forming liquid. Due to the dissolution of the alkaline component, the pH of the stripping liquid forming liquid near the treatment film rises, thereby forming (modulating) a stripping liquid that strips the treatment film from the substrate W. Due to the dissolution of the alkaline component, traces (holes) of the dissolution of the alkaline component are generated on the treatment film. Due to the dissolution of the alkaline component, the pH of the stripping liquid near the treatment film rises, which can improve the effect of stripping the treatment film from the substrate. Moreover, the trace formed by the dissolution of the alkaline component becomes the beginning of the stripping of the treatment film, and with this as the starting point, the crack expands. The treatment film that is broken due to the expansion of the crack is removed from the substrate while the particles are maintained.

[0289] When the processing liquid is composed of (A) a low-soluble substance, (B) a stripping liquid-forming substance, (C) a solvent, and (D) a high-soluble substance, the formation of the processing film and the stripping of the processing film from the substrate can also be described as follows.

[0290] By dripping a treatment liquid onto the substrate W to which particles are attached and drying it, a low-soluble substance (polymer) is formed into a film. By forming a film of a low-soluble substance, a treatment film is formed. A stripping liquid forming substance (alkaline component) remains on the treatment film. Then, a stripping liquid forming liquid is supplied to the treatment film, and the alkaline component is dissolved into the stripping liquid forming liquid. Due to the dissolution of the alkaline component, the pH of the stripping liquid forming liquid near the treatment film rises, thereby forming (modulating) a stripping liquid that strips the treatment film from the substrate W. In addition, a highly soluble substance (crack promoting component) remains on the treatment film. The crack promoting component is dissolved into the stripping liquid forming liquid / stripping liquid, and traces (holes) of the dissolution of the crack promoting component are generated on the treatment film. The trace formed by the dissolution of the crack promoting component becomes the beginning of the stripping of the treatment film, and with this as the starting point, the crack expands. The treatment film that is broken by the crack expansion is removed from the substrate W while the particles are retained.

[0291] It is believed that when the (F) stripping liquid forming liquid removes (strips off) the treated film (particle retaining layer), the (B) stripping liquid forming substance and / or (D) highly soluble substance remaining in the treated film form a portion that becomes the beginning of film stripping. Therefore, preferably, the solubility of the (B) stripping liquid forming substance and the (D) highly soluble substance relative to the (F) stripping liquid forming liquid is higher than that of the (A) low soluble substance. The solubility can be evaluated by a known method. For example, under the conditions 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 closed, and the oscillation is performed for 3 hours using an oscillator, thereby determining whether (A) or (B) is dissolved. In order to evaluate the solubility, the pure water can also be changed to an alkaline liquid (for example, 5.0% by mass ammonia water).

[0292] It is a preferred embodiment of the present invention that the treatment film is not completely dissolved by the (F) stripping solution forming liquid and is removed from the substrate in a particle state. The treatment film is removed in a state of being finely cut by the "part to be the start of stripping", for example.

[0293] The present invention will be described below by way of examples. In addition, the processing liquid and the stripping liquid forming liquid are not limited to these examples.

[0294] Preparation of patterned substrate

[0295] A KrF resist composition (AZ DX-6270P, Merck Performance Materials Plasma Co., Ltd., hereinafter referred to as MPM) was dripped onto an 8-inch Si substrate and spin-coated onto the substrate at 1500 rpm. The substrate was soft-baked at 120°C for 90 seconds. A KrF stepper (FPA-3000EX5, Canon) was used at 20 mJ / cm 2Expose, perform PEB (post-exposure baking) at 130°C for 90 seconds, and develop with a developer (AZ MIF-300, MPM strain). Thus, a resist pattern with a line space of 360nm spacing and a duty ratio of 1:1 is obtained. Using the resist pattern as an etching mask, the substrate is etched using a dry etching device (NE-5000N, ULVAC). Then, the substrate is cleaned with a stripper (AZ400T, MPM strain) to strip off the resist pattern and resist residue. Thus, a pattern substrate with a spacing of 360nm, a duty ratio of 1:1, and a line height of 150nm is prepared.

[0296] Bare substrate preparation

[0297] An 8-inch Si substrate was used.

