Substrate Processing Method and Substrate Processing Apparatus

Abstract

The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method includes: a hydrophilization step of hydrophilizing the surface of the substrate; a processing liquid supply step of supplying a processing liquid to the surface of the hydrophilized substrate; a processing film formation step of curing or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; and a peeling step of supplying a peeling liquid to the surface of the substrate to peel the processing film holding the object to be removed from the surface of the substrate. The peeling step includes a through-hole formation step of partially dissolving the processing film in the peeling liquid to form through-holes in the processing film.

Description

[0001] [Related Application]

[0002] This application corresponds to Japanese Patent Application No. 2020-53310 filed with the Japan Patent Office on March 24, 2020, and Japanese Patent Application No. 2020-53309 filed with the Japan Patent Office on March 24, 2020. The entire description of these applications is incorporated herein by reference. Technical Field

[0003] The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Substrates to be processed include, for example, semiconductor wafers, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, substrates for solar cells, and substrates for flat panel displays (FPDs) such as liquid crystal display devices, plasma display devices, and organic EL (Electroluminescence) display devices. Background Art

[0004] In the manufacturing steps of semiconductor devices, a step of removing various contaminants attached to the substrate, residues of processing liquids or resists used in previous steps, or various fine particles, etc. (hereinafter sometimes collectively referred to as "objects to be removed") is performed.

[0005] Specifically, common methods include: removing the objects to be removed by supplying deionized water (DIW) or the like to the substrate and utilizing the physical action of the DIW; or chemically removing the objects to be removed by supplying a chemical solution that reacts with the objects to be removed to the substrate.

[0006] However, the uneven patterns formed on the substrate are becoming increasingly finer and more complex. Therefore, it is becoming increasingly difficult to remove the objects to be removed by DIW or a chemical solution while suppressing damage to the uneven patterns.

[0007] Therefore, a method has been proposed in which a processing liquid is supplied to the surface of the substrate, a holding layer that holds the objects to be removed present on the substrate is formed by condensing the processing liquid on the substrate, and then a stripping liquid is supplied to the upper surface of the substrate, thereby stripping and removing the holding layer together with the objects to be removed from the surface of the substrate (see the specification of U.S. Patent Application Publication No. 2019 / 091737). Summary of the Invention

[0008] U.S. Patent Application Publication No. 2019 / 091737 describes that an entry path for the stripping liquid is formed by the stripping liquid to allow the stripping liquid to enter the holding layer. However, depending on the surface state of the substrate, it may not be possible to allow the stripping liquid to fully enter the interface between the substrate and the holding layer, resulting in insufficient stripping of the holding layer from the surface of the substrate.

[0009] Therefore, there is a need to find a method for effectively stripping a holding layer that holds an object to be removed from a substrate. Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can effectively strip a processing film that holds an object to be removed from the surface of a substrate.

[0010] One embodiment of the present invention provides a substrate processing method, including: a hydrophilization step of hydrophilizing the surface of the substrate; a processing liquid supply step of supplying a processing liquid to the surface of the hydrophilized substrate; a processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; and a stripping step of supplying a stripping liquid to the surface of the substrate to strip the processing film that holds the object to be removed from the surface of the substrate. Moreover, the stripping step includes a through-hole formation step of partially dissolving the processing film in the stripping liquid to form through-holes in the processing film.

[0011] The inventors of the present application have found that the stripping action of the stripping liquid for stripping the processing film from the substrate varies depending on the surface state of the substrate. Specifically, the higher the hydrophilicity of the surface of the substrate, the easier it is to strip the processing film with the stripping liquid. More specifically, the higher the hydrophilicity of the surface of the substrate, the easier it is for the stripping liquid to act on the interface between the processing film and the substrate, so that the processing film can be effectively stripped from the surface of the substrate.

[0012] Therefore, if a method of forming a processing film on the surface of a hydrophilized substrate and supplying a stripping liquid to the surface of the substrate on which the processing film is formed is adopted, the processing film can be effectively stripped from the substrate.

[0013] Furthermore, through the stripping liquid supplied to the surface of the substrate, through-holes are formed in the processing film, so that the stripping liquid can reach the interface between the processing film and the substrate via the through-holes. Thereby, the stripping liquid can act on the interface between the portion of the processing film surrounding the through-holes and the substrate. Therefore, compared with the method of not forming through-holes in the processing film but allowing the stripping liquid to penetrate into the processing film to reach the interface between the processing film and the substrate, the stripping liquid can act on the interface between the processing film and the substrate more quickly. Although the processing film will be partially dissolved by the stripping liquid due to the formation of through-holes, the remaining portion will maintain a solid state. Therefore, the processing film that holds the object to be removed can be effectively stripped from the surface of the substrate.

[0014] As described above, the stripping liquid can quickly act on the interface between the processing film and the substrate, and most of the processing film can be maintained in a solid state. Therefore, the processing film holding the object to be removed can be effectively stripped from the substrate.

[0015] In one embodiment of the present invention, the stripping step includes a stripping liquid introduction step of introducing the stripping liquid between the surface of the substrate and the processing film.

[0016] The inventors of the present application found that the higher the hydrophilicity of the surface of the substrate, the higher the wettability (affinity) of the stripping liquid to the substrate, and the easier it is for the stripping liquid to enter between the substrate and the processing film. Therefore, if a method of forming a processing film on the surface of a substrate that has been hydrophilized and supplying the stripping liquid to the surface of the substrate on which the processing film is formed is adopted, the stripping liquid can effectively enter between the substrate and the processing film. Thereby, the processing film can be effectively stripped from the surface of the substrate.

[0017] In one embodiment of the present invention, the hydrophilization step includes a step of hydrophilizing the surface of the substrate by supplying a hydrophilizing liquid to the surface of the substrate. By supplying the hydrophilizing liquid to the surface of the substrate, the hydrophilizing liquid diffuses on the surface of the substrate, so that the hydrophilizing liquid can cover the entire surface of the substrate. Therefore, the entire surface of the substrate can be hydrophilized without omission. Since the entire surface of the substrate has been hydrophilized, in the subsequent stripping step, the stripping liquid can easily act on the interface between the processing film and the substrate on the entire surface of the substrate. Therefore, the non-uniformity of the stripping of the processing film on the surface of the substrate can be reduced.

[0018] In one embodiment of the present invention, the hydrophilizing liquid is an oxidizing liquid or an organic solvent. When these liquids are used as the hydrophilizing liquid, the surface of the substrate can be hydrophilized by removing the hydrophobic organic substances present on the surface of the substrate. When an organic solvent is used as the hydrophilizing liquid, the hydrophobic organic substances present on the surface of the substrate will dissolve in the organic solvent, and the surface of the substrate will be hydrophilized.

[0019] On the other hand, when an oxidizing liquid is used as the hydrophilizing liquid, a part near the surface of the substrate will be oxidized. Since the part near the surface of the substrate is oxidized, the hydrophilicity of the surface of the substrate is improved.

[0020] When an oxidizing liquid is used as the hydrophilizing liquid, the surface of the substrate can be hydrophilized regardless of the presence of organic substances. That is, even if there are organic substances on the surface of the substrate that are difficult to dissolve in organic solvents, the surface of the substrate can be hydrophilized. Therefore, when an oxidizing liquid is used as the hydrophilizing liquid, the hydrophilicity of the surface of the substrate can be further improved.

[0021] In one embodiment of the present invention, at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate. If these substances are exposed from the surface of the substrate, the surface of the substrate can be hydrophilized by a hydrophilization step.

[0022] In one embodiment of the present invention, the surface layer of the substrate includes a TiN layer exposed from the surface of the substrate, and the hydrophilizing liquid is an oxidizing liquid. By supplying an oxidizing liquid such as hydrofluoric acid (HF, DHF) or an ammonia-hydrogen peroxide water mixture (APM) to the surface of the substrate as the hydrophilizing liquid, an oxide film can be formed on the surface of the TiN layer. APM is also called SC1 (Standard Clean 1, standard cleaning liquid 1). By forming an oxide film on the surface of the TiN layer, the surface of the substrate can be hydrophilized.

[0023] In one embodiment of the present invention, the hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water on the surface of the substrate so that the contact angle is less than 41.7°. The higher the hydrophilicity of the surface of the substrate, the smaller the contact angle of pure water on the surface of the substrate. The inventors of the present application have found that if the contact angle of pure water on the surface of the substrate is less than 41.7°, the stripping liquid can fully act on the interface between the substrate and the processing film.

[0024] Therefore, if the surface of the substrate is hydrophilized to reduce the contact angle of pure water on the surface of the substrate so that the contact angle is less than 41.7°, the stripping liquid can fully act on the interface between the substrate and the processing film. Thereby, the processing film holding the object to be removed can be effectively peeled off from the substrate.

[0025] In one embodiment of the present invention, the contact angle of pure water on the processing film is greater than 52° and less than 61°. The inventors of the present application have found that if the contact angle of pure water on the processing film is greater than 52° and less than 61°, the stripping liquid can fully act on the interface between the substrate and the processing film.

[0026] Therefore, if the contact angle of pure water on the processing film is greater than 52° and less than 61°, the stripping liquid can fully act on the interface between the substrate and the processing film, thereby effectively peeling off the processing film.

[0027] In one embodiment of the present invention, the treatment liquid contains a solvent and a solute. The solute has a highly soluble component and a low-soluble component that is less soluble in the stripping liquid than the highly soluble component. The treatment film forming step includes a step of forming the treatment film, which has a highly soluble solid formed from the highly soluble component and a low-soluble solid formed from the low-soluble component. Further, in the stripping step, the highly soluble solid is dissolved in the stripping liquid, and the treatment film holding the object to be removed is stripped from the surface of the substrate.

[0028] According to this method, the solubility of the highly soluble component in the stripping liquid is higher than that of the low-soluble component in the stripping liquid. Therefore, the highly soluble solid formed from the highly soluble component is more easily dissolved in the stripping liquid than the low-soluble solid formed from the low-soluble component.

[0029] Therefore, the stripping liquid is supplied to the surface of the substrate to dissolve the highly soluble solid in the stripping liquid, thereby forming a gap in the treatment film. On the other hand, the low-soluble solid does not dissolve in the stripping liquid and remains in a solid state.

[0030] Therefore, both the highly soluble solid can be dissolved in the stripping liquid and the low-soluble solid can remain in a solid state without dissolving in the stripping liquid. Therefore, the stripping liquid passes through the gap (space, path) formed by the dissolution of the highly soluble solid and reaches the interface between the substrate and the low-soluble solid.

[0031] Therefore, the object to be removed can be held by the low-soluble solid, and the stripping liquid can act on the interface between the low-soluble solid and the substrate. As a result, the treatment film can be quickly stripped from the substrate, and the object to be removed can be efficiently removed from the substrate together with the treatment film.

[0032] One embodiment of the present invention provides a substrate treatment method, including: a hydrophilization step of hydrophilizing the surface of the substrate; a treatment liquid supply step of supplying a treatment liquid to the surface of the hydrophilized 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 holds an object to be removed existing on the surface of the substrate; and a stripping step of supplying a stripping liquid to the surface of the substrate to strip the treatment film holding the object to be removed from the surface of the substrate; and the hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water on the surface of the substrate so that the contact angle is less than 41.7°.

[0033] According to this method, a treatment film is formed on the surface of a hydrophilized substrate, and a stripping liquid is supplied to the surface of the substrate on which the treatment film is formed. As described above, the higher the hydrophilicity of the surface of the substrate, the easier it is for the stripping liquid to act on the interface between the treatment film and the substrate, so that the treatment film can be effectively stripped from the surface of the substrate. In this method, the surface of the substrate is hydrophilized in such a way that the contact angle of pure water on the surface of the substrate is less than 41.7°. Therefore, the stripping liquid can fully act on the interface between the substrate and the treatment film. Thus, the treatment film holding the object to be removed can be effectively stripped from the substrate.

[0034] In one embodiment of the present invention, the contact angle of pure water on the treatment film is greater than 52° and less than 61°. Therefore, the stripping liquid can fully act on the interface between the substrate and the treatment film, so that the treatment film can be effectively stripped.

[0035] One embodiment of the present invention provides a substrate treatment method, comprising: a hydrophilization step of hydrophilizing the surface of a substrate; a treatment liquid supply step of supplying a treatment liquid to the surface of the hydrophilized substrate; a treatment film formation step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; and a stripping step of supplying a stripping liquid to the surface of the substrate to strip the treatment film holding the object to be removed from the surface of the substrate; and the treatment liquid contains a solvent and a solute, and the solute has a highly soluble component and a low soluble component with a lower solubility in the stripping liquid than the highly soluble component. In this substrate treatment method, the treatment film formation step includes a step of forming the treatment film, and the treatment film has a highly soluble solid formed from the highly soluble component and a low soluble solid formed from the low soluble component. Moreover, in the stripping step, the highly soluble solid is dissolved in the stripping liquid, and the treatment film holding the object to be removed is stripped from the surface of the substrate.

[0036] According to this method, a treatment film is formed on the surface of a hydrophilized substrate, and a stripping liquid is supplied to the surface of the substrate on which the treatment film is formed. As described above, the higher the hydrophilicity of the surface of the substrate, the easier it is for the stripping liquid to act on the interface between the treatment film and the substrate, so that the treatment film can be effectively stripped from the surface of the substrate. Therefore, the treatment film can be effectively stripped from the substrate.

[0037] According to this method, furthermore, the solubility of the highly soluble component in the stripping liquid is higher than the solubility of the low soluble component in the stripping liquid. Therefore, the highly soluble solid formed from the highly soluble component is more easily dissolved in the stripping liquid than the low soluble solid formed from the low soluble component.

[0038] Therefore, a stripping liquid is supplied to the surface of the substrate, and the highly soluble solid is dissolved in the stripping liquid, thereby forming a gap in the treatment film. On the other hand, the low-soluble solid does not dissolve in the stripping liquid and remains in a solid state.

[0039] Therefore, both the highly soluble solid can be dissolved in the stripping liquid, and the low-soluble solid can be maintained in a solid state without dissolving in the stripping liquid. Therefore, the stripping liquid passes through the gap (space, path) formed by the dissolution of the highly soluble solid and reaches the interface between the substrate and the low-soluble solid.

[0040] Therefore, the object to be removed can be held by the low-soluble solid, and the stripping liquid can act on the interface between the low-soluble solid and the substrate. Thereby, the treatment film holding the object to be removed can be effectively stripped from the substrate.

[0041] As a result, the treatment film can be quickly stripped from the substrate, and the object to be removed can be efficiently removed from the substrate together with the treatment film.

[0042] In this substrate treatment method, at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate. If these substances are exposed from the surface of the substrate, the surface of the substrate can be hydrophilized by a hydrophilization step.

[0043] In this substrate treatment method, the hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water on the surface of the substrate to make the contact angle less than 41.7°. Therefore, the stripping liquid can act sufficiently on the interface between the substrate and the treatment film. Thereby, the treatment film holding the object to be removed can be effectively stripped from the substrate.

[0044] One embodiment of the present invention provides a substrate treatment apparatus, comprising: a hydrophilization liquid supply unit that supplies a hydrophilization liquid for hydrophilizing the surface of the substrate to the surface of the substrate; a treatment liquid supply unit that supplies a treatment liquid to the surface of the substrate; a treatment film forming unit that cures or hardens the treatment liquid in contact with the surface of the substrate to form a treatment film; a stripping liquid supply unit that supplies a stripping liquid for stripping the treatment film formed on the surface of the substrate to the surface of the substrate; and a controller that controls the hydrophilization liquid supply unit, the treatment liquid supply unit, the treatment film forming unit, and the stripping liquid supply unit.

[0045] Moreover, the controller included in the substrate processing apparatus is programmed as follows: hydrophilize the surface of the substrate by supplying a hydrophilizing liquid from the hydrophilizing liquid supply unit to the surface of the substrate; supply a processing liquid from the processing liquid supply unit to the substrate whose surface has been hydrophilized; solidify or harden the processing liquid supplied to the surface of the substrate through the processing film forming unit to form a processing film on the surface of the substrate that holds the object to be removed existing on the surface of the substrate; supply a stripping liquid from the stripping liquid supply unit to the surface of the substrate to strip the processing film holding the object to be removed from the surface of the substrate; and partially dissolve the processing film with the stripping liquid to form a through-hole in the processing film.

[0046] According to this configuration, the same effects as those of the substrate processing method can be obtained.

[0047] One embodiment of the present invention provides a substrate processing apparatus including: a hydrophilizing liquid supply unit that supplies a hydrophilizing liquid for hydrophilizing the surface of the substrate to the surface of the substrate; a processing liquid supply unit that supplies a processing liquid to the surface of the substrate; a processing film forming unit that solidifies or hardens the processing liquid in contact with the surface of the substrate to form a processing film; a stripping liquid supply unit that supplies a stripping liquid for stripping the processing film formed on the surface of the substrate to the surface of the substrate; and a controller that controls the hydrophilizing liquid supply unit, the processing liquid supply unit, the processing film forming unit, and the stripping liquid supply unit; and the processing liquid contains a solvent and a solute, the solute has a highly soluble component and a low-soluble component whose solubility in the stripping liquid is lower than that of the highly soluble component, and the processing film has a highly soluble solid formed by the highly soluble component and a low-soluble solid formed by the low-soluble component.