[0298] Evaluation of substrate modulation

[0299] The particles are attached to the pattern substrate and the bare substrate.

[0300] As the particles used in the experiment, ultra-high purity colloidal silica (PL-10H, Fuso Chemical Industry, average primary particle size 90nm) was used. By dripping 50mL of the silica microparticle composition, rotating at 500rpm for 5 seconds, coating was performed. Then, by rotating at 1000rpm for 30 seconds, the solvent of the silica microparticle composition was spin-dried. Thus, the evaluation substrate was obtained.

[0301] Comparative test of the presence or absence of each component in the treatment liquid

[0302] Add 5 g of phenolic varnish (Mw about 5,000 (A) low solubility substance) to 95 g of isopropyl alcohol ((C) solvent). Stir it with a stirring piece for 1 hour to obtain a liquid with a concentration of (A) low solubility substance of 5 mass%. Add 2.5 g each of diethanolamine ((B) stripping liquid forming substance) and 3,6-dimethyl-4-octyne-3,6-diol (Tokyo Chemical Industry, hereinafter referred to as TCI, (D) high solubility substance) to the above liquid. Stir it with a stirring piece for 1 hour. Filter the liquid with Optimizer UPE (Japan Integrated Co., Ltd.). Thus, a treatment liquid containing (A), (B) and (D) is obtained.

[0303] A treatment liquid containing (A) and (B) was obtained in the same manner except that the component (D) was not added.

[0304] A treatment liquid containing (A) and (D) was obtained in the same manner except that the component (B) was not added.

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

[0306] Using a coater-developer RF3 (SOKUDO), 10 cc of each treatment solution was dripped onto each evaluation substrate, and the substrate was rotated at 1500 rpm for 60 seconds, thereby coating and drying. While rotating the substrate at 100 rpm, DIW was dripped for 10 seconds, and the entire substrate was covered with DIW, and this state was maintained for 20 seconds. The substrate was dried by rotating the substrate at 1500 rpm. By this rotation, the film was peeled off and removed if there was a film.

[0307] The residual particle amounts of these substrates were compared. The patterned substrates were evaluated using a bright field defect inspection device (UVision4, AMAT), and the bare substrates were evaluated using a dark field defect inspection device (LS-9110, Hitachi High-Tech Corporation).

[0308] Preparation Example 1 of Treatment Solution 1

[0309] Add 5 g of phenolic varnish (Mw about 5,000 (A) low solubility substance) to 95 g of isopropyl alcohol ((C) solvent). Stir it with a stirring piece for 1 hour to obtain a liquid with a concentration of (A) low solubility substance of 5 mass%. Add 2.5 g each of N-benzylethanolamine (TCI strain, (B) stripping liquid forming substance) and 2,2-bis(4-hydroxyphenyl)propane (TCI strain, (D) high solubility substance) to the above liquid. Stir it with a stirring piece for 1 hour. Filter the liquid with Optimizer UPE (Japan Integration Co., Ltd.). Thus, treatment liquid 1 is obtained. The results are recorded in Table 1.

[0310] In the following Tables 1 to 3, the above-mentioned phenolic varnish 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-soluble substance is added to the (C) solvent. The numbers in parentheses in the (B) column refer to the concentration (mass %) when the (B) stripping liquid forming substance is added to the liquid compared to the (A) low-soluble substance. The numbers in parentheses in the (D) column refer to the concentration (mass %) when the (D) high-soluble substance is added to the liquid compared to the (A) low-soluble substance.

[0311] Table 1

[0312]

[0313] Table 2

[0314]

[0315] Table 3

[0316]

[0317] In the above Tables 1 to 3,

[0318] The phenol novolac (Mw about 10,000) is referred to as A2.

[0319] The phenol novolac (Mw about 100,000) is referred to as A3.

[0320] Polyhydroxystyrene (Mw about 1,000) is referred to as A4.

[0321] Polyhydroxystyrene (Mw about 10,000) is referred to as A5.

[0322] Polyhydroxystyrene (Mw about 100,000) is referred to as A6.

[0323] The polyacrylic acid derivative (Mw about 1,000) having the structure shown in the following chemical formula 8 is referred to as A7.