[0048] Moreover, the controller included in the substrate processing apparatus is programmed as follows: hydrophilize the surface of the substrate by supplying a hydrophilizing liquid from the hydrophilizing liquid supply unit to the surface of the substrate; supply a processing liquid from the processing liquid supply unit to the surface of the substrate that has been hydrophilized; solidify or harden the processing liquid supplied to the surface of the substrate through the processing film forming unit to form a processing film on the surface of the substrate that holds the object to be removed existing on the surface of the substrate; and supply a stripping liquid from the stripping liquid supply unit to the surface of the substrate to dissolve the highly soluble solid in the stripping liquid and strip the processing film holding the object to be removed from the surface of the substrate.

[0049] According to this configuration, the same effects as those of the substrate processing method can be obtained.

[0050] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supply step of supplying a processing liquid to the surface of a substrate; a processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; a stripping and removal step of partially dissolving the processing film in the stripping liquid by supplying the stripping liquid to the surface of the substrate, stripping the processing film holding the object to be removed from the surface of the substrate, and discharging the stripped processing film out of the substrate; and a residue removal step of supplying a residue removal liquid to the surface of the substrate after the stripping and removal step to remove the residue of the processing film remaining on the surface of the substrate. Moreover, the stripping liquid is a mixed liquid of an organic solvent and water, and the residue removal liquid is an organic solvent composed of the same substance as the organic solvent in the mixed liquid.

[0051] According to this method, a processing film that holds an object to be removed is formed by solidifying or hardening the processing liquid supplied to the surface of the substrate. Then, a stripping liquid is supplied to the surface of the substrate. By supplying the stripping liquid, the processing film is partially dissolved, the processing film holding the object to be removed is stripped from the surface of the substrate, and the stripped processing film is discharged out of the substrate.

[0052] According to this method, the stripping liquid is a mixed liquid of an organic solvent and water. The processing film is more soluble in the organic solvent than in water. Therefore, the stripping liquid, which is a mixed liquid of an organic solvent and water, is less likely to dissolve the processing film than the organic solvent. Therefore, the stripping liquid causes the processing film to partially dissolve, forming gaps (spaces, paths) in the processing film.

[0053] The stripping liquid can pass through the gaps to reach the surface of the substrate. The stripping liquid reaching the surface of the substrate acts on the interface between the processing film and the substrate. Therefore, compared with the method of allowing the stripping liquid to penetrate into the processing film and reach the interface between the processing film and the substrate without forming gaps in the processing film, a large amount of the stripping liquid can quickly reach the interface between the processing film and the substrate.

[0054] Since the processing film is more soluble in the organic solvent than in water, the mixed liquid of the organic solvent and water is more likely to dissolve the processing film than water. Although the processing film partially dissolves to form gaps, the remaining part will maintain a solid state. Therefore, the surface of the part of the processing film that maintains a solid state can be moderately dissolved by the stripping liquid. Therefore, the processing film holding the object to be removed can be effectively stripped from the surface of the substrate and discharged from the substrate.

[0055] By continuously supplying the stripping liquid, the processing film is removed from the surface of the substrate. Sometimes, after the processing film is removed from the surface of the substrate, residues of the processing film still adhere to the surface of the substrate. In this case, the residues of the processing film are removed by the residue removing liquid. Thus, the surface of the substrate can be cleaned well.

[0056] According to this method, the residue removing liquid is an organic solvent composed of the same substance as the organic solvent in the mixed liquid. That is, the organic solvent in the mixed liquid used as the stripping liquid is the same organic compound as the organic solvent used as the residue removing liquid. Compared with the method in which the organic solvent in the mixed liquid used as the stripping liquid and the organic solvent used as the residue removing liquid are different substances, the types of liquids used can be reduced. Therefore, the cost required to remove the object to be removed from the substrate can be reduced.

[0057] In one embodiment of the present invention, the stripping and removing step includes a step of forming a through-hole in the processing film by partially dissolving the processing film in the stripping liquid.

[0058] According to this method, the stripping liquid forms a through-hole in the processing film. Therefore, the stripping liquid passes through the through-hole and reaches the surface of the substrate. The stripping liquid reaching the surface of the substrate acts on the interface between the portion of the processing film surrounding the through-hole and the substrate. Therefore, compared with the method in which the stripping liquid does not form a through-hole in the processing film but penetrates into the processing film to reach the interface between the processing film and the substrate, a large amount of the stripping liquid can quickly reach the interface between the processing film and the substrate.

[0059] In one embodiment of the present invention, the processing liquid contains a solvent and a solute dissolved in the solvent. The solute has a highly soluble component and a low-soluble component with lower solubility in the stripping liquid than the highly soluble component. The processing film forming step includes a step of forming the processing film having a highly soluble solid formed by the highly soluble component and a low-soluble solid formed by the low-soluble component. Moreover, the stripping and removing step includes a step of dissolving the highly soluble solid in the stripping liquid to strip the processing film in the state of holding the object to be removed from the surface of the substrate.

[0060] According to this method, the solubility of the highly soluble component in the stripping liquid is higher than the solubility of the low-soluble component in the stripping liquid. Therefore, the highly soluble solid formed by the highly soluble component is more easily dissolved in the stripping liquid than the low-soluble solid formed by the low-soluble component. Therefore, the highly soluble solid is dissolved by the stripping liquid to form a gap in the processing film. On the other hand, the low-soluble solid does not dissolve in the stripping liquid and maintains a solid state.

[0061] Therefore, it is possible to dissolve highly soluble solids in the stripping liquid and keep low-soluble solids undissolved in the stripping liquid to maintain a solid state. Therefore, the stripping liquid passes through the gaps formed by the dissolution of highly soluble solids and reaches the interface between the substrate and the low-soluble solids.

[0062] As a result, it is possible to hold the object to be removed with the low-soluble solids and allow the stripping liquid to act on the interface between the low-soluble solids and the substrate. Thus, it is possible to quickly strip the processing film from the substrate and effectively remove the object to be removed from the substrate.

[0063] In one embodiment of the present invention, the stripping exclusion step includes a stripping liquid introduction step of introducing the stripping liquid between the surface of the substrate and the processing film. Therefore, the stripping liquid can act on the interface between the processing film and the substrate, so that the processing film can be stripped from the surface of the substrate more efficiently.

[0064] In one embodiment of the present invention, the stripping exclusion step includes a hydrophilization step of hydrophilizing the surface of the substrate with the stripping liquid.

[0065] The higher the hydrophilicity of the upper surface of the substrate, the easier it is for the stripping liquid to act on the interface between the substrate and the processing film, so that the processing film can be effectively stripped from the surface of the substrate. Therefore, by using the stripping liquid to hydrophilize the surface of the substrate, the processing film can be effectively stripped.

[0066] In one embodiment of the present invention, the organic solvent is IPA, and the mass percentage concentration of IPA in the mixed liquid is 12% or more and 33% or less. If the mass percentage concentration of IPA in the mixed liquid is 12% or more and 33% or less, the surface of the processing film can be moderately dissolved. Therefore, the object to be removed will not detach from the processing film, and the processing film holding the object to be removed can be stripped from the surface of the substrate.

[0067] In one embodiment of the present invention, the substrate processing method further includes a pre-hydrophilization step of hydrophilizing the surface of the substrate before supplying a processing liquid to the surface of the substrate.

[0068] According to this method, before supplying the processing liquid to the surface of the substrate, the surface of the substrate has been hydrophilized. That is to say, the surface of the substrate has been pre-hydrophilized. Therefore, the processing film will be formed on the surface of the pre-hydrophilized substrate. Therefore, the processing film can be effectively stripped from the substrate by the stripping liquid.

[0069] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supply step of supplying a processing liquid to the surface of a substrate; a processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; a through-hole formation step of partially dissolving the processing film in the dissolving liquid by supplying the dissolving liquid to the surface of the substrate to form through-holes in the processing film; and a peeling step of supplying a peeling liquid to the surface of the substrate, whereby the peeling liquid passes through the through-holes to peel the processing film holding the object to be removed from the surface of the substrate.

[0070] According to this method, a processing film that holds an object to be removed is formed by solidifying or hardening the processing liquid supplied to the surface of the substrate. Then, a dissolving liquid is supplied to the surface of the substrate. Thereby, the processing film is partially dissolved to form through-holes in the processing film. Then, a peeling liquid is supplied to the surface of the substrate. Thereby, the peeling liquid passes through the through-holes to reach the interface between the substrate and the peeling liquid, and the processing film holding the object to be removed is peeled from the surface of the substrate by the peeling liquid.

[0071] Since through-holes are formed in the processing film by the dissolving liquid, the peeling liquid can pass through the through-holes to reach the surface of the substrate. The peeling liquid that reaches the surface of the substrate acts on the interface between the portion of the processing film surrounding the through-holes and the substrate. Therefore, compared with the method of making the peeling liquid pass through the inside of the processing film to reach the interface between the processing film and the substrate without forming through-holes in the processing film, a large amount of peeling liquid can reach the interface between the processing film and the substrate quickly.

[0072] Although the processing film is partially dissolved to form through-holes, the remaining portion will maintain a solid state. Therefore, the processing film holding the object to be removed can be effectively peeled from the surface of the substrate.

[0073] In addition, according to this method, the formation of through-holes and the peeling of the processing film are carried out by different liquids (the dissolving liquid and the peeling liquid). Therefore, the peeling liquid and the dissolving liquid can be selected from liquids suitable for their respective functions. That is to say, a liquid suitable for partial dissolution of the processing film can be selected as the dissolving liquid, and a liquid suitable for peeling of the processing film can be selected as the peeling liquid. Therefore, the dissolution of the processing film by the dissolving liquid can be inhibited, and the situation where the object to be removed detaches from the processing film can be inhibited. Therefore, the processing film holding the object to be removed can be effectively peeled.

[0074] In one embodiment of the present invention, the treatment liquid contains a solvent and a solute dissolved in the solvent. The solute has a highly soluble component and a poorly soluble component whose solubility in the solution is lower than that of the highly soluble component. The treatment film forming step includes a step of forming the treatment film, and the treatment film has a highly soluble solid formed from the highly soluble component and a poorly soluble solid formed from the poorly soluble component. Further, the through-hole forming step includes a step of dissolving the highly soluble solid in the solution to form the through-hole in the treatment film.

[0075] According to this method, the solubility of the highly soluble component in the solution is higher than that of the poorly soluble component in the solution. Therefore, the highly soluble solid formed from the highly soluble component is more easily dissolved in the solution than the poorly soluble solid formed from the poorly soluble component. Therefore, the highly soluble solid is dissolved by the solution, thereby forming a through-hole in the treatment film. On the other hand, the poorly soluble solid does not dissolve in the solution and remains in a solid state.

[0076] Therefore, it is possible to dissolve the highly soluble solid in the solution and keep the poorly soluble solid undissolved in the solution and in a solid state. Therefore, the stripping liquid passes through the through-hole formed by the dissolution of the highly soluble solid and reaches the interface between the substrate and the poorly soluble solid.

[0077] As a result, it is possible to hold the object to be removed with the poorly soluble solid and allow the stripping liquid to act on the interface between the poorly soluble solid and the substrate. Thereby, it is possible to quickly strip the treatment film from the substrate and effectively remove the object to be removed together with the treatment film from the substrate.

[0078] In one embodiment of the present invention, the stripping step includes a stripping liquid introduction step of introducing the stripping liquid between the surface of the substrate and the treatment film. Therefore, the stripping liquid can act on the interface between the treatment film and the substrate, so that the treatment film can be stripped from the surface of the substrate more efficiently.

[0079] In one embodiment of the present invention, the stripping liquid is a mixed liquid of an organic solvent and water. The treatment film is easily dissolved in the organic solvent but hardly dissolved in water. If the stripping liquid is a mixed liquid of an organic solvent and water, it is possible to maintain the holding of the object to be removed and dissolve only the surface of the treatment film to an extent that allows the treatment film to be stripped from the surface of the substrate. For example, when the organic solvent is IPA, if the mass percentage concentration of IPA in the mixed liquid is 12% or more and 33% or less, the surface of the treatment film can be moderately dissolved. Therefore, the object to be removed does not detach from the treatment film, and the treatment film holding the object to be removed can be stripped from the surface of the substrate.

[0080] In one embodiment of the present invention, the substrate processing method further includes: an exclusion step of continuously supplying the stripping liquid to the surface of the substrate even after stripping the processing film from the substrate, thereby excluding the processing film stripped from the surface of the substrate outside the substrate; and a residue removal step of supplying a residue removal liquid to the surface of the substrate after the exclusion step, thereby removing the residue of the processing film remaining on the surface of the substrate. Moreover, the residue removal liquid is an organic solvent composed of the same substance as the organic solvent in the mixed liquid.

[0081] According to this method, the processing film is removed from the surface of the substrate by continuously supplying the stripping liquid. Sometimes, after removing the processing film from the surface of the substrate, residues of the processing film still adhere to the surface of the substrate. In such a case, the residues of the processing film are removed by the residue removal liquid. Thus, the surface of the substrate can be cleaned well.

[0082] According to this method, the residue removal liquid is an organic solvent composed of the same substance as the organic solvent in the mixed liquid. That is, the organic solvent in the mixed liquid used as the stripping liquid and the organic solvent used as the residue removal liquid are the same organic compound. Compared with the case where the organic solvent in the mixed liquid used as the stripping liquid and the organic solvent used as the residue removal liquid are different, the types of liquids used can be reduced. Therefore, the cost required to remove the object to be removed from the substrate can be reduced.

[0083] In one embodiment of the present invention, the substrate processing method further includes: an exclusion step of continuously supplying the stripping liquid to the surface of the substrate even after stripping the processing film from the substrate, thereby excluding the processing film stripped from the surface of the substrate outside the substrate; and a residue removal step of supplying a residue removal liquid to the surface of the substrate after the exclusion step, thereby removing the residue of the processing film remaining on the surface of the substrate.

[0084] According to this method, the processing film is excluded outside the substrate by continuously supplying the stripping liquid. Sometimes, after removing the processing film from the surface of the substrate, residues of the processing film still adhere to the surface of the substrate. In such a case, the residues of the processing film are removed by the residue removal liquid. Thus, the surface of the substrate can be cleaned well.

[0085] In one embodiment of the present invention, the stripping step includes a hydrophilicity step of hydrophilizing the surface of the substrate with the stripping liquid.

[0086] According to this method, the surface of the substrate is hydrophilized by the stripping liquid. Therefore, while the portion of the surface of the substrate exposed due to the formation of the through-holes is hydrophilized by the stripping liquid, the stripping liquid acts on the interface between the portion of the treatment film surrounding the through-holes and the substrate. Therefore, the treatment film holding the object to be removed can be effectively stripped from the surface of the substrate.

[0087] In one embodiment of the present invention, the substrate treatment method further includes a hydrophilization step of supplying a hydrophilizing liquid to the surface of the substrate before the stripping step, whereby the hydrophilizing liquid passes through the through-holes to hydrophilize the surface of the substrate.

[0088] According to this method, a hydrophilizing liquid is supplied to the surface of the substrate. Since the hydrophilizing liquid passes through the through-holes to reach the surface of the substrate, the portion of the surface of the substrate exposed due to the formation of the through-holes is hydrophilized.

[0089] The higher the hydrophilicity of the upper surface of the substrate, the easier it is for the stripping liquid to act on the interface between the substrate and the treatment film, so that the treatment film can be effectively stripped from the surface of the substrate. Therefore, if the portion of the surface of the substrate exposed due to the formation of the through-holes is hydrophilized before supplying the stripping liquid to the surface of the substrate, the stripping liquid can act on the interface between the portion of the treatment film surrounding the through-holes and the substrate, and the treatment film can be effectively stripped.

[0090] In one embodiment of the present invention, the hydrophilizing liquid is an oxidizing liquid capable of oxidizing the surface of the substrate. When an oxidizing liquid is used as the hydrophilizing liquid, a portion (surface layer) near the surface of the substrate is oxidized. By oxidizing the surface layer of the substrate, oxygen atoms bond to the substances exposed from the surface of the substrate. By the bonding of oxygen atoms to the substances exposed from the surface of the substrate, the surface of the substrate is hydrophilized.

[0091] In one embodiment of the present invention, the dissolving liquid, the hydrophilizing liquid, and the stripping liquid contain different substances from each other.

[0092] In one embodiment of the present invention, the stripping liquid and the dissolving liquid contain different substances from each other.

[0093] In one embodiment of the present invention, the dissolving liquid is an alkaline liquid.

[0094] In one embodiment of the present invention, the substrate treatment method further includes a pre-hydrophilization step of hydrophilizing the surface of the substrate before supplying a treatment liquid to the surface of the substrate.

[0095] According to this method, the surface of the substrate is hydrophilized in advance, that is, before supplying the treatment liquid to the surface of the substrate. Therefore, the treatment film is formed on the hydrophilized surface of the substrate. Therefore, the treatment film can be effectively stripped from the substrate by the stripping liquid.

[0096] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supply step of supplying a processing liquid to the surface of a substrate; a processing film formation step of curing or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; a dissolution step of partially dissolving the processing film in the dissolution liquid by supplying the dissolution liquid to the surface of the substrate; and a peeling step of supplying a peeling liquid to the surface of the substrate after the dissolution step, thereby peeling the processing film holding the object to be removed from the surface of the substrate by the peeling liquid; and the processing liquid contains a solvent and a solute dissolved in the solvent, the solute has a highly soluble component and a low-soluble component whose solubility in the dissolution liquid is lower than that of the highly soluble component, the processing film formation step includes a step of forming the processing film, the processing film has a highly soluble solid formed by the highly soluble component and a low-soluble solid formed by the low-soluble component, and the dissolution step includes a step of dissolving the highly soluble solid in the dissolution liquid.

[0097] According to this method, by curing or hardening the processing liquid supplied to the surface of the substrate, a processing film that holds the object to be removed is formed. Then, the dissolution liquid is supplied to the surface of the substrate. As a result, the processing film is partially dissolved to form a gap in the processing film. Then, the peeling liquid is supplied to the surface of the substrate. As a result, the peeling liquid passes through the gap in the processing film to reach the interface between the substrate and the peeling liquid, and the processing film holding the object to be removed is peeled from the surface of the substrate by the peeling liquid.

[0098] The solubility of the highly soluble component in the dissolution liquid is higher than that of the low-soluble component in the dissolution liquid. Therefore, the highly soluble solid formed by the highly soluble component is more easily dissolved in the dissolution liquid than the low-soluble solid formed by the low-soluble component. Therefore, the highly soluble solid is dissolved by the dissolution liquid to form a gap in the processing film. On the other hand, the low-soluble solid does not dissolve in the peeling liquid and maintains a solid state.

[0099] Therefore, both the highly soluble solid can be dissolved in the dissolution liquid and the low-soluble solid can be maintained in a solid state without dissolving in the dissolution liquid. Therefore, the peeling liquid passes through the gap formed by the dissolution of the highly soluble solid and reaches the interface between the substrate and the low-soluble solid.

[0100] As a result, both the object to be removed can be held by the low-soluble solid and the peeling liquid can act on the interface between the low-soluble solid and the substrate. Thus, the processing film can be quickly peeled from the substrate, and the object to be removed can be effectively removed from the substrate together with the processing film.

[0101] In addition, according to this method, the dissolution of highly soluble solids and the stripping of the treatment film are carried out using different liquids (dissolution liquid and stripping liquid). Therefore, the stripping liquid and the dissolution liquid can be selected from liquids suitable for their respective functions. That is, a liquid suitable for partial dissolution of highly soluble solids can be selected as the dissolution liquid, and a liquid suitable for stripping the treatment film can be selected as the stripping liquid.

[0102] For example, if a liquid in which the difference in solubility between highly soluble solids and low-soluble solids is greater than that of the stripping liquid is used as the dissolution liquid, the loss of the dissolution liquid to the low-soluble solids can be suppressed, and the detachment of the object to be removed from the low-soluble solids can be suppressed. Therefore, the treatment film maintaining the state of the object to be removed can be effectively stripped.

[0103] One embodiment of the present invention provides a substrate processing apparatus, comprising: a treatment liquid supply unit that supplies a treatment liquid to the surface of a substrate; a treatment film forming unit that cures or hardens the treatment liquid in contact with the surface of the substrate to form a treatment film; a stripping liquid supply unit that supplies a stripping liquid for stripping the treatment film formed on the surface of the substrate to the surface of the substrate; a residue removal liquid supply unit that supplies a residue removal liquid for removing the residue of the treatment film present on the surface of the substrate to the surface of the substrate; and a controller that controls the treatment liquid supply unit, the treatment film forming unit, the stripping liquid supply unit, and the residue removal liquid supply unit.

[0104] Moreover, the controller is programmed as follows: supply a treatment liquid from the treatment liquid supply unit to the substrate; through the treatment film forming unit, cure or harden the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that holds the object to be removed present on the surface of the substrate; by supplying the stripping liquid from the stripping liquid supply unit to the substrate, partially dissolve the treatment film in the stripping liquid, strip the treatment film maintaining the state of the object to be removed from the surface of the substrate, and discharge the stripped treatment film outside the substrate; and by supplying a residue removal liquid from the residue removal liquid supply unit to the surface of the substrate, remove the residue of the treatment film remaining on the surface of the substrate. Further, the stripping liquid is a mixed liquid of an organic solvent and water, and the residue removal liquid is an organic solvent composed of the same substance as the organic solvent in the mixed liquid.

[0105] According to this apparatus, the same effects as those of the substrate processing method can be obtained.

[0106] One embodiment of the present invention provides a substrate processing apparatus, comprising: a processing liquid supply unit configured to supply a processing liquid to a surface of a substrate; a processing film forming unit configured to solidify or harden the processing liquid in contact with the surface of the substrate to form a processing film; a dissolving liquid supply unit configured to supply a dissolving liquid to the surface of the substrate to partially dissolve the processing film formed on the surface of the substrate; a stripping liquid supply unit configured to supply a stripping liquid to the surface of the substrate to strip the processing film formed on the surface of the substrate; and a controller configured to control the processing liquid supply unit, the processing film forming unit, the dissolving liquid supply unit, and the stripping liquid supply unit.

[0107] Moreover, the controller is programmed as follows: supply a processing liquid from the processing liquid supply unit to the substrate; solidify or harden the processing liquid supplied to the surface of the substrate through the processing film forming unit to form a processing film on the surface of the substrate that holds an object to be removed existing on the surface of the substrate; partially dissolve the processing film in the dissolving liquid by supplying the dissolving liquid from the dissolving liquid supply unit to the substrate to form a through-hole in the processing film; and supply a stripping liquid from the stripping liquid supply unit to the substrate, whereby the stripping liquid passes through the through-hole to strip the processing film holding the object to be removed from the surface of the substrate.

[0108] According to this apparatus, the same effect as the substrate processing method can be obtained.

[0109] One embodiment of the present invention provides a substrate processing apparatus, comprising: a processing liquid supply unit configured to supply a processing liquid to a surface of a substrate; a processing film forming unit configured to solidify or harden the processing liquid in contact with the surface of the substrate to form a processing film; a dissolving liquid supply unit configured to supply a dissolving liquid to the surface of the substrate to partially dissolve the processing film formed on the surface of the substrate; a stripping liquid supply unit configured to supply a stripping liquid to the surface of the substrate to strip the processing film formed on the surface of the substrate; and a controller configured to control the processing liquid supply unit, the processing film forming unit, the dissolving liquid supply unit, and the stripping liquid supply unit; and the processing liquid contains a solvent and a solute dissolved in the solvent, and the solute has a highly soluble component and a low soluble component having a lower solubility in the stripping liquid supplied from the stripping liquid supply unit than the highly soluble component.

[0110] Furthermore, the controller included in the substrate processing apparatus is programmed as follows: supply a processing liquid from the processing liquid supply unit to the substrate; through the processing film forming unit, solidify or harden the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate, the processing film having a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component to hold the object to be removed existing on the surface of the substrate; dissolve the highly soluble solid of the processing film in the dissolution liquid by supplying the dissolution liquid from the dissolution liquid supply unit to the substrate; and supply a stripping liquid from the stripping liquid supply unit to the substrate to strip the processing film holding the object to be removed from the surface of the substrate.

[0111] According to this apparatus, the same effect as the substrate processing method can be obtained.

[0112] The objects, features, and effects of the present invention, or other objects, features, and effects, are clarified by the description of the embodiments described below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0113] Figure 1 It is a top view schematic diagram showing the layout of the substrate processing apparatus according to the first embodiment of the present invention.

[0114] Figure 2 It is a partial cross-sectional schematic diagram showing the schematic configuration of the processing unit included in the substrate processing apparatus.

[0115] Figure 3 It is a schematic diagram of a droplet of pure water on a substrate and its surroundings.

[0116] Figure 4A It is a schematic diagram for explaining the hydrophilization of the surface of the substrate by an organic solvent.

[0117] Figure 4B It is a schematic diagram for explaining the hydrophilization of the surface of the substrate by an oxidizing liquid.

[0118] Figure 5 It is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus.

[0119] Figure 6 It is an example of the structure of the surface layer of the substrate to be processed.

[0120] Figure 7 It is another example of the structure of the surface layer of the substrate to be processed.

[0121] Figure 8 It is a flowchart for explaining an example of processing a substrate by the substrate processing apparatus.

[0122] Fig.9A It is a schematic diagram for explaining the hydrophilic treatment step (step S2) of the substrate treatment.

[0123] Fig. 9B It is a schematic diagram for explaining the first cleaning step (step S3) of the substrate treatment.

[0124] Fig. 9C It is a schematic diagram for explaining the replacement step (step S4) of the substrate treatment.

[0125] Fig.9D It is a schematic diagram for explaining the treatment liquid supply step (step S5) of the substrate treatment.

[0126] Fig.9E It is a schematic diagram for explaining the treatment film formation step (step S6) of the substrate treatment.

[0127] Fig.9F It is a schematic diagram for explaining the treatment film formation step (step S6) of the substrate treatment.

[0128] Figure 9G It is a schematic diagram for explaining the stripping step (step S7) of the substrate treatment.

[0129] Figure 9H It is a schematic diagram for explaining the second cleaning step (step S8) of the substrate treatment.

[0130] Fig.9I It is a schematic diagram for explaining the residue removal step (step S9) of the substrate treatment.

[0131] Fig. 10A It is a schematic diagram for explaining the situation of stripping the treatment film from the surface of the substrate.

[0132] Fig. 10B It is a schematic diagram for explaining the situation of stripping the treatment film from the surface of the substrate.

[0133] Fig. 10C It is a schematic diagram for explaining the situation of stripping the treatment film from the surface of the substrate.

[0134] Fig.11 It is a flowchart for explaining another example of substrate treatment by the substrate treatment apparatus.

[0135] Fig. 12A It is a schematic diagram for explaining the sequence of measuring the contact angle of pure water on the surface of the experimental substrate.

[0136] Fig. 12BIt is a schematic diagram for explaining the order of peeling the processing film from the experimental substrate.

[0137] Fig.13 It is a table showing the contact angle of pure water on the surface of the experimental substrate and whether the processing film can be peeled off by the peeling liquid.

[0138] Fig.14 It is a schematic diagram for explaining the order of measuring the contact angle of pure water on the surface of the processing film.

[0139] Fig.15 It is a table showing the contact angle of pure water on the surface of the processing film.

[0140] Fig.16 It is a partial cross-sectional schematic diagram showing the schematic configuration of the processing unit included in the substrate processing apparatus according to the second embodiment of the present invention.

[0141] Fig.17 It is a schematic diagram for explaining the hydrophilization of the surface of the substrate by the peeling liquid.

[0142] Fig.18 It is a flowchart for explaining an example of processing a substrate by the substrate processing apparatus according to the second embodiment.

[0143] Fig.19A It is a schematic diagram for explaining the case of the processing liquid supply step (step S22) of the substrate processing according to the second embodiment.

[0144] Fig.19B It is a schematic diagram for explaining the case of the processing film formation step (step S23) of the substrate processing according to the second embodiment.

[0145] Fig.19C It is a schematic diagram for explaining the case of the processing film formation step (step S23) of the substrate processing according to the second embodiment.

[0146] Fig.19D It is a schematic diagram for explaining the case of the peeling liquid supply step (step S24) of the substrate processing according to the second embodiment.

[0147] Fig.19E It is a schematic diagram for explaining the case of the cleaning step (step S25) of the substrate processing according to the second embodiment.

[0148] Fig.19F It is a schematic diagram for explaining the case of the residue removal liquid supply step (step S26) of the substrate processing according to the second embodiment.

[0149] Fig. 20A It is a schematic diagram for explaining the case of peeling the processing film from the surface of the substrate.

[0150] Fig. 20B It is a schematic diagram for explaining the situation of peeling the processing film from the surface of the substrate.

[0151] Fig. 20C It is a schematic diagram for explaining the situation of peeling the processing film from the surface of the substrate.

[0152] Fig.21 It is a schematic diagram for explaining the situation of the stripping liquid supply step (step S24) of substrate processing in a variation of the substrate processing apparatus according to the second embodiment.

[0153] Fig. 22 It is a partial cross-sectional schematic diagram showing the schematic configuration of the processing unit included in the substrate processing apparatus according to the third embodiment of the present invention.

[0154] Fig.23 It is a flowchart for explaining an example of substrate processing according to the third embodiment.

[0155] Fig.24A It is a schematic diagram for explaining the situation of the dissolution liquid supply step (step S30) of substrate processing according to the third embodiment.

[0156] Fig. 24B It is a schematic diagram for explaining the situation of the cleaning step (step S31) of substrate processing according to the third embodiment.

[0157] Fig.25A It is a schematic diagram for explaining the situation of peeling the processing film from the surface of the substrate in the substrate processing according to the third embodiment.

[0158] Fig.25B It is a schematic diagram for explaining the situation of peeling the processing film from the surface of the substrate in the substrate processing according to the third embodiment.

[0159] Fig.25C It is a schematic diagram for explaining the situation of peeling the processing film from the surface of the substrate in the substrate processing according to the third embodiment.

[0160] Fig.25D It is a schematic diagram for explaining the situation of peeling the processing film from the surface of the substrate in the substrate processing according to the third embodiment.

[0161] Fig.26 It is a partial cross-sectional schematic diagram showing the schematic configuration of the processing unit included in the substrate processing apparatus according to the fourth embodiment of the present invention.

[0162] Fig. 27 It is a schematic diagram for explaining the situation of hydrophilizing the surface of the substrate with a hydrophilizing liquid.

[0163] Fig.28It is a flowchart showing an example of substrate processing in the fourth embodiment.

[0164] Fig.29A It is a schematic diagram showing the case of the hydrophilic liquid supply step (step S40) of the substrate processing in the fourth embodiment.

[0165] Fig.29B It is a schematic diagram showing the case of the cleaning step (step S41) of the substrate processing in the fourth embodiment.

[0166] Fig. 30A It is a schematic diagram showing the case of peeling the processing film from the surface of the substrate in the substrate processing of the fourth embodiment.

[0167] Fig. 30B It is a schematic diagram showing the case of peeling the processing film from the surface of the substrate in the substrate processing of the fourth embodiment.

[0168] Fig. 30C It is a schematic diagram showing the case of peeling the processing film from the surface of the substrate in the substrate processing of the fourth embodiment.

[0169] Fig.30D It is a schematic diagram showing the case of peeling the processing film from the surface of the substrate in the substrate processing of the fourth embodiment.

[0170] Fig.30E It is a schematic diagram showing the case of peeling the processing film from the surface of the substrate in the substrate processing of the fourth embodiment.

[0171] Fig.31 It is a flowchart showing another example of substrate processing in the fourth embodiment.

[0172] Fig.32A It is a schematic diagram showing the case of the pre-hydrophilic step (step S50) performed in another example of the substrate processing in the fourth embodiment.

[0173] Fig.32B It is a schematic diagram showing the case of the cleaning step (step S51) performed in another example of the substrate processing in the fourth embodiment.

[0174] Fig.32C It is a schematic diagram showing the case of the replacement step (step S52) performed in another example of the substrate processing in the fourth embodiment.

[0175] Fig.33 It is a graph showing the relationship between the concentration of IPA in diluted IPA and the contact angle of diluted IPA on the surface of the experimental substrate.

[0176] Fig.34 This is a microscopic image showing the surface of a test substrate when diluted IPA is dropped onto a test substrate with a treatment film formed on its surface. Detailed implementation mode

[0177] <Configuration of the substrate processing apparatus according to the first embodiment>

[0178] Figure 1 This is a top view schematic diagram showing the layout of a substrate processing apparatus 1 according to an embodiment of the present invention.

[0179] The substrate processing apparatus 1 is a single - wafer type apparatus for processing substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a disc - shaped substrate.

[0180] As the substrate W, a substrate having at least one of Si (silicon), SiN (silicon nitride), SiO2 (silicon oxide), SiGe (silicon germanide), Ge (germanium), SiCN (silicon carbonitride), W (tungsten), TiN (titanium nitride), Co (cobalt), Cu (copper), Ru (ruthenium), and a - C (amorphous carbon) exposed on its surface can be used. That is, the surface of the substrate W may expose only one of the above - mentioned substances or may expose a plurality of the above - mentioned substances.

[0181] The substrate processing apparatus 1 includes: a plurality of processing units 2 for processing the substrate W using a fluid; a load port LP for placing and accommodating a carrier C carrying a plurality of substrates W to be processed by the processing units 2; transfer robots IR and CR for transferring the substrate W between the load port LP and the processing units 2; and a controller 3 for controlling the substrate processing apparatus 1.

[0182] The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing units 2. The plurality of processing units 2 have, for example, the same configuration. The processing fluids supplied to the substrate W in the processing unit 2 include a hydrophilic liquid, a cleaning liquid, a replacement liquid, a processing liquid, a stripping liquid, a residue removal liquid, a dissolving liquid, a heat medium, an inert gas (gas), etc., and the details will be described below.

[0183] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and the substrate W is processed in the processing cup 7. In the chamber 4, an entrance / exit (not shown) for the transfer robot CR to carry the substrate W in or out is formed. The chamber 4 includes a shutter unit (not shown) for opening and closing the entrance / exit.

[0184] Figure 2It is a schematic diagram for explaining the configuration example of the processing unit 2. The processing unit 2 includes a rotary chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11, a central nozzle 12, and a bottom nozzle 13.

[0185] The rotary chuck 5 is an example of a substrate holding and rotating unit that horizontally holds the substrate W and rotates the substrate W around the rotation axis A1 (vertical axis). The rotation axis A1 is a vertical straight line passing through the central portion of the substrate W. The rotary chuck 5 includes a plurality of chuck pins 20, a rotary base 21, a rotary shaft 22, and a rotary motor 23.

[0186] The rotary base 21 has a disc shape along the horizontal direction. On the upper surface of the rotary base 21, a plurality of chuck pins 20 for holding the periphery of the substrate W are arranged at intervals along the circumferential direction of the rotary base 21. The rotary base 21 and the plurality of chuck pins 20 constitute a substrate holding unit for horizontally holding the substrate W. The substrate holding unit is also called a substrate holder.