[0324]

Chemical formula 8

[0325]

[0326] The polyacrylic acid derivative (Mw about 10,000) composed of the above repeating units is referred to as A8.

[0327] The polyacrylic acid derivative (Mw about 100,000) composed of the above repeating units is referred to as A9.

[0328] Polymethyl methacrylate (Mw about 5,000) is referred to as A10.

[0329] Diethanolamine is referred to as B2.

[0330] Monoethanolamine is referred to as B3.

[0331] 2-(2-aminoethylamino)ethanol is referred to as B4.

[0332] 4,4'-diaminodiphenylmethane is referred to as B5.

[0333] 1,4-diazabicyclo[2.2.2]octane is abbreviated as B6.

[0334] Hexamethylenetetramine is referred to as B7.

[0335] 2-(Butylamino)ethanol is referred to as B8.

[0336] 3,6-dimethyl-4-octyne-3,6-diol is referred to as D2.

[0337] Polyacrylic acid (Mw about 1,000) is referred to as D3.

[0338] Polyacrylic acid (Mw about 10,000) is referred to as D4.

[0339] The maleic acid acrylic acid copolymer (Mw about 3,000) composed of the following Chemical Formula 9 is abbreviated as D5.

[0340]

Chemical formula 9

[0341]

[0342] Preparation Examples 1 to 27 of Treatment Liquids 1 to 27

[0343] The substances listed in Tables 1 to 3 are used as (A) low-soluble substances, (B) stripping liquid forming substances, (C) solvents, and (D) high-soluble substances. Treatment liquids 2 to 27 are prepared in the same manner as in Preparation Example 1, except that the concentrations are adjusted to the concentrations listed in Tables 1 to 3.

[0344] Evaluation of the amount of residual particles in treatment solutions 1 to 27

[0345] The evaluation substrate prepared as described in the preparation of the above-mentioned evaluation substrate was used.

[0346] Using a coater-developer RF3 (SOKUDO), 10 cc of each treatment solution was dripped onto each evaluation substrate, and the substrate was rotated at 1500 rpm for 60 seconds, thereby coating and drying. While rotating the substrate at 100 rpm, DIW was dripped for 10 seconds, and the entire substrate was covered with DIW, and this state was maintained for 20 seconds. The substrate was dried by rotating the substrate at 1500 rpm. By this rotation, the film was peeled off and removed if there was a film.

[0347] The residual particle amounts of these substrates were compared. The patterned substrates were evaluated using a bright field defect inspection device (UVision4, AMAT), and the bare substrates were evaluated using a dark field defect inspection device (LS-9110, Hitachi High-Tech Corporation).

[0348] The coating condition and film removal condition were confirmed, the number of remaining particles was counted, and evaluation was performed according to the following criteria. The evaluation results are shown in Tables 1 to 3.

[0349] AA: ≤10

[0350] A: >10, ≤100

[0351] B: >100, ≤1000

[0352] C: >1000

[0353] D: The film was not evenly applied or the film was not removed

[0354] Other variations

[0355] The present invention is not limited to the above-described embodiments, and can be implemented in other forms.

[0356] For example, unlike the substrate processing in the above-described embodiment, the chemical solution supplying step (step S2 ), the first rinsing step (step S3 ), and the first organic solvent supplying step (step S4 ) may be omitted.

[0357] In the substrate processing in the above-mentioned embodiment, in the process film forming step (step S6 and step S7), the solvent of the process liquid is evaporated by heating the substrate W with a heat medium. However, the present invention is not limited to the supply of a heat medium, and for example, the substrate W may be heated by a heater (not shown) built into the spin base 21 or the opposing member 6. In this case, the heater functions as a substrate heating unit and an evaporation unit (evaporation promotion unit).

[0358] In the substrate processing in the above-described embodiment, the second rinsing step (step S9) is performed after the stripping and removing step (step S8). However, the second rinsing step may be omitted.