[0187] The rotary shaft 22 extends in the vertical direction along the rotation axis A1. The upper end portion of the rotary shaft 22 is connected to the center of the lower surface of the rotary base 21. The rotary motor 23 applies a rotational force to the rotary shaft 22. By rotating the rotary shaft 22 using the rotary motor 23, the rotary base 21 rotates. Thereby, the substrate W rotates around the rotation axis A1. The rotary motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

[0188] The rotary chuck 5 is not limited to a clamping type chuck that brings the plurality of chuck pins 20 into contact with the peripheral end surface of the substrate W, and can also be a vacuum type chuck that horizontally holds the substrate W by adsorbing the lower surface of the substrate W to the upper surface of the rotary base 21.

[0189] The opposing member 6 faces the substrate W held by the rotary chuck 5 from above. The opposing member 6 is formed in a disc shape, and the disc shape has a diameter approximately the same as that of the substrate W or a diameter larger than that of the substrate W. The opposing member 6 has an opposing surface 6a that faces the upper surface (upper side surface) of the substrate W. The opposing surface 6a is located above the rotary chuck 5 and is disposed substantially along the horizontal plane.

[0190] A hollow shaft 60 is fixed to the opposite side of the opposing surface 6a of the opposing member 6. A communication hole 6b that penetrates the opposing member 6 vertically is formed in a portion that coincides with the rotation axis A1 when the opposing member 6 is viewed from above. The communication hole 6b communicates with the internal space 60a of the hollow shaft 60.

[0191] The opposing member 6 blocks the atmosphere in the space between the opposing surface 6a 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.

[0192] The processing unit 2 further includes: an opposing member lifting unit 61 that drives the lifting of the opposing member 6; and an opposing member rotating unit 62 that rotates the opposing member 6 about the rotation axis A1.

[0193] The opposing member lifting unit 61 can move the opposing member 6 to any position (height) between the lower position and the upper position in the vertical direction. The lower position refers to the position where the opposing surface 6a is closest to the substrate W within the movable range of the opposing member 6. The upper position refers to the position where the opposing surface 6a is farthest from the substrate W within the movable range of the opposing member 6. When the opposing member 6 is in the upper position, the transfer robot CR can approach the rotary chuck 5 to load and unload the substrate W.

[0194] The opposing member lifting unit 61 includes, for example, a ball screw mechanism (not shown) connected to a support member (not shown) that supports the hollow shaft 60, and an electric motor (not shown) that applies a driving force to the ball screw mechanism. The opposing member lifting unit 61 is also referred to as an opposing member lifter (blocking plate lifter). The opposing member rotating unit 62 includes, for example, a motor (not shown) that rotates the hollow shaft 60.

[0195] The processing cup 7 includes: a plurality of guards 71 that block the liquid flying outward from the substrate W held by the rotary chuck 5; a plurality of cup holders 72 that catch the liquid guided downward by the plurality of guards 71; and a cylindrical outer wall member 73 that surrounds the plurality of guards 71 and the plurality of cup holders 72.

[0196] In this embodiment, an example is given in which two guards 71 (the first guard 71A and the second guard 71B) and two cup holders 72 (the first cup holder 72A and the second cup holder 72B) are provided.

[0197] The first cup holder 72A and the second cup holder 72B each have the form of an upwardly open annular groove.

[0198] The first guard 71A is arranged to surround the rotary base 21. The second guard 71B is arranged outside the first guard 71A and surrounds the rotary base 21.

[0199] The first guard 71A and the second guard 71B each have a substantially cylindrical shape. The upper end portions of the respective guards 71 are inclined inwardly toward the rotary base 21.

[0200] The first cup holder 72A catches the liquid guided downward by the first guard 71A. The second cup holder 72B is integrated with the first guard 71A and catches the liquid guided downward by the second guard 71B.

[0201] The processing unit 2 includes a shutter lifting unit 74 that lifts and lowers the first shutter 71A and the second shutter 71B in the vertical direction respectively. The shutter lifting unit 74 lifts and lowers the first shutter 71A between the lower position and the upper position. The shutter lifting unit 74 lifts and lowers the second shutter 71B between the lower position and the upper position.

[0202] When both the first shutter 71A and the second shutter 71B are in the upper position, the liquid scattered from the substrate W is blocked by the first shutter 71A. When the first shutter 71A is in the lower position and the second shutter 71B is in the upper position, the liquid scattered from the substrate W is blocked by the second shutter 71B. When both the first shutter 71A and the second shutter 71B are in the lower position, the transfer robot CR can approach the rotary chuck 5 to carry in and out the substrate W.

[0203] The shutter lifting unit 74 includes, for example, a first ball screw mechanism (not shown) connected to the first shutter 71A, a first motor (not shown) that applies a driving force to the first ball screw mechanism, a second ball screw mechanism (not shown) connected to the second shutter 71B, and a second motor (not shown) that applies a driving force to the second ball screw mechanism. The shutter lifting unit 74 is also called a shutter lifter.

[0204] The first moving nozzle 9 is an example of a hydrophilic liquid nozzle (hydrophilic liquid supply unit) that supplies (ejects) a hydrophilic liquid to the upper surface of the substrate W held by the rotary chuck 5.

[0205] The first moving nozzle 9 moves in the horizontal direction and the vertical direction through the first nozzle moving unit 35. In the horizontal direction, the first moving nozzle 9 can move between the center position and the initial position (retracted position). When the first moving nozzle 9 is located at the center position, it faces the central region of the upper surface of the substrate W. The central region of the upper surface of the substrate W refers to the region on the upper surface of the substrate W that includes the rotation center of the substrate W and its surroundings.

[0206] When the first moving nozzle 9 is located at the initial position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a top view. By moving in the vertical direction, the first moving nozzle 9 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W.

[0207] The first nozzle moving unit 35 includes, for example, an arm (not shown) connected to the first moving nozzle 9 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending along the vertical direction, and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0208] The rotation axis drive unit swings the arm by rotating the rotation axis about a vertical rotation axis. Further, the rotation axis drive unit raises and lowers the arm by raising and lowering the rotation axis in the vertical direction. As the arm swings and moves up and down, the first moving nozzle 9 moves in the horizontal and vertical directions.

[0209] The first moving nozzle 9 is connected to a hydrophilic liquid pipe 40 that guides the hydrophilic liquid. After opening the hydrophilic liquid valve 50 inserted in the hydrophilic liquid pipe 40, the hydrophilic liquid is continuously sprayed downward from the first moving nozzle 9. If the hydrophilic liquid valve 50 is opened when the first moving nozzle 9 is in the central position, the hydrophilic liquid is supplied to the central region of the upper surface of the substrate W.

[0210] The hydrophilic liquid ejected from the first moving nozzle 9 is, for example, an oxidizing liquid such as hydrofluoric acid (HF, DHF), an ammonia-hydrogen peroxide water mixture (SC1), and a sulfuric acid-hydrogen peroxide water mixture (SPM); an organic solvent such as isopropyl alcohol (IPA); and a first hydrophilic liquid such as hydrochloric acid (HCl). The hydrophilic liquid is a liquid used to hydrophilize (improve hydrophilicity) the surface of the substrate W.

[0211] The oxidizing liquid is a liquid containing a substance with oxidizing power (oxidizing agent). For example, SC1 contains hydrogen peroxide as an oxidizing agent, hydrofluoric acid contains hydrogen fluoride as an oxidizing agent, and SPM contains persulfuric acid as an oxidizing agent.

[0212] Hydrophilicity refers to the affinity for water. Hydrophilicity is also called wettability. As an index of hydrophilicity, the contact angle can be cited. The contact angle is an angle obtained by numericalizing the bulge (height of the liquid) of a liquid droplet formed after dropping a liquid onto a certain solid. Specifically, the contact angle is the angle formed between the liquid surface and the surface of the solid when observing the liquid attached to the surface of the solid horizontally. The larger the contact angle, the lower the wettability of the solid surface, and the smaller the contact angle, the higher the wettability of the solid surface.

[0213] Figure 3 It is a schematic diagram of a pure water droplet on the substrate W and its surroundings. As Figure 3 shown, the contact angle θ of pure water on the surface of the substrate W is preferably greater than 0° and less than 41.7°. In this embodiment, DIW is used as the pure water. If the contact angle of pure water on the surface of the substrate W is greater than 0° and less than 41.7°, it is easy to peel the treatment film (to be described below) from the surface of the substrate W with a stripping liquid (to be described below). The contact angle θ of pure water on the surface of the substrate W is more preferably greater than 0° and less than or equal to 36.0°. The contact angle θ of pure water on the surface of the substrate W is further preferably greater than 0° and less than or equal to 32.7°.

[0214] Next, the case of hydrophilizing the surface of the substrate W will be described. Figure 4A and Figure 4B This is a schematic diagram for explaining the hydrophilization of the surface of substrate W by the first hydrophilizing liquid.

[0215] When an organic solvent such as IPA is used as the first hydrophilizing liquid, the surface of substrate W is hydrophilized by removing the hydrophobic organic matter 170 attached to the surface of substrate W. Specifically, as Figure 4A shown, the hydrophobic organic matter 170 present on the surface of substrate W is dissolved in the organic solvent, thereby hydrophilizing the surface of substrate W. Therefore, there is a case where the organic matter 170A that is difficult to dissolve in the first hydrophilizing liquid remains on the surface of substrate W. Therefore, when hydrophilization is achieved by an organic solvent, it is affected by the type of organic matter 170 present on the surface of substrate W.

[0216] The organic matter is only a part of the object to be removed present on the surface of substrate W. Even if the organic matter is removed by an organic solvent, the removal of the object to be removed is not sufficient. Therefore, when the surface of substrate W is hydrophilized by an organic solvent, as described below, it is still necessary to remove the object to be removed by peeling the treatment film.

[0217] On the other hand, when an oxidizing liquid such as hydrofluoric acid or SC1 is used as the first hydrophilizing liquid, as Figure 4B shown, the surface of substrate W is oxidized to form an oxide film 171 on the surface of substrate W. Since the surface of substrate W is oxidized, oxygen atoms bond to the substances exposed from the surface of substrate W. Since oxygen atoms bond to the substances exposed from the surface of substrate W, the hydrophilicity of the surface of substrate W is improved.

[0218] When an oxidizing liquid is used as the first hydrophilizing liquid, the surface of substrate W can be hydrophilized regardless of the presence of organic matter 170. That is, even if there is organic matter 170A that is difficult to dissolve in the organic solvent on the surface of substrate W, the surface of substrate W can be hydrophilized. Therefore, using an oxidizing liquid as the first hydrophilizing liquid can improve the hydrophilicity of the surface of substrate W more efficiently than using an organic solvent as the first hydrophilizing liquid.

[0219] A substrate W having a surface exposing at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C can be hydrophilized by the first hydrophilizing liquid. In particular, a substrate W having a surface exposing at least any one of Si, SiN, SiO2, W, TiN, Co, Cu, Ru, and a-C is more easily hydrophilized by the first hydrophilizing liquid, and a substrate W having a surface exposing any one of Si, SiN, SiO2, W, TiN, Co, and Cu is even more easily hydrophilized by the first hydrophilizing liquid.

[0220] Refer to again Figure 2 , the second moving nozzle 10 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (ejects) a processing liquid to the upper surface of the substrate W held by the rotating chuck 5.

[0221] The second moving nozzle 10 moves in the horizontal and vertical directions by the second nozzle moving unit 36. In the horizontal direction, the second moving nozzle 10 can move between the center position and the initial position (retracted position). When the second moving nozzle 10 is located at the center position, it faces the central region of the upper surface of the substrate W.

[0222] When the second moving nozzle 10 is located at the initial position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a top view. By moving in the vertical direction, the second moving nozzle 10 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W.

[0223] The second nozzle moving unit 36 has the same configuration as the first nozzle moving unit 35. That is, the second nozzle moving unit 36 may also include an arm (not shown) connected to the second moving nozzle 10 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending along the vertical direction, and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0224] The second moving nozzle 10 is connected to a processing liquid pipe 44 that guides the processing liquid. After opening the processing liquid valve 54 inserted in the processing liquid pipe 44, the processing liquid is ejected downward from the second moving nozzle 10 in a continuous flow. If the processing liquid valve 54 is opened when the second moving nozzle 10 is located at the center position, the processing liquid is supplied to the central region of the upper surface of the substrate W.

[0225] The processing liquid contains a solute and a solvent. The processing liquid solidifies or hardens by at least a part of the solvent contained in the processing liquid volatilizing (evaporating). The processing liquid forms a solid processing film that holds the removal objects such as fine particles present on the substrate W by solidifying or hardening on the substrate W.

[0226] Here, the so-called "solidification" means, for example, that as the solvent volatilizes, the solute condenses due to the forces acting between molecules or atoms, etc. The so-called "hardening" means, for example, that the solute condenses due to chemical changes such as polymerization or crosslinking. Therefore, the so-called "solidification or hardening" means that the solute "condenses" due to various factors.

[0227] The processing liquid contains a low solubility component and a high solubility component as solutes.

[0228] The processing liquid ejected from the second moving nozzle 10 may also contain an anti-corrosion component. The anti-corrosion component is, for example, BTA (benzotriazole), and the relevant details will be described below.

[0229] As the low-solubility component and the high-solubility component, substances with different solubilities in the following stripping liquid can be used. The low-solubility component is, for example, phenol formaldehyde. The high-solubility component is, for example, 2,2-bis(4-hydroxyphenyl)propane.

[0230] The solvent contained in the treatment liquid only needs to be a liquid that can dissolve the low-solubility component and the high-solubility component. The solvent contained in the treatment liquid is preferably a liquid that is compatible (miscible) with the stripping liquid. By compatibility is meant the property that two liquids are mutually soluble and mix.

[0231] The treatment film is mainly composed of the low-solubility component in a solid state and the high-solubility component in a solid state. The treatment film may also contain a residual solvent. Details of each component (solvent, low-solubility component, high-solubility component, and anti-corrosion component) contained in the treatment liquid will be described below.

[0232] If the contact angle of pure water on the treatment film is greater than 52° and less than 61°, then the following stripping liquid can act sufficiently on the interface between the substrate W and the treatment film. If the following treatment liquid is used, a treatment film with a contact angle of pure water greater than 52° and less than 61° can be formed.

[0233] The third moving nozzle 11 is an example of a stripping liquid nozzle (stripping liquid supply unit) that supplies (ejects) a stripping liquid such as ammonia water in a continuous flow to the upper surface of the substrate W held by the rotating chuck 5. The stripping liquid is a liquid used to strip the treatment film in a state holding the object to be removed from the upper surface of the substrate W.

[0234] The third moving nozzle 11 moves in the horizontal direction and the vertical direction through the third nozzle moving unit 37. In the horizontal direction, the third moving nozzle 11 can move between the center position and the initial position (retracted position).

[0235] When the third moving nozzle 11 is located at the center position, it faces the central region of the upper surface of the substrate W. When the third moving nozzle 11 is located at the initial position, it does not face the upper surface of the substrate W and is located outside the treatment cup 7 in a top view. The third moving nozzle 11 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0236] The third nozzle moving unit 37 has the same configuration as the first nozzle moving unit 35. That is, the third nozzle moving unit 37 may also include an arm (not shown) connected to the third moving nozzle 11 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending along the vertical direction, and a rotating shaft driving unit (not shown) that raises or rotates the rotating shaft.

[0237] The third moving nozzle 11 is connected to an upper stripping liquid pipe 45 that guides the stripping liquid to the upper side of the third moving nozzle 11. After opening an upper stripping liquid valve 55 inserted in the upper stripping liquid pipe 45, the stripping liquid is continuously ejected downward from the ejection port of the third moving nozzle 11 in a flow shape. If the upper stripping liquid valve 55 is opened when the third moving nozzle 11 is in the central position, the stripping liquid is supplied to the central region of the upper surface of the substrate W.

[0238] In this embodiment, as the stripping liquid, the first stripping liquid is used. As the first stripping liquid, a liquid that is more likely to dissolve the highly soluble components contained in the treatment liquid than the low-soluble components contained in the treatment liquid can be used. The first stripping liquid is, for example, ammonia water, and the mass percentage concentration of ammonia in the stripping liquid is 0.4%.

[0239] The first stripping liquid may also be an alkaline aqueous solution (alkaline liquid) other than ammonia water. Specific examples of the alkaline aqueous solution other than ammonia water include an aqueous solution of TMAH (tetramethylammonium hydroxide) and an aqueous solution of choline, and any combination thereof. The first stripping liquid may be pure water (preferably DIW), or a neutral or acidic aqueous solution (non-alkaline aqueous solution).

[0240] The first stripping liquid is preferably an alkaline solution. The pH of the first stripping liquid is preferably 7 to 13. Specifically, the pH of the first stripping liquid is preferably 8 to 13, more preferably 10 to 13, and further preferably 11 to 12.5. In order to avoid the influence of the dissolution of carbon dioxide gas in the air, the measurement of the pH is preferably performed after degassing.

[0241] Most of the solvent of the first stripping liquid is pure water. The ratio of pure water in the solvent of the first stripping liquid is 50 to 100% by mass (preferably 70% by mass to 100%, more preferably 90% by mass to 100%, further preferably 95% by mass to 100%, and even further preferably 99 to 100%). The term "mass%" refers to the ratio of the mass of a certain component in the total mass of the liquid. The mass percentage concentration of the solute of the first stripping liquid is 0.1% to 10% (preferably 0.2% to 8%, more preferably 0.3% to 6%).

[0242] The central nozzle 12 is housed in an internal space 60a of a hollow shaft 60 of the opposing member 6. An ejection port 12a provided at the front end of the central nozzle 12 is exposed from the communication hole 6b and faces the central region of the upper surface of the substrate W from above.

[0243] The central nozzle 12 includes a plurality of tubes (a first tube 31, a second tube 32, and a third tube 33) that eject fluid downward, and a cylindrical shell 30 that surrounds the plurality of tubes. The plurality of tubes and the shell 30 extend in the vertical direction along the rotation axis A1. The ejection port 12a of the central nozzle 12 is the ejection port of the first tube 31, the ejection port of the second tube 32, and the ejection port of the third tube 33.

[0244] The first tube 31 (central nozzle 12) is an example of a cleaning liquid supply unit that supplies a cleaning liquid such as DIW to the upper surface of the substrate W. The second tube 32 (central nozzle 12) 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. The third tube 33 (central nozzle 12) is an example of a gas supply unit that supplies a gas such as nitrogen (N2) to the facing surface 6a between the upper surface of the substrate W and the facing member 6. The central nozzle 12 is a cleaning liquid nozzle, an organic solvent nozzle, and a gas nozzle.

[0245] The first tube 31 is connected to an upper cleaning liquid pipe 41 that guides the cleaning liquid to the upper side of the first tube 31. After opening the upper cleaning liquid valve 51 inserted in the upper cleaning liquid pipe 41, the cleaning liquid is ejected from the first tube 31 (central nozzle 12) in a continuous flow shape toward the central region of the upper surface of the substrate W.

[0246] The cleaning liquid is a liquid that flushes away the liquid attached to the surface of the substrate W. Examples of the cleaning liquid include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid water diluted to a certain concentration (for example, about 1 ppm to 100 ppm), ammonia water diluted to a certain concentration (for example, about 1 ppm to 100 ppm), reduced water (hydrogen water), etc.

[0247] The second tube 32 is connected to an organic solvent pipe 42 that guides an organic solvent such as IPA to the second tube 32. After opening the organic solvent valve 52 inserted in the organic solvent pipe 42, the organic solvent is ejected from the second tube 32 (central nozzle 12) in a continuous flow shape toward the central region of the upper surface of the substrate W.

[0248] The organic solvent ejected from the second tube 32 is preferably compatible with the cleaning liquid and the processing liquid. The organic solvent ejected from the second tube 32 functions as a residue removal liquid for dissolving and removing the residue of the processing film, which is a substance remaining on the upper surface of the substrate W after the processing film is peeled off from the upper surface of the substrate W by the stripping liquid and removed. Therefore, the residue removal liquid is also called the residue dissolution liquid.

[0249] In the following substrate processing, the organic solvent ejected from the second tube 32 is supplied to the upper surface of the substrate W covered by the liquid film of the cleaning liquid, and the processing liquid is supplied to the upper surface of the substrate W covered by the liquid film of the organic solvent. After the organic solvent is supplied to the upper surface of the substrate W covered by the liquid film of the cleaning liquid, almost all the cleaning liquid on the substrate W will be pushed by the organic solvent and discharged from the substrate W. The remaining trace amount of cleaning liquid will be dissolved in the organic solvent and diffused in the organic solvent. The diffused cleaning liquid will be discharged from the substrate W together with the organic solvent. Therefore, the cleaning liquid on the substrate W can be efficiently replaced with the organic solvent. Based on the same reason, the organic solvent on the substrate W can be efficiently replaced with the processing liquid. Thus, the cleaning liquid contained in the processing liquid on the substrate W can be reduced. The organic solvent ejected from the second tube 32 functions as a replacement liquid for replacing the cleaning liquid.

[0250] In addition, the organic solvent sprayed from the second pipe 32 is preferably a low surface tension liquid having a lower surface tension than that of the cleaning liquid. In the following substrate processing, the upper surface of the substrate W is not dried by shaking off the cleaning liquid on the substrate W, but the cleaning liquid on the substrate W is first replaced with an organic solvent, and then the organic solvent on the substrate W is shaken off, thereby drying the upper surface of the substrate W. Therefore, if the organic solvent is a low surface tension liquid, the surface tension acting on the upper surface of the substrate W can be reduced when the upper surface of the substrate W is dried.

[0251] Examples of organic solvents that function as a residue removing liquid, a low surface tension liquid, and a replacement liquid include liquids containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.

[0252] The organic solvent that functions as a residue removing liquid, a low surface tension liquid, and a replacement liquid is not necessarily composed of a single component, but may be a liquid mixed with other components, for example, a mixed liquid of IPA and DIW, or a mixed liquid of IPA and HFE.

[0253] The third tube 33 is connected to a gas pipe 43 that guides the gas to the third tube 33. When a gas valve 53 inserted in the gas pipe 43 is opened, the gas is ejected downward from the third tube 33 (central nozzle 12) in a continuous flow.

[0254] The gas ejected from the third tube 33 is, for example, an inert gas such as nitrogen. The gas ejected from the third tube 33 may also be air. The so-called inert gas is not limited to nitrogen, but refers to a gas that is inert to the upper surface of the substrate W. Examples of the inert gas include, in addition to nitrogen, rare gases such as argon.

[0255] The lower nozzle 13 is inserted into a through hole 21a formed in the central portion of the upper surface of the rotary base 21. The ejection port 13a of the lower nozzle 13 is exposed from the upper surface of the rotary base 21. The ejection port 13a of the lower nozzle 13 faces the central region of the lower surface (the lower side surface) of the substrate W from below. The central region of the lower surface of the substrate W refers to the region of the lower surface of the substrate W that includes the rotation center of the substrate W.

[0256] One end of a common pipe 80 that commonly guides a cleaning liquid, a stripping liquid, and a heat medium to the lower nozzle 13 is connected to the lower nozzle 13. At the other end of the common pipe 80, a lower cleaning liquid pipe 81 that guides the cleaning liquid to the common pipe 80, a lower stripping liquid pipe 82 that guides the stripping liquid to the common pipe 80, and a heat medium pipe 83 that guides the heat medium to the common pipe 80 are connected.

[0257] After opening a lower cleaning liquid valve 86 inserted in the lower cleaning liquid pipe 81, the cleaning liquid is continuously ejected from the lower nozzle 13 toward the central region of the lower surface of the substrate W. After opening a lower stripping liquid valve 87 inserted in the lower stripping liquid pipe 82, the stripping liquid is continuously ejected from the lower nozzle 13 toward the central region of the lower surface of the substrate W. After opening a heat medium valve 88 inserted in the heat medium pipe 83, the heat medium is continuously ejected from the lower nozzle 13 toward the central region of the lower surface of the substrate W.

[0258] The lower nozzle 13 is an example of a lower cleaning liquid supply unit that supplies a cleaning liquid to the lower surface of the substrate W. In addition, the lower nozzle 13 is an example of a lower stripping liquid supply unit that supplies a stripping liquid to the lower surface of the substrate W. In addition, the lower nozzle 13 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 nozzle 13 is also an example of a substrate heating unit that heats the substrate W.

[0259] Since the cleaning liquid ejected from the lower nozzle 13 is the same as the cleaning liquid ejected from the central nozzle 12, the relevant description is omitted. Since the stripping liquid ejected from the lower nozzle 13 is the same as the first stripping liquid ejected from the third moving nozzle 11, the relevant description is omitted.

[0260] The heat medium ejected from the lower nozzle 13 is, for example, high-temperature DIW whose temperature is higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid. When the solvent contained in the processing liquid is IPA, for example, DIW at 60°C to 80°C can be used as the heat medium. The heat medium ejected from the lower nozzle 13 is not limited to high-temperature DIW, and can also be a high-temperature gas such as high-temperature inert gas or high-temperature air whose temperature is higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid.

[0261] Figure 5It is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus 1. The controller 3 includes a microcomputer and controls the controlled objects equipped in the substrate processing apparatus 1 according to a specified control program.

[0262] 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 processing the substrate by the processor 3A executing the control program.

[0263] Moreover, the controller 3 is programmed to control the transfer robots IR, CR, the rotation motor 23, the first nozzle moving unit 35, the second nozzle moving unit 36, the third nozzle moving unit 37, the opposing member lifting unit 61, the opposing member rotating unit 62, the guard lifting unit 74, the hydrophilic liquid valve 50, the upper cleaning liquid valve 51, the organic solvent valve 52, the gas valve 53, the processing liquid valve 54, the upper stripping liquid valve 55, the lower cleaning liquid valve 86, the lower stripping liquid valve 87, and the heat medium valve 88. By the controller 3 controlling the valves, it controls the presence or absence of the ejection of the processing fluid from the corresponding nozzle and the ejection flow rate of the processing fluid from the corresponding nozzle.

[0264] <Configuration of the Substrate to be Processed>

[0265] Figure 6 Shows an example of the details of the surface layer of the substrate W that is the object to be processed by the substrate processing apparatus 1. On the surface layer 150 of the substrate W, a semiconductor layer 151, an insulating layer 152, and a barrier layer 153 are provided. The semiconductor layer 151 is formed of, for example, Si (silicon). In the surface layer portion of the semiconductor layer 151, an impurity region 154 is formed.

[0266] The insulating layer 152 is formed of, for example, SiO2 (silicon oxide). Above the impurity region 154, a contact hole 155 penetrating the insulating layer 152 is provided.

[0267] The barrier layer 153 is formed on the upper surface of the insulating layer 152 and the inner surface of the contact hole 155. The barrier layer 153 is a TiN layer formed of TiN (titanium nitride) and is formed by a method such as ALD (atomic layer deposition). Therefore, TiN is exposed on the surface of the substrate W.

[0268] The contact holes 155 are provided at equal intervals in the insulating layer 152, and a fine concavo-convex pattern can also be formed through the insulating layer 152 and the contact holes 155. In this case, the barrier layer 153 has a shape similar to the concavo-convex pattern.

[0269] Figure 7 Shows another example of the details of the surface layer of the substrate W that is the object to be processed by the substrate processing apparatus 1. As Figure 7As shown, on the surface layer 150 of the substrate W that is the object to be processed by the substrate processing apparatus 1, in addition to the semiconductor layer 151, the insulating layer 152, and the barrier layer 153, a metal layer 156 may be provided. The metal layer 156 is, for example, a tungsten layer formed of W (tungsten) and is formed by a method such as CVD (chemical vapor deposition). The metal layer 156 fills the contact hole 155 and covers the barrier layer 153. Therefore, the surface of the metal layer 156 is a flat surface. Figure 7 The metal constituting the metal layer 156 is exposed on the surface of the substrate W shown. When the metal layer 156 is formed of tungsten, tungsten is exposed on the surface of the substrate W.

[0270] <Substrate Processing of the First Embodiment>

[0271] Figure 8 It is a flowchart for explaining an example of the substrate processing by the substrate processing apparatus 1. Figure 8 It mainly shows the processing realized by executing a program by the controller 3. FIG. 9A to FIG. 9I It is a schematic diagram for explaining the respective steps of the substrate processing.

[0272] In the substrate processing performed by the substrate processing apparatus 1, for example, as Figure 8 shown, the substrate loading step (step S1), the hydrophilic treatment step (step S2), the first cleaning step (step S3), the replacement step (step S4), the processing liquid supply step (step S5), the processing film formation step (step S6), the stripping step (step S7), the second cleaning step (step S8), the residue removal step (step S9), the spin drying step (step S10), and the substrate unloading step (step S11) are sequentially executed.

[0273] Next, mainly referring to Figure 2 and Figure 8 . Optionally referring to FIG. 9A to FIG. 9I .

[0274] First, the unprocessed substrate W is loaded from the carrier C into the processing unit 2 by the transfer robots IR and CR (refer to Figure 1 ) and delivered to the rotating chuck 5 (step S1). Thereby, the substrate W is horizontally held by the rotating chuck 5 (substrate holding step). When loading the substrate W, the opposing member 6 retracts to the upper position.

[0275] The holding of the substrate W by the rotating chuck 5 continues until the end of the spin drying step (step S10). During the period from the start of the substrate holding step to the end of the spin drying step (step S10), the guard lifting unit 74 adjusts the height positions of the first guard 71A and the second guard 71B so that at least one guard 71 is in the upper position.

[0276] While the substrate W is held by the rotary chuck 5, the rotary motor 23 rotates the rotary base 21. Thereby, the horizontally held substrate W starts to rotate (substrate rotation step). The opposing member rotation unit 62 can also rotate the opposing member 6 in synchronization with the rotary base 21. Synchronous rotation means rotating the opposing member 6 and the rotary base 21 in the same rotation direction at the same rotation speed.

[0277] Next, after the transfer robot CR retreats outside the processing unit 2, the hydrophilic treatment step (step S2) is started. In the hydrophilic treatment step, first, with the opposing member 6 in the retracted position, the first nozzle moving unit 35 moves the first moving nozzle 9 to the processing position. The processing position of the first moving nozzle 9 is, for example, the central position. When the opposing member 6 is in the retracted position, each moving nozzle can move horizontally between the opposing member 6 and the substrate W. The retracted position can also be the upper position.

[0278] Then, the hydrophilic liquid valve 50 is opened. Thereby, as Fig.9A shown, a first hydrophilic liquid such as hydrofluoric acid is supplied (sprayed) from the first moving nozzle 9 to the central region of the upper surface of the rotating substrate W (hydrophilic liquid supply step, hydrophilic liquid spraying step). The first hydrophilic liquid supplied to the upper surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire upper surface of the substrate W. Thereby, the upper surface of the substrate W is hydrophilized, so that the contact angle of pure water on the upper surface of the substrate W is less than 41.7° (contact angle reduction step).

[0279] The supply of the first hydrophilic liquid from the first moving nozzle 9 continues for a specified time, for example, 30 seconds. In the hydrophilic treatment step, the substrate W rotates at a specified hydrophilic rotation speed, for example, 800 rpm.

[0280] Next, the first cleaning step (step S3) is performed, that is, the first hydrophilic liquid on the substrate W is rinsed off.

[0281] Specifically, the hydrophilic liquid valve 50 is closed. Thereby, the supply of the first hydrophilic liquid to the substrate W is stopped. Then, the first nozzle moving unit 35 moves the first moving nozzle 9 to the initial position. Then, the opposing member lifting unit 61 moves the opposing member 6 to the processing position between the upper position and the lower position. When the opposing member 6 is in the processing position, the distance between the upper surface of the substrate W and the opposing surface 6a is, for example, 30 mm.

[0282] With the opposing member 6 in the processing position, the upper side cleaning liquid valve 51 is opened. Thereby, as Fig. 9BAs shown, cleaning liquid is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W. The cleaning liquid supplied from the central nozzle 12 to the upper surface of the substrate W is subjected to centrifugal force and spreads radially to cover the entire upper surface of the substrate W. Thereby, the first hydrophilic liquid on the upper surface of the substrate W is washed out of the substrate W.

[0283] Substantially simultaneously with the opening of the upper cleaning liquid valve 51, the lower cleaning liquid valve 86 is opened. Thereby, as Fig. 9B shown, cleaning liquid is supplied (sprayed) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W. The cleaning liquid supplied from the lower nozzle 13 to the lower surface of the substrate W is subjected to centrifugal force and spreads radially to cover the entire lower surface of the substrate W. Even if the first hydrophilic liquid that adhered to the upper surface of the substrate W during the hydrophilic treatment step splashes from the substrate W and adheres to the lower surface of the substrate W, the cleaning liquid supplied from the lower nozzle 13 will wash away the first hydrophilic liquid adhering to the lower surface.

[0284] The spraying of the cleaning liquid from the central nozzle 12 and the lower nozzle 13 continues for a specified time, for example, 30 seconds. In the first cleaning step, the substrate W rotates at a specified first cleaning rotation speed, for example, 800 rpm.

[0285] Next, the replacement step (step S4) is started. In the replacement step, the cleaning liquid on the substrate W is replaced with an organic solvent (for example, IPA) as the replacement liquid.

[0286] Specifically, the upper cleaning liquid valve 51 and the lower cleaning liquid valve 86 are closed. Thereby, the supply of the cleaning liquid to the upper surface and the lower surface of the substrate W is stopped. The opposing member 6 is maintained at the processing position.

[0287] While the opposing member 6 is maintained at the processing position, the organic solvent valve 52 is opened. Thereby, as Fig. 9C shown, an organic solvent as the replacement liquid is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (replacement liquid supply step, replacement liquid spraying step). The central nozzle 12 is an example of a replacement liquid nozzle.

[0288] The organic solvent supplied from the central nozzle 12 to the upper surface of the substrate W is subjected to centrifugal force and spreads radially to cover the entire upper surface of the substrate W. Thereby, the cleaning liquid on the substrate W is replaced with the organic solvent.

[0289] In the replacement step, the organic solvent ejected from the central nozzle 12 is ejected for a specified time, for example, 10 seconds. In the replacement step, the substrate W is rotated at a specified replacement rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not necessarily rotate at a fixed rotation speed in the replacement step. For example, the rotation motor 23 may also rotate the substrate W at 300 rpm at the start of the supply of the organic solvent, and while supplying the organic solvent to the substrate W, accelerate the rotation of the substrate W until the rotation speed of the substrate W reaches 1500 rpm.

[0290] Next, a treatment liquid supply step (step S5) is performed, that is, a treatment liquid is supplied to the upper surface of the substrate W. Specifically, the organic solvent valve 52 is closed, and the facing member lifting unit 61 moves the facing member 6 to the retracted position. In a state where the facing member 6 is in the retracted position, the second nozzle moving unit 36 moves the second moving nozzle 10 to the treatment position. The treatment position of the second moving nozzle 10 is, for example, the central position. Then, the treatment liquid valve 54 is opened. Thus, as Fig.9D shown, the treatment liquid (treatment liquid supply step, treatment liquid ejection step) is supplied (ejected) from the second moving nozzle 10 to the central region of the upper surface of the rotating substrate W. The treatment liquid supplied to the upper surface of the substrate W diffuses to the entire substrate W by centrifugal force. Thus, a treatment liquid film 101 (treatment liquid film) is formed on the substrate W (treatment liquid film formation step).

[0291] The supply of the treatment liquid from the second moving nozzle 10 is continued for a specified time, for example, 2 seconds to 4 seconds. In the treatment liquid supply step, the substrate W is rotated at a specified treatment liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0292] Next, the Fig.9E and Fig.9F shown treatment film formation step (step S8) is performed. In the treatment film formation step, the treatment liquid on the substrate W is solidified or hardened, and a treatment film 100 for holding the object to be removed existing on the substrate W is formed on the upper surface of the substrate W (refer to Fig.9F ).

[0293] In the treatment film formation step, first, a treatment liquid thinning step (treatment liquid rotation stop step) is performed, that is, the thickness of the treatment liquid film 101 on the substrate W is thinned. Specifically, the treatment liquid valve 54 is closed. Thus, the supply of the treatment liquid to the substrate W is stopped. Then, the second nozzle moving unit 36 moves the second moving nozzle 10 to the initial position.

[0294] As Fig.9EAs shown, in the step of thinning the processing liquid film, the substrate W is rotated in a state where the supply of the processing liquid to the upper surface of the substrate W is stopped. Therefore, a part of the processing liquid is excluded from the upper surface of the substrate W. As a result, the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness. After the second moving nozzle 10 is moved to the initial position, the opposing member 6 remains in the retracted position.

[0295] In the step of thinning the processing liquid film, the rotation motor 23 changes the rotation speed of the substrate W to a specified processing liquid thinning speed. The processing liquid thinning speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept fixed within the range of 300 rpm to 1500 rpm, or can be appropriately changed within the range of 300 rpm to 1500 rpm during the middle of the processing liquid thinning step. The processing liquid thinning step is continuously executed for a specified time, for example, 30 seconds.

[0296] In the processing film formation step, after the processing liquid thinning step, a processing liquid solvent evaporation step is performed, that is, a part of the solvent is evaporated (volatilized) from the liquid film 101 of the processing liquid. In the processing liquid solvent evaporation step, since a part of the solvent of the processing liquid on the substrate W is evaporated, the liquid film 101 on the substrate W is heated.

[0297] Specifically, as Fig.9F shown, the opposing member lifting unit 61 moves the opposing member 6 to the proximity position. The proximity position can also be the lower position. The proximity position is a position where the distance from the upper surface of the substrate W to the opposing surface 6a is, for example, 1 mm.

[0298] Then, the gas valve 53 is opened. As a result, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 101) and the opposing surface 6a of the opposing member 6 (gas supply step).

[0299] By blowing gas onto the liquid film 101 on the substrate W, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (processing liquid solvent evaporation step, processing liquid solvent evaporation promotion step). Therefore, the time required to form the processing film 100 can be shortened. In the processing film formation step, the central nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0300] After a part of the processing liquid is excluded from the substrate W through the step of thinning the processing liquid film of the liquid film 101, the opposing member 6 and the substrate W still continue to rotate. Therefore, the centrifugal force generated by the rotation of the opposing member 6 and the substrate W acts on the gas ejected from the central nozzle 12. Due to the action of the centrifugal force, the gas forms an air flow from the center side to the peripheral side of the substrate W. Therefore, the solvent in the gas state in contact with the liquid film 101 is promoted to be excluded from the space between the opposing member 6 and the substrate W. Thereby, the evaporation of the solvent in the liquid film 101 is promoted. As described above, the opposing member 6 and the rotation motor 23 function as an evaporation unit (evaporation promotion unit) for evaporating (volatilizing) the solvent in the processing liquid. It is also possible that the opposing member 6 does not rotate and only the substrate W rotates.

[0301] In addition, the heat medium valve 88 is opened. Thereby, the heat medium (heat medium supply step, heat medium ejection step) is supplied (ejected) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W. The heat medium supplied to the lower surface of the substrate W from the lower nozzle 13 is subjected to centrifugal force and spreads radially, covering the entire lower surface of the substrate W.

[0302] The supply of the heat medium to the substrate W continues for a specified time, for example, 60 seconds. In the processing liquid solvent evaporation step, the substrate W rotates at a specified evaporation rotation speed, for example, 1000 rpm.

[0303] By supplying the heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated across the substrate W. Thereby, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (processing liquid solvent evaporation step, processing liquid solvent evaporation promotion step). Therefore, the time required to form the processing film 100 can be shortened. In the processing film formation step, the lower nozzle 13 also functions as an evaporation unit (evaporation promotion unit) for evaporating (volatilizing) the solvent in the processing liquid.

[0304] By performing the processing liquid thinning step and the processing liquid solvent evaporation step, the processing liquid is solidified or hardened. Thereby, a processing film 100 for holding the object to be removed is formed on the entire upper surface of the substrate W.

[0305] As described above, the substrate rotation unit (rotation motor 23), the opposing member rotation unit 62, the central nozzle 12, and the lower nozzle 13 constitute a processing film formation unit for solidifying or hardening the processing liquid to form a solid processing film 100.

[0306] By using the blowing of the gas, the rotation of the substrate W, and the heating of the substrate W, the processing film 100 can be formed quickly, but the processing film 100 can also be formed by the blowing of the gas and the rotation of the substrate W. That is, the formation of the processing film 100 does not necessarily require the step of heating with the heat medium. Therefore, the supply of the heat medium to the substrate W can be omitted.

[0307] In the processing liquid solvent evaporation step, the substrate W is preferably heated in such a way that the temperature of the substrate W is lower than the boiling point of the solvent. By heating the substrate W to a temperature lower than the boiling point of the solvent, the situation where the solvent evaporates completely can be suppressed, so that an appropriate amount of the solvent can remain in the processing film 100. As a result, compared with the case where no solvent remains in the processing film 100, in the subsequent peeling step (step S6), it is easier for the first peeling liquid to act on the processing film 100.

[0308] Next, the peeling step (step S6) is performed, that is, the processing film 100 is peeled off. Specifically, the heat medium valve 88 is closed. As a result, the supply of the heat medium to the lower surface of the substrate W is stopped. In addition, the gas valve 53 is closed. As a result, the supply of the gas to the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is stopped.

[0309] Then, the opposing member lifting unit 61 moves the opposing member 6 to the retracted position. In a state where the opposing member 6 is in the retracted position, the third nozzle moving unit 37 moves the third moving nozzle 11 to the processing position. The processing position of the third moving nozzle 11 is, for example, the central position.

[0310] Then, with the third moving nozzle 11 in the processing position, the upper side peeling liquid valve 55 is opened. As a result, as Figure 9G shown, the first peeling liquid (upper side peeling liquid supply step, upper side peeling liquid ejection step) is supplied (ejected) from the third moving nozzle 11 to the central region of the upper surface of the rotating substrate W. The first peeling liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. As a result, the processing film 100 on the upper surface of the substrate W is peeled off and discharged outside the substrate W together with the first peeling liquid.

[0311] While opening the upper side peeling liquid valve 55, the lower side peeling liquid valve 87 is opened. As a result, as Figure 9G shown, the first peeling liquid (lower side peeling liquid supply step, lower side peeling liquid ejection step) is supplied (ejected) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W. The first peeling liquid supplied to the lower surface of the substrate W diffuses to the entire lower surface of the substrate W by centrifugal force.

[0312] The supply of the first peeling liquid to the upper surface and the lower surface of the substrate W continues for a specified time, for example, 60 seconds. In the peeling step, the substrate W rotates at a specified peeling rotation speed, for example, 800 rpm.

[0313] Here, in Fig.9D the processing liquid supply step (step S5) shown, the processing liquid supplied to the upper surface of the substrate W may adhere to the lower surface of the substrate W along the periphery of the substrate W, and the processing liquid adhering to the lower surface of the substrate W solidifies or hardens to form a solid.

[0314] As Figure 9G shown, in the stripping step (step S6), during the supply of the first stripping liquid to the upper surface of the substrate W, the first stripping liquid is supplied (sprayed) from the lower nozzle 13 to the lower surface of the substrate W. Therefore, even if a solid of the processing liquid is formed on the lower surface of the substrate W, the solid can be stripped and removed from the lower surface of the substrate W.

[0315] After the stripping step (step S6), a second cleaning step (step S7) is performed, that is, the first stripping liquid is flushed from the substrate W by the cleaning liquid. Specifically, the upper stripping liquid valve 55 and the lower stripping liquid valve 87 are closed. Thereby, the supply of the first stripping liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to the initial position. Then, as Figure 9H shown, the facing member lifting unit 61 moves the facing member 6 to the processing position.

[0316] Then, with the facing member 6 in the processing position, the upper cleaning liquid valve 51 is opened. Thereby, as Figure 9H shown, the cleaning liquid is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (upper cleaning liquid supply step, upper cleaning liquid spraying step). The cleaning liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, the first stripping liquid attached to the upper surface of the substrate W is flushed away by the cleaning liquid (cleaning step).

[0317] In addition, while the upper cleaning liquid valve 51 is opened, the lower cleaning liquid valve 86 is opened. Thereby, as Figure 9H shown, the cleaning liquid is supplied (sprayed) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W (lower cleaning liquid supply step, lower cleaning liquid spraying step). Thereby, the first stripping liquid attached to the lower surface of the substrate W is flushed away by the cleaning liquid.

[0318] The supply of the cleaning liquid to the upper surface and the lower surface of the substrate W continues for a specified time, for example, 30 seconds. In the second cleaning step, the substrate W rotates at a specified second cleaning rotation speed, for example, 800 rpm.

[0319] Next, a residue removal step (step S8) is performed. In the residue removal step, the residue of the processing film 100 remaining on the upper surface of the substrate W after the stripping step is removed by an organic solvent (for example, IPA) as the residue removal liquid. Specifically, the upper cleaning liquid valve 51 and the lower cleaning liquid valve 86 are closed. Thereby, the supply of the cleaning liquid to the upper surface and the lower surface of the substrate W is stopped.

[0320] Then, with the facing member 6 in the processing position, the organic solvent valve 52 is opened. Thereby, as Fig.9IAs shown, an organic solvent as a residue removal liquid is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (residue removal liquid supply step, residue removal liquid spraying step).

[0321] The organic solvent supplied from the central nozzle 12 to the upper surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire upper surface of the substrate W. After the organic solvent dissolves the residue of the processing film remaining on the upper surface of the substrate W, it is discharged from the periphery of the upper surface of the substrate W. The central nozzle 12 is an example of a residue removal liquid nozzle.

[0322] In the residue removal step, the spraying of the organic solvent from the central nozzle 12 continues for a specified time, for example, 30 seconds. In the residue removal step, the substrate W rotates at a specified residue removal rotation speed, for example, 300 rpm.

[0323] Next, a spin drying step (step S10) is performed, that is, the substrate W is rotated at a high speed to dry the upper surface of the substrate W.

[0324] Specifically, the organic solvent valve 52 is closed. Thereby, the supply of the organic solvent to the upper surface of the substrate W is stopped. Then, the opposing member lifting unit 61 moves the opposing member 6 to a drying position lower than the processing position. When the opposing member 6 is in the drying position, the distance between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 53 is opened. Thereby, gas is supplied to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6.

[0325] Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed. The substrate W in the spin drying step rotates at a drying speed, for example, 1500 rpm. The spin drying step continues to be performed for a specified time, for example, 30 seconds. Thereby, a huge centrifugal force acts on the organic solvent on the substrate W, and the organic solvent on the substrate W is flung toward the periphery of the substrate W. In the spin drying step, gas is supplied to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6, thereby promoting the evaporation of the organic solvent.

[0326] Then, the rotation motor 23 stops the rotation of the substrate W. The guard lifting unit 74 moves the first guard 71A and the second guard 71B to the lower position. The gas valve 53 is closed. Then, the opposing member lifting unit 61 moves the opposing member 6 to the upper position.

[0327] The transfer robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pin 20 of the rotary chuck 5, and carries it out of the processing unit 2 (step S11). This substrate W is handed over from the transfer robot CR to the transfer robot IR and stored in the carrier C by the transfer robot IR.

[0328] <Situation of stripping of the processing film in the first embodiment>

[0329] Using Figure 10A to Figure 10C , the removal situation of the processing film 100 will be described in detail. Figures 10A to 10C It is a schematic diagram for explaining the situation of stripping the processing film 100 from the substrate W.

[0330] As Fig. 10A shown, the processing film 100 holds the removal object 103 attached to the surface layer 150 of the substrate W. The processing film 100 has highly soluble solids 110 (highly soluble components in solid state) and poorly soluble solids 111 (poorly soluble components in solid state). The highly soluble solids 110 and the poorly soluble solids 111 are formed by evaporation of at least a part of the solvent contained in the processing liquid.

[0331] In the processing film 100, the highly soluble solids 110 and the poorly soluble solids 111 are mixed. Strictly speaking, in the processing film 100, the highly soluble solids 110 and the poorly soluble solids 111 are not uniformly distributed throughout the processing film 100. In the processing film 100, there are parts where the highly soluble solids 110 are concentrated and parts where the poorly soluble solids 111 are concentrated.

[0332] Referring to Fig. 10B , the highly soluble solids 110 are dissolved by the first stripping liquid. That is, the processing film 100 is partially dissolved (dissolving step, partial dissolving step). By dissolving the highly soluble solids 110, through holes 102 are formed in the parts where the highly soluble solids 110 are concentrated in the processing film 100 (through hole forming step).

[0333] The through holes 102 are particularly likely to be formed in the parts where the highly soluble solids 110 extend along the thickness direction T of the processing film 100. The through holes 102 are, for example, several nanometers in diameter when viewed from above. The through holes 102 are gaps formed in the processing film 100 by dissolving the highly soluble solids 110.

[0334] Here, when an appropriate amount of solvent remains in the processing film 100, the first stripping liquid will dissolve into the solvent remaining on the processing film 100 while partially dissolving the processing film 100. Specifically, the stripping liquid will dissolve into the solvent remaining on the highly soluble solids 110 while dissolving the highly soluble solids 110 in the processing film 100 to form through holes 102. Therefore, the first stripping liquid easily enters the processing film 100 (dissolving and entering step).

[0335] The first stripping liquid passes through the through hole 102 to reach the interface between the processing film 100 and the substrate W, and acts on this interface. The so-called action of the first stripping liquid on the interface between the processing film 100 and the substrate W means that the first stripping liquid only dissolves the part in contact with the substrate W and strips the processing film 100 from the substrate W.

[0336] The solubility of the low-solubility component in the first stripping liquid is low, and the low-solubility solid 111 is hardly dissolved by the first stripping liquid. Therefore, only the vicinity of the surface of the low-solubility solid 111 will be dissolved by the first stripping liquid. Therefore, the first stripping liquid reaching the vicinity of the upper surface of the substrate W via the through hole 102 only dissolves the part of the low-solubility solid 111 near the upper surface of the substrate W. Thus, as magnified Fig. 10B As shown, the first stripping liquid slowly dissolves the low-solubility solid 111 near the upper surface of the substrate W while entering the gap G1 (stripping liquid entry step) between the processing film 100 and the upper surface of the substrate W.

[0337] Then, for example, the processing film 100 splits starting from the periphery of the through hole 102 and becomes a film piece 105. As Fig. 10C shown, the film piece 105 of the processing film 100 is stripped from the substrate W while holding the object to be removed 103 (processing film splitting step, processing film stripping step).

[0338] Then, the first stripping liquid is continuously supplied, and thereby the processing film 100 that has become the film piece 105 is washed away while holding the object to be removed 103. In other words, the film piece 105 holding the object to be removed 103 is pushed out of the substrate W and removed from the upper surface of the substrate W (processing film removal step, object to be removed removal step). Thus, the upper surface of the substrate W can be cleaned well.

[0339] <Summary of the First Embodiment>

[0340] The strength (stripping force) of the stripping action of the first stripping liquid for stripping the processing film 100 from the substrate W varies according to the surface state of the upper surface of the substrate W. Specifically, the higher the hydrophilicity of the upper surface of the substrate W, the easier it is to strip the processing film 100 by the first stripping liquid. More specifically, the higher the hydrophilicity of the upper surface of the substrate W, the higher the wettability (affinity) of the stripping liquid to the substrate W, and the easier it is for the first stripping liquid to enter between the substrate W and the processing film 100. That is, the higher the hydrophilicity of the upper surface of the substrate W, the easier it is to strip the processing film 100 from the upper surface of the substrate W.

[0341] According to this embodiment, the processing film 100 is formed on the upper surface of the hydrophilized substrate W, and then the processing film 100 is stripped by the first stripping liquid. Therefore, the processing film 100 can be effectively stripped from the substrate W.

[0342] When stripping the treatment film 100, through-holes 102 are formed in the treatment film 100 by the first stripping liquid. Therefore, the first stripping liquid can reach the interface between the treatment film 100 and the substrate W via the through-holes 102. Thereby, the first stripping liquid can enter between the portion surrounding the through-holes 102 in the treatment film 100 and the upper surface of the substrate W. Therefore, compared with a configuration in which the stripping liquid penetrates into the treatment film 100 without forming through-holes 102 in the treatment film 100 to allow the stripping liquid to reach the interface between the treatment film 100 and the substrate W, the first stripping liquid can act quickly on the interface between the treatment film 100 and the substrate W. Although the treatment film 100 will be partially dissolved by the first stripping liquid due to the formation of the through-holes 102, the remaining portion will maintain a solid state. Therefore, the treatment film 100 holding the object to be removed 103 can be effectively stripped from the upper surface of the substrate W.

[0343] As described above, since the first stripping liquid can act quickly on the interface between the treatment film 100 and the substrate W and most of the treatment film 100 can maintain a solid state, the treatment film 100 holding the object to be removed 103 can be effectively stripped from the substrate W.

[0344] According to the present embodiment, the solubility of the highly soluble component in the first stripping liquid is higher than the solubility of the low-soluble component in the first stripping liquid. Therefore, the highly soluble solid 110 is more easily dissolved in the first stripping liquid than the low-soluble solid 111.

[0345] Therefore, by supplying the first stripping liquid to the upper surface of the substrate W, the highly soluble solid 110 is dissolved in the first stripping liquid to form through-holes 102 in the treatment film 100. On the other hand, the low-soluble solid 111 does not dissolve in the first stripping liquid and maintains a solid state.

[0346] Therefore, the highly soluble solid 110 can be dissolved in the first stripping liquid and the low-soluble solid 111 can be maintained in a solid state without dissolving in the first stripping liquid. Therefore, the first stripping liquid passes through the through-holes 102 formed by the dissolution of the highly soluble solid 110 and reaches the interface between the substrate W and the low-soluble solid 111.

[0347] Therefore, the object to be removed 103 can be held by the low-soluble solid 111 and the first stripping liquid can act on the interface between the low-soluble solid 111 and the substrate W. As a result, the treatment film 100 can be quickly stripped from the substrate W and the object to be removed 103 can be efficiently removed from the substrate W together with the treatment film 100.

[0348] In addition, according to the present embodiment, the poorly soluble solid 111 contained in the processing film 100 can be slightly dissolved in the first stripping liquid, and the first stripping liquid can effectively enter between the substrate W and the processing film 100. Therefore, the processing film 100 can be effectively stripped.

[0349] According to the present embodiment, the upper surface of the substrate W is hydrophilized by supplying the first hydrophilizing liquid to the upper surface of the substrate W. By supplying the first hydrophilizing liquid to the upper surface of the substrate W, the first hydrophilizing liquid diffuses on the upper surface of the substrate W, so that the first hydrophilizing liquid can cover the entire upper surface of the substrate W. Therefore, the entire upper surface of the substrate W can be hydrophilized without omission. Since the entire upper surface of the substrate W has been hydrophilized, in the subsequent stripping step, the first stripping liquid can easily act on the interface between the processing film 100 and the substrate W on the entire upper surface of the substrate W. Therefore, the processing film 100 can be uniformly stripped from the entire upper surface of the substrate W.

[0350] According to the present embodiment, the upper surface of the substrate W is hydrophilized in such a manner that the contact angle of pure water on the upper surface of the substrate W is less than 41.7°. Therefore, the first stripping liquid can fully act on the interface between the substrate W and the processing film 100. Thereby, the processing film 100 holding the object to be removed 103 can be effectively stripped from the substrate W.

[0351] According to the present embodiment, the contact angle of pure water on the processing film 100 is greater than 52° and less than 61°. As long as the contact angle of pure water on the processing film 100 is within this range, the affinity between the first stripping liquid and the processing film 100 is high enough. Therefore, the stripping liquid can fully enter between the substrate W and the processing film 100 to effectively strip the processing film 100 from the substrate W.

[0352] According to the present embodiment, at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the upper surface of the substrate W, so the upper surface of the substrate W can be hydrophilized through the hydrophilization step. For example, when the surface layer 150 of the substrate W includes a TiN layer (barrier layer 153), if an oxidizing liquid is used as the first hydrophilizing liquid, an oxide film 171 will be formed on the surface of the TiN layer, thereby hydrophilizing the upper surface of the substrate W. By hydrophilizing the upper surface of the substrate W in the above manner in advance, the processing film 100 can be effectively stripped from the substrate W.

[0353] <Another example of the substrate treatment of the first embodiment>

[0354] Fig.11 It is a flowchart for explaining another example of the substrate treatment device 1 for treating the substrate. Fig.11 The substrate treatment shown and Figure 8The difference in the substrate treatment shown is that the first cleaning step (step S3) and the replacement step (step S4) are omitted. As long as the first hydrophilic liquid used in the hydrophilization step is a liquid compatible with the treatment liquid, such as Fig.11 shown, the first cleaning step (step S3) and the replacement step (step S4) can be omitted. The first hydrophilic liquid is preferably a liquid the same as the solvent contained in the treatment liquid. The so-called same liquid means it is composed of the same substance. As an example of the first hydrophilic liquid compatible with the treatment liquid, organic solvents such as IPA can be cited.

[0355] <Treatment Film Stripping Experiment>

[0356] Next, the results of the treatment film stripping experiment conducted to investigate the relationship between the contact angle of pure water on the substrate and the ability to strip the treatment film will be described. Fig. 12A is a schematic diagram for explaining the order of measuring the contact angle of pure water on the surface of the experimental substrate 200. Fig. 12B is a schematic diagram for explaining the order of stripping the treatment film from the experimental substrate 200.

[0357] In this experiment, a substrate with any one of Si (bare silicon: Bare-Si), SiN, SiO2, W, TiN, Co, Cu, Ru, and amorphous carbon (a-C) exposed on the surface is used as the experimental substrate 200, and any one of hydrochloric acid, SC1, hydrofluoric acid, SPM, and IPA is used as the hydrophilic liquid.

[0358] The experimental substrate 200 used in this experiment is a square small substrate with a side length of 3 cm when viewed from above.

[0359] The mass percentage concentration of hydrogen chloride in the hydrochloric acid used in this experiment is 0.4%. The SC1 used in this experiment is a mixed solution of ammonia water with a mass percentage concentration of 0.4% of ammonia and hydrogen peroxide water with a mass percentage concentration of 3.5% of hydrogen peroxide.

[0360] The mass percentage concentration of hydrogen fluoride in the hydrofluoric acid used in this experiment is 0.5%. The SPM used in this experiment is a mixed solution of heated dilute sulfuric acid with a mass percentage concentration of 64.0% of sulfuric acid and hydrogen peroxide water with a mass percentage concentration of 10.0% of hydrogen peroxide. The pure water used in this experiment is DIW.

[0361] This experiment is carried out under various combinations of the substrate and the hydrophilic liquid.

[0362] To measure the contact angle of pure water on the experimental substrate 200, as Fig. 12AAs shown, the experimental substrate 200 was immersed in the hydrophilizing liquid. Then, the experimental substrate 200 was washed with DIW to remove the hydrophilizing liquid from the experimental substrate 200, but the relevant situation is not shown in the figure. A droplet 202 of pure water (DIW) was formed on the hydrophilized experimental substrate 200, and the contact angle θ1 of the droplet 202 was measured.

[0363] In addition, in order to investigate whether the treatment film 201 can be peeled off from the experimental substrate 200, as Fig. 12B shown, the untreated experimental substrate 200 was immersed in the hydrophilizing liquid. Then, as needed, the experimental substrate 200 was washed with pure water and / or IPA, but the relevant situation is not shown in the figure. Then, while supplying the treatment liquid to the experimental substrate 200, the experimental substrate 200 was rotated at 10 rpm for about 2 seconds, and then the experimental substrate 200 was rotated at 1500 rpm for 30 seconds to form the treatment film 201. While rotating the experimental substrate 200 on which the treatment film 201 was formed at 800 rpm, the stripping liquid was supplied to the experimental substrate 200. The surface of the experimental substrate 200 was observed before and after supplying the treatment liquid and after supplying the stripping liquid to determine whether the treatment film could be peeled off. As the stripping liquid, ammonia water with a mass percentage concentration of 0.4% was used.

[0364] The treatment liquid used in the treatment film peeling experiment contains at least one low-solubility component selected from the following low-solubility components and at least one high-solubility component selected from the following high-solubility components as solutes. The treatment liquid used in the treatment film peeling experiment is the treatment liquid PL4 used in the contact angle measurement experiment described below with reference to Fig.14 and Fig.15 The table shows the contact angle θ1 of pure water on the surface of the experimental substrate 200 and whether the treatment film 201 can be peeled off by the stripping liquid.

[0365] Fig.13 is a table listing the contact angle θ1 of pure water on the surface of the experimental substrate 200 and whether the treatment film 201 can be peeled off by the stripping liquid. Fig.13 is a summary table of the results of the treatment film peeling experiment.

[0366] Fig.13 The table shown lists columns of "surface of the substrate", "hydrophilizing liquid", "contact angle of pure water (°)", and "peeling of the treatment film".

[0367] Each row in "surface of the substrate" records the name of the substance exposed from the surface of the experimental substrate 200. Each row in "hydrophilizing liquid" records the name of the hydrophilizing liquid used in the hydrophilization treatment of the experimental substrate 200. If "-" is recorded in a certain row of "hydrophilizing liquid", it means that the treatment film peeling experiment was performed on the substrate without hydrophilization treatment.

[0368] Each row of "Contact angle (°) of pure water" shows the contact angle θ1 of pure water on the experimental substrate 200 after hydrophilization with the same hydrophilizing liquid shown in the same row.

[0369] Each row of "Peeling of treatment film" shows whether the treatment film 201 has been peeled from the experimental substrate 200 after hydrophilization with the same hydrophilizing liquid shown in the same row using a peeling liquid. "OK" indicates that the treatment film 201 has been sufficiently peeled, and "NG" indicates that the peeling of the treatment film 201 is insufficient.

[0370] For example, Fig.13 The first row of the table shows that the contact angle θ1 of pure water on the experimental substrate 200 after hydrophilizing the experimental substrate 200 with the surface exposed to SiN using HCl is 4.8°, and the treatment film 201 has been sufficiently peeled from the experimental substrate 200 by the peeling liquid.

[0371] As Fig.13 shown, when the contact angle θ1 of pure water is 41.7° or more, the treatment film 201 is not sufficiently peeled.

[0372] As Fig.13 shown, even if the substances exposed on the surface of the experimental substrate 200 are the same, as long as the hydrophilizing liquid is different, the contact angle θ1 of pure water on the surface of the experimental substrate 200 is different. For example, when using HF as the hydrophilizing liquid to hydrophilize the experimental substrate 200 with the surface exposed to TiN, the contact angle θ1 of pure water is 15.2°, and the removal of the treatment film 201 is sufficient. When using SC1 as the hydrophilizing liquid to hydrophilize the experimental substrate 200 with the surface exposed to TiN, the contact angle θ1 of pure water is 28.3°, and the removal of the treatment film 201 is sufficient. On the other hand, when using IPA as the hydrophilizing liquid to hydrophilize the experimental substrate 200 with the surface exposed to TiN, the contact angle θ1 of pure water is 41.7°, and the removal of the treatment film 201 is insufficient.

[0373] Therefore, it is speculated that using an oxidizing liquid as the hydrophilizing liquid can improve the hydrophilicity of the substrate surface compared to using an organic solvent as the hydrophilizing liquid. Regarding the reasons, the following reasons can be cited.

[0374] When using an organic solvent as the hydrophilizing liquid, the hydrophobic organic substances attached to the surface of the substrate will dissolve in the organic solvent to hydrophilize the surface of the substrate. Depending on the type of organic substances attached to the surface of the substrate, etc., there are sometimes components that do not dissolve in the organic solvent. Therefore, not all organic substances will be removed.

[0375] On the other hand, when using an oxidation solution as the hydrophilic treatment solution, the portion near the surface of the substrate is oxidized to form an oxide film on the surface of the substrate. Therefore, regardless of the type of organic matter attached to the surface of the substrate, etc., the hydrophilicity of the surface of the substrate can be efficiently improved.

[0376] In addition, when no hydrophilic treatment is performed, the contact angle of pure water on the experimental substrate 200 with exposed TiN on the surface is 59.6°. Therefore, regardless of which hydrophilic treatment solution among IPA, HF, and SC1 is used, the experimental substrate 200 with exposed TiN on the surface is hydrophilized.

[0377] <Regarding the contact angle measurement experiment of the treatment film>

[0378] Next, the results of the contact angle measurement experiment for measuring the contact angle of pure water on the treatment film formed on the surface of the experimental substrate will be described. Fig.14 It is a schematic diagram for explaining the order of measuring the contact angle of pure water on the surface of the treatment film.

[0379] In this experiment, a substrate with exposed Si (bare silicon: Bare-Si) on the surface was used as the experimental substrate 203, and IPA was used as the hydrophilic treatment solution. Four treatment solutions PL1 to PL4 were used as the treatment solutions. Each of the treatment solutions PL1 to PL4 contained IPA as a solvent. Each of the treatment solutions PL1 to PL4 contained at least one poorly soluble component selected from the following poorly soluble components and at least one highly soluble component selected from the following highly soluble components as solutes. The poorly soluble components contained in the treatment solutions PL1 to PL4 were common. The highly soluble components contained in the treatment solutions PL1 to PL4 were different substances from each other.

[0380] As Fig.15 shown, the experimental substrate 203 was immersed in IPA as the hydrophilic treatment solution. Then, the experimental substrate 203 was washed with DIW, but the relevant situation is not shown in the figure. Then, the treatment solution was dropped onto the surface of the experimental substrate 203. Then, the solvent in the treatment solution was evaporated, thereby forming a treatment film 204 on the surface of the experimental substrate 203. Then, a droplet 205 of pure water (DIW) was formed on the treatment film 204 formed on the experimental substrate 203, and the contact angle θ2 of the droplet 205 was measured.

[0381] Fig.15 It is a table listing the contact angle θ2 of pure water on the surface of the treatment film 204 and whether the treatment film 204 can be peeled off by the stripping solution.

[0382] Fig.15The table shown lists two columns: "Processing Liquid" and "Contact Angle of Pure Water (°)". Each row in "Processing Liquid" records which one of the processing liquids PL1 to PL4 was used when forming the processing film 204. Each row in "Contact Angle of Pure Water (°)" records the contact angle θ2 of pure water on the processing film 204 formed using the processing liquid shown in the same row. The contact angle θ2 of pure water on the processing film 204 is an angle within the range of 52° or more and 61° or less. Therefore, it is speculated that if the contact angle θ2 of pure water on the processing film 204 is used, the processing film formed on the hydrophilized substrate can be effectively peeled off using the stripping liquid.

[0383] <Configuration of the Substrate Processing Apparatus of the Second Embodiment>

[0384] Fig.16 It is a schematic diagram for explaining a configuration example of the processing unit 2 of the substrate processing apparatus 1P of the second embodiment. Fig.16 In it, for the configuration equivalent to the Figure 1 to Figure 15 shown configuration, the same reference signs as Figure 1 etc. are marked, and the related description is omitted. In the following Figures 17 to 21 as well, the same reference signs as Figure 1 etc. are marked, and the related description is omitted.

[0385] The main difference between the substrate processing apparatus 1P of the second embodiment and the substrate processing apparatus 1 of the first embodiment is that the stripping liquid ejected from the third moving nozzle 11 is a second stripping liquid such as diluted IPA for the upper surface of the substrate W, and the surface of the substrate W is hydrophilized by the second stripping liquid. Therefore, the first moving nozzle 9 for ejecting the hydrophilizing liquid is not provided.

[0386] The processing film is more soluble in an organic solvent than an alkaline aqueous solution (alkaline liquid) such as ammonia water, pure water, and a neutral or acidic aqueous solution (non-alkaline aqueous solution). The respective components (solvent, low-solubility component, high-solubility component, and anti-corrosion component) contained in the processing liquid are the same as those in the first embodiment, and the relevant details will be described below.

[0387] As the second stripping liquid, a liquid that can dissolve the high-solubility component contained in the processing liquid more easily than the low-solubility component contained in the processing liquid can be used. The second stripping liquid is, for example, a diluted organic solvent such as diluted IPA. A diluted organic solvent means a solvent obtained by diluting an organic solvent with pure water, and is a mixed liquid of an organic solvent and pure water. In this embodiment, as pure water, DIW is used.

[0388] When the second stripping liquid is diluted IPA, the mass percentage concentration of IPA in the second stripping liquid is preferably 1% or more and 33% or less, more preferably 12% or more and 33% or less, and still more preferably 20% or more and 33% or less.

[0389] When the mass percentage concentration of IPA in the second stripping liquid is 1% or more and 33% or less, the processing film on the substrate W can be dissolved moderately while the processing film is stripped from the substrate W.

[0390] The second stripping liquid is a liquid that can hydrophilize (improve hydrophilicity) the upper surface of the substrate W.

[0391] When the mass percentage concentration of IPA in the diluted IPA is 12% or more, the contact angle of the diluted IPA on the surface of the substrate W is less than 41.7°. When the mass percentage concentration of IPA in the diluted IPA is 12% or more, the surface of the substrate W can be moderately hydrophilized.

[0392] Next, the case of hydrophilizing the surface of the substrate W will be described. Fig.17 It is a schematic diagram for explaining the case of hydrophilizing the surface of the substrate W by the second stripping liquid. When a diluted organic solvent such as diluted IPA is used as the second stripping liquid, as Fig.17 shown, the hydrophobic organic matter 170 present on the surface of the substrate W is dissolved in the second stripping liquid, and the surface of the substrate W is hydrophilized. When there is an organic matter 170A on the surface of the substrate W that is difficult to dissolve in the diluted organic solvent, after hydrophilizing the surface of the substrate W, the organic matter 170A still remains on the substrate W.