[0359] In detail, in the stripping and removing step, pure water is used as the stripping liquid forming liquid. When the processed film 100 is discharged to the outside of the substrate W by the pure water as the stripping liquid forming liquid, it is not necessary to wash away the stripping liquid forming liquid, so the second rinsing step can be omitted. In addition, when the stripping liquid forming liquid supplied to the substrate W in the stripping and removing step and the organic solvent (residue removing liquid) supplied to the substrate W in the second organic solvent supplying step (step S10) performed after the second rinsing step are compatible, it is not necessary to perform the second rinsing step.

[0360] In addition, it is not necessary to heat the substrate W during the formation of the process film 100. That is, in the thin film forming step (step S6), if the solvent is sufficiently volatilized, the subsequent heating step (step S7) may not be performed. In particular, if the solvent can be left inside the process film 100, it is easy to evaporate the solvent to a desired degree even without heating the substrate W.

[0361] Although the embodiments of the present invention have been described in detail, these are merely specific examples used to clarify the technical content of the present invention, and the present invention should not be construed as being limited to these specific examples. The scope of the present invention is limited only by the appended claims.

[0362] This application claims priority based on Japanese Patent Application No. 2018-234733 filed on December 14, 2018, and the entire contents of this application are incorporated herein by reference.

Claims

1. A substrate processing method, include: The process liquid supplying step is to supply the process liquid containing the solute and the solvent toward the surface of the substrate. a treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that retains the removal object present on the surface of the substrate, a stripping step of supplying a stripping liquid forming liquid to the surface of the substrate so that the stripping liquid forming liquid contacts the processing film to form a stripping liquid, and stripping the processing film holding the removal object from the surface of the substrate by the stripping liquid, a removal step of continuously supplying the stripping liquid forming liquid after the treatment film is stripped, washing away the treatment film while keeping the treatment film on the state of the removal object, thereby removing the treatment film from the surface of the substrate, The solute has a stripping solution-forming substance, The processing film forming step includes the step of forming the processing film having the stripping liquid forming substance in a solid state. The stripping step includes a step of forming the stripping solution by dissolving the stripping solution forming substance in a solid state in the processing film in the stripping solution forming liquid supplied to the surface of the substrate.

2. The substrate processing method according to claim 1, wherein: The stripping liquid is an alkaline liquid.

3. The substrate processing method according to claim 1, wherein: The stripping solution forming liquid is pure water.

4. The substrate processing method according to claim 1, wherein: The stripping process comprises: In the through-hole forming step, the stripping liquid forming solution is supplied to the surface of the substrate to partially dissolve the processing film and form a through-hole in the processing film.

5. The substrate processing method according to claim 4, wherein: The solute includes a high-soluble substance and a low-soluble substance having a lower solubility in the stripping solution than the high-soluble substance. The process film forming step includes forming the process film having the high-solubility substance and the low-solubility substance in a solid state. The through-hole forming step includes a step of forming the through-hole in the processing film by dissolving the highly soluble substance in a solid state in the processing film in the stripping liquid formed on the substrate.

6. The substrate processing method according to claim 5, wherein: The solubility of the low-soluble substance in the stripping solution forming liquid is lower than the solubility of the high-soluble substance in the stripping solution forming liquid, The through-hole forming step includes a step of forming the through-hole in the processing film by dissolving the highly soluble substance in a solid state in the processing film in the stripping solution forming liquid supplied to the surface of the substrate.

7. The substrate processing method according to claim 4, wherein: The solute includes a high-soluble substance and a low-soluble substance having a solubility lower than that of the high-soluble substance in the stripping solution forming solution. The process film forming step includes forming the process film having the high-solubility substance and the low-solubility substance in a solid state. The through-hole forming step includes a step of forming the through-hole in the processing film by dissolving the highly soluble substance in a solid state in the processing film in the stripping solution forming liquid supplied to the surface of the substrate.

8. A substrate processing method, include: The process liquid supplying step is to supply a process liquid having a solute containing an alkaline component and a solvent toward the surface of the substrate. a treatment film forming 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 retains the removal object present on the surface of the substrate and contains the alkaline component, a stripping step of supplying pure water to the surface of the substrate so that the pure water contacts the treatment film, dissolving the alkaline component in the treatment film into the pure water to form an alkaline aqueous solution, and stripping the treatment film, which retains the removal object, from the surface of the substrate by the alkaline aqueous solution, In the removal step, the pure water is continuously supplied after the process film is peeled off, so that the process film is washed away while the process film is kept holding the removal object, thereby removing the process film from the surface of the substrate.