[0393] The organic matter is only a part of the object to be removed present on the surface of the substrate W. Even if the organic matter is removed by an organic solvent, the removal of the object to be removed is not sufficient. Therefore, when the surface of the substrate W is hydrophilized by a diluted organic solvent, it is still necessary to remove the object to be removed by stripping the processing film.

[0394] The substrate W having a surface exposing at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C can be hydrophilized by the second stripping liquid. In particular, the substrate W having a surface exposing at least any one of Si, SiN, SiO2, W, TiN, Co, Cu, and Ru is more easily hydrophilized by the second stripping liquid, and the substrate W having a surface exposing any one of Si, SiN, SiO2, W, TiN, Co, and Cu is even more easily hydrophilized by the second stripping liquid.

[0395] When the contact angle of pure water on the processing film is greater than 52° and less than 61°, the following second stripping liquid can act sufficiently on the interface between the substrate W and the processing film. When a processing liquid is used, a processing film with a contact angle of pure water greater than 52° and less than 61° can be formed.

[0396] The organic solvent ejected from the central nozzle 12 is composed of the same substance (organic compound) as the organic solvent in the diluted organic solvent that serves as the second stripping liquid. Therefore, the organic solvent is compatible with the second stripping liquid. The organic solvent dissolves and removes the residue of the processing film, which is the substance remaining on the upper surface of the substrate W after the processing film is stripped from the upper surface of the substrate W by the second stripping liquid and removed. The organic solvent functions as a residue removal liquid. The residue removal liquid is also called a residue dissolving liquid. Regarding the properties of the residue removal liquid, refer to the above description. As the organic solvent ejected from the central nozzle 12, for example, the organic solvent exemplified as the organic solvent ejected from the central nozzle 12 in the first embodiment can be used.

[0397] In this embodiment, the second stripping liquid ejected from the lower nozzle 13 is the same as the second stripping liquid ejected from the third moving nozzle 11, so the relevant description is omitted.

[0398] <Substrate Processing of the Second Embodiment>

[0399] Fig.18 It is a flowchart for explaining an example of the substrate processing by the substrate processing apparatus 1P. Fig.18 It mainly represents the processing implemented by executing a program by the controller 3. Figures 19A to 19F It is a schematic diagram for explaining the respective steps of the substrate processing.

[0400] In the substrate processing performed by the substrate processing apparatus 1P, for example, as Fig.18 shown, the substrate loading step (step S21), the processing liquid supply step (step S22), the processing film formation step (step S23), the stripping liquid supply step (step S24), the cleaning step (step S25), the residue removal liquid supply step (step S26), the spin drying step (step S27), and the substrate unloading step (step S28) are sequentially executed.

[0401] Next, mainly with reference to Fig.16 and Fig.18 . Optionally refer to Figures 19A to 19F .

[0402] First, the unprocessed substrate W is loaded into the processing unit 2 from the carrier C by the transfer robots IR and CR (refer to Figure 1 ) and delivered to the rotary chuck 5 (step S21). Thereby, the substrate W is horizontally held by the rotary chuck 5 (substrate holding step). When loading the substrate W, the opposing member 6 retracts to the upper position.

[0403] The holding of the substrate W by the rotary chuck 5 continues until the end of the spin drying step (step S27). During the period from the start of the substrate holding step to the end of the spin drying step (step S27), the guard lift unit 74 adjusts the height positions of the first guard 71A and the second guard 71B so that at least one guard 71 is in the upper position.

[0404] While the substrate W is held by the rotary chuck 5, the rotation motor 23 rotates the rotary base 21. Thereby, the horizontally held substrate W starts to rotate (substrate rotation step). The facing member rotation unit 62 may also rotate the facing member 6 in synchronization with the rotary base 21. Synchronous rotation means that the facing member 6 and the rotary base 21 rotate in the same rotation direction at the same rotation speed.

[0405] Next, after the transfer robot CR retreats outside the processing unit 2, a processing liquid supply step (step S22) is performed, that is, the processing liquid is supplied to the upper surface of the substrate W. Specifically, in a state where the facing member 6 is in the retracted position, the second nozzle moving unit 36 moves the second moving nozzle 10 to the processing position. The processing position of the second moving nozzle 10 is, for example, the central position. When the facing member 6 is in the retracted position, each moving nozzle can move horizontally between the facing member 6 and the substrate W. The retracted position may also be the upper position.

[0406] With the second moving nozzle 10 in the processing position, the processing liquid valve 54 is opened. Thereby, as Fig.19A shown, the processing liquid is supplied (sprayed) from the second moving nozzle 10 to the central region of the upper surface of the rotating substrate W (processing liquid supply step, processing liquid spraying step). The processing liquid supplied to the upper surface of the substrate W diffuses to the entire substrate W by centrifugal force. Thereby, a liquid film 101 (processing liquid film) of the processing liquid is formed on the substrate W (processing liquid film forming step).

[0407] The supply of the processing liquid from the second moving nozzle 10 continues for a specified time, for example, 2 seconds to 4 seconds. In the processing liquid supply step, the substrate W rotates at a specified processing liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0408] Next, the Fig.19B and Fig.19C shown processing film forming step (step S23) is performed. In the processing film forming step, the processing liquid on the substrate W is solidified or hardened, and a processing film 100 for holding the removal object existing on the substrate W is formed on the upper surface of the substrate W (refer to Fig.19C ).

[0409] In the processing film formation step, first, a processing liquid thinning step (processing liquid rotation stop step) is performed, that is, the thickness of the liquid film 101 of the processing liquid on the substrate W is thinned. Specifically, the processing liquid valve 54 is closed. Thus, as Fig.19B shown, the supply of the processing liquid to the substrate W is stopped. Then, the second moving nozzle 10 is moved to the initial position by the second nozzle moving unit 36.

[0410] As Fig.19B shown, in the processing liquid thinning step, the substrate W rotates in a state where the supply of the processing liquid to the upper surface of the substrate W is stopped, so a part of the processing liquid is excluded from the upper surface of the substrate W. Thus, the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness. After moving the second moving nozzle 10 to the initial position, the opposing member 6 still remains in the retracted position.

[0411] In the processing liquid thinning step, the rotation motor 23 changes the rotation speed of the substrate W to the specified processing liquid thinning speed. The processing liquid thinning speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept fixed within the range of 300 rpm to 1500 rpm, or can be appropriately changed within the range of 300 rpm to 1500 rpm in the middle of the processing liquid thinning step. The processing liquid thinning step is continuously performed for a specified time, for example, 30 seconds.

[0412] In the processing film formation step, after the processing liquid thinning step, a processing liquid solvent evaporation step is performed, that is, a part of the solvent is evaporated (volatilized) from the liquid film 101 of the processing liquid. In the processing liquid solvent evaporation step, since a part of the solvent of the processing liquid on the substrate W is to be evaporated, the liquid film 101 on the substrate W is heated.

[0413] Specifically, as Fig.19C shown, the opposing member lifting unit 61 moves the opposing member 6 to the proximity position. The proximity position can also be the lower position. The proximity position is a position where the distance from the upper surface of the substrate W to the opposing surface 6a is, for example, 1 mm.

[0414] Then, the gas valve 53 is opened. Thus, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 101) and the opposing surface 6a of the opposing member 6 (gas supply step).

[0415] By blowing gas onto the liquid film 101 on the substrate W, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (processing liquid solvent evaporation step, processing liquid solvent evaporation promotion step). Therefore, the time required to form the processing film 100 can be shortened. In the processing film formation step, the central nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0416] After a part of the processing liquid is excluded from the substrate W through the step of thinning the processing liquid film of the liquid film 101, the opposing member 6 and the substrate W still continue to rotate. Therefore, the centrifugal force generated by the rotation of the opposing member 6 and the substrate W acts on the gas ejected from the central nozzle 12. Due to the action of the centrifugal force, the gas forms an air flow from the center side to the peripheral side of the substrate W. Therefore, the solvent in the gas state in contact with the liquid film 101 is promoted to be excluded from the space between the opposing member 6 and the substrate W. Thereby, the evaporation of the solvent in the liquid film 101 is promoted. As described above, the opposing member 6 and the rotation motor 23 function as an evaporation unit (evaporation promotion unit) for evaporating (volatilizing) the solvent in the processing liquid. It is also possible that the opposing member 6 does not rotate and only the substrate W rotates.

[0417] In addition, the heat medium valve 88 is opened. Thereby, as Fig.19C shown, the heat medium (heat medium supply step, heat medium ejection step) is supplied (ejected) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W. The heat medium supplied to the lower surface of the substrate W from the lower nozzle 13 is subjected to centrifugal force and diffuses radially, covering the entire lower surface of the substrate W.

[0418] The supply of the heat medium to the substrate W continues for a specified time, for example, 60 seconds. In the processing liquid solvent evaporation step, the substrate W rotates at a specified evaporation rotation speed, for example, 1000 rpm.

[0419] By supplying the heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated through the substrate W. Thereby, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (processing liquid solvent evaporation step, processing liquid solvent evaporation promotion step). Therefore, the time required to form the processing film 100 can be shortened. In the processing film forming step, the lower nozzle 13 also functions as an evaporation unit (evaporation promotion unit) for evaporating (volatilizing) the solvent in the processing liquid.

[0420] By performing the processing liquid thinning step and the processing liquid solvent evaporation step, the processing liquid is solidified or hardened. Thereby, a processing film 100 for holding the object to be removed is formed on the entire upper surface of the substrate W.

[0421] As described above, the substrate rotation unit (rotation motor 23), the opposing member rotation unit 62, the central nozzle 12, and the lower nozzle 13 constitute a processing film forming unit for solidifying or hardening the processing liquid to form a solid processing film 100.

[0422] By using the blowing of gas, the rotation of the substrate W, and the heating of the substrate W, the processing film 100 can be formed quickly, but the processing film 100 can also be formed by the blowing of gas and the rotation of the substrate W. That is, the formation of the processing film 100 does not necessarily require the step of heating with a heat medium. Therefore, the supply of the heat medium to the substrate W can be omitted.

[0423] In the step of evaporating the solvent of the treatment liquid, it is preferable to heat the substrate W in such a way that the temperature of the substrate W is lower than the boiling point of the solvent. By heating the substrate W to a temperature lower than the boiling point of the solvent, it is possible to suppress the situation where the solvent evaporates completely, and thus it is possible to moderately retain the solvent in the treatment film 100. As a result, compared with the case where no solvent remains in the treatment film 100, in the subsequent stripping liquid supply step (step S24), it is easier for the second stripping liquid to act on the treatment film 100.

[0424] Next, the stripping liquid supply step (step S24) is executed, that is, the second stripping liquid is supplied to the upper surface of the substrate W. Specifically, the heat medium valve 88 is closed. As a result, the supply of the heat medium to the lower surface of the substrate W is stopped. In addition, the gas valve 53 is closed. As a result, the supply of gas to the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is stopped.

[0425] Then, the opposing member lifting unit 61 moves the opposing member 6 to the retracted position. In a state where the opposing member 6 is in the retracted position, the third nozzle moving unit 37 moves the third moving nozzle 11 to the treatment position. The treatment position of the third moving nozzle 11 is, for example, the central position.

[0426] Then, with the third moving nozzle 11 in the treatment position, the upper side stripping liquid valve 55 is opened. As a result, as Fig.19D shown, the second stripping liquid (upper side stripping liquid) is supplied (sprayed) from the third moving nozzle 11 to the central region of the upper surface of the rotating substrate W (upper side stripping liquid supply step, upper side stripping liquid spraying step). The second stripping liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. As a result, the treatment film 100 on the upper surface of the substrate W is peeled off and discharged outside the substrate W together with the second stripping liquid.

[0427] While opening the upper side stripping liquid valve 55, the lower side stripping liquid valve 87 is opened. As a result, as Fig.19D shown, the second stripping liquid (lower side stripping liquid) is supplied (sprayed) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W (lower side stripping liquid supply step, lower side stripping liquid spraying step). The second stripping liquid supplied to the lower surface of the substrate W diffuses to the entire lower surface of the substrate W by centrifugal force.

[0428] The supply of the second stripping liquid to the upper surface and the lower surface of the substrate W continues for a specified time, for example, 60 seconds. In the stripping liquid supply step, the substrate W rotates at a specified stripping rotation speed, for example, 800 rpm.

[0429] Here, in Fig.19AIn the processing liquid supply step (step S22) shown, the processing liquid supplied to the upper surface of the substrate W may sometimes adhere to the lower surface of the substrate W along the periphery of the substrate W, and the processing liquid adhering to the lower surface of the substrate W solidifies or hardens to form a solid.

[0430] Similarly in this case, as Fig.19D shown, in the stripping liquid supply step (step S24), while supplying the second stripping liquid to the upper surface of the substrate W, the second stripping liquid is supplied (sprayed) from the lower nozzle 13 to the lower surface of the substrate W. Therefore, even if a solid of the processing liquid is formed on the lower surface of the substrate W, the solid can be stripped and removed from the lower surface of the substrate W.

[0431] After the stripping liquid supply step (step S24), a cleaning step (step S25) is performed, that is, the second stripping liquid is flushed from the substrate W by the cleaning liquid. Since the second stripping liquid is discharged out of the substrate W by the cleaning liquid, the cleaning step (step S25) is also called the stripping liquid discharge step.

[0432] Specifically, the upper stripping liquid valve 55 and the lower stripping liquid valve 87 are closed. Thereby, the supply of the second stripping liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to the initial position. Then, as Fig.19E shown, the facing member lifting unit 61 moves the facing member 6 to the processing position between the retracted position and the lower position. When the facing member 6 is located at the processing position, the distance between the upper surface of the substrate W and the facing surface 6a is, for example, 30 mm.

[0433] Then, with the facing member 6 located at the processing position, the upper cleaning liquid valve 51 is opened. Thereby, as Fig.19E shown, the cleaning liquid (upper cleaning liquid supply step, upper cleaning liquid spraying step) is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W. The cleaning liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, the second stripping liquid adhering to the upper surface of the substrate W is discharged out of the substrate W together with the cleaning liquid, and the stripping liquid is replaced with the cleaning liquid (stripping liquid discharge step).

[0434] In addition, while opening the upper cleaning liquid valve 51, the lower cleaning liquid valve 86 is opened. Thereby, as Fig.19E shown, the cleaning liquid (lower cleaning liquid supply step, lower cleaning liquid spraying step) is supplied (sprayed) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W. Thereby, the second stripping liquid adhering to the lower surface of the substrate W is discharged out of the substrate W together with the cleaning liquid, and the stripping liquid is replaced with the cleaning liquid (lower stripping liquid discharge step).

[0435] The supply of the cleaning liquid to the upper and lower surfaces of the substrate W is continued for a specified time, for example, 30 seconds. In the cleaning step (step S25), the substrate W is rotated at a specified stripping liquid removal rotation speed, for example, 800 rpm.

[0436] Next, a residue removal liquid supply step (step S28) is performed, that is, a residue removal liquid such as IPA is supplied.

[0437] Specifically, the upper side cleaning liquid valve 51 and the lower side cleaning liquid valve 86 are closed. Thereby, the supply of the cleaning liquid to the upper and lower surfaces of the substrate W is stopped. Then, with the facing member 6 in the processing position, the organic solvent valve 52 is opened. Thereby, as Fig.19F shown, the residue removal liquid (organic solvent) is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (residue removal liquid supply step, residue removal liquid spraying step).

[0438] The residue removal liquid supplied from the central nozzle 12 to the upper surface of the substrate W is subjected to centrifugal force and spreads radially to cover the entire upper surface of the substrate W. Sometimes, after the processing film is peeled off from the substrate W by the second stripping liquid and removed from the substrate W, residues of the processing film still remain on the upper surface of the substrate W. The residue removal liquid supplied to the upper surface of the substrate W dissolves such residues of the processing film. The residue removal liquid after dissolving the residues of the processing film is discharged from the periphery of the upper surface of the substrate W by centrifugal force. Thereby, the residues of the processing film on the substrate W are removed (residue removal step).

[0439] In the residue removal liquid supply step, the spraying of the residue removal liquid from the central nozzle 12 is continued for a specified time, for example, 30 seconds. In the residue removal liquid supply step, the substrate W is rotated at a specified residue removal rotation speed, for example, 300 rpm.

[0440] Next, a rotation drying step (step S7) is performed, that is, the substrate W is rotated at a high speed to dry the upper surface of the substrate W. Specifically, the organic solvent valve 52 is closed. Thereby, the supply of the organic solvent to the upper surface of the substrate W is stopped. Then, the facing member lifting unit 61 moves the facing member 6 to a drying position lower than the processing position. When the facing member 6 is in the drying position, the distance between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 53 is opened. Thereby, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

[0441] Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed. The substrate W in the spin-drying step rotates at a drying speed, for example, 1500 rpm. The spin-drying step is continuously performed for a specified time, for example, 30 seconds. Thus, a huge centrifugal force acts on the organic solvent on the substrate W, and the organic solvent on the substrate W is flung toward the periphery of the substrate W. In the spin-drying step, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6, thereby promoting the evaporation of the organic solvent.

[0442] Then, the rotation motor 23 stops the rotation of the substrate W. The guard elevation unit 74 moves the first guard 71A and the second guard 71B to the lower position. The gas valve 53 is closed. Then, the facing member elevation unit 61 moves the facing member 6 to the upper position.

[0443] The transfer robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pin