9. A substrate processing device, include: The processing liquid supply unit supplies the processing liquid containing the solute and the solvent to the surface of the substrate. a solid forming unit for solidifying or hardening the treatment liquid, a stripping liquid forming liquid supply unit for supplying the stripping liquid forming liquid to the surface of the substrate, a controller for controlling the processing liquid supply unit, the solid forming unit, and the stripping liquid forming liquid supply unit, The controller is set up to execute: a processing liquid supplying step of supplying the processing liquid from the processing liquid supplying unit to the surface of the substrate, a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate by the solid forming unit, thereby forming a treatment film on the surface of the substrate that retains the removal object on the surface of the substrate, 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 processing film to form a stripping liquid, and stripping the processing film holding the removal object from the surface of the substrate by the stripping liquid, a removing step of removing the processing film from the surface of the substrate while keeping the processing film as the object to be removed by continuously supplying the stripping liquid forming liquid from the stripping liquid forming liquid supply unit after the processing film is stripped, The solute has a stripping solution-forming substance, In the process film forming step, the process film having the stripping liquid forming substance in a solid state is formed. In the stripping step, the stripping solution is formed by dissolving the stripping solution forming substance in a solid state in the processing film in the stripping solution forming liquid supplied to the surface of the substrate.

10. The substrate processing apparatus according to claim 9, wherein: The stripping liquid is an alkaline liquid.

11. The substrate processing apparatus according to claim 9, wherein: The stripping solution forming liquid supply unit supplies pure water as the stripping solution forming liquid to the surface of the substrate.

12. The substrate processing apparatus according to claim 9, wherein: In the stripping step, the stripping solution forming liquid is supplied to the surface of the substrate, whereby the processing film is partially dissolved and a through hole is formed in the processing film.

13. The substrate processing apparatus according to claim 12, wherein: The solute includes a high-soluble substance and a low-soluble substance having a lower solubility in the stripping solution than the high-soluble substance. In the treatment film forming step, the treatment film having the high-solubility substance and the low-solubility substance in a solid state is formed. In the stripping 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 stripping liquid formed on the substrate.

14. The substrate processing apparatus according to claim 13, wherein: The solubility of the low-soluble substance in the stripping solution forming liquid is lower than the solubility of the high-soluble substance in the stripping solution forming liquid, In the process film forming step, the through hole is formed in the process film by dissolving the highly soluble substance in a solid state in the process film in the stripping solution forming liquid supplied to the surface of the substrate.

15. The substrate processing apparatus according to claim 12, wherein: The solute includes a high-soluble substance and a low-soluble substance having a solubility lower than that of the high-soluble substance in the stripping solution forming solution. In the treatment film forming step, the treatment film having the high-solubility substance and the low-solubility substance in a solid state is formed. In the stripping 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 stripping solution forming liquid supplied to the surface of the substrate.

16. A substrate processing device, include: The processing liquid supply unit supplies a processing liquid having a solute containing an alkaline component and a solvent to the surface of the substrate. a solid forming unit for solidifying or hardening the treatment liquid, a pure water supply unit for supplying pure water to the surface of the substrate; a controller for controlling the treatment liquid supply unit, the solid forming unit and the pure water supply unit, The controller is set up to execute: a processing liquid supplying step of supplying the processing liquid from the processing liquid supplying unit to the surface of the substrate, a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate by the solid forming unit, thereby forming a treatment film on the surface of the substrate that retains the removal object existing on the surface of the substrate and contains the alkaline component, a stripping step of supplying the pure water from the pure water supply unit to the surface of the substrate so that the pure water contacts the treatment film, dissolving the alkaline component in the treatment film into the pure water to form an alkaline aqueous solution, and stripping the treatment film, which retains the state of the removal object, from the surface of the substrate by the alkaline aqueous solution, In the removing step, the processing film is removed from the surface of the substrate while the processing film holds the removal object by continuing to supply the pure water from the pure water supply unit after the processing film is peeled off.

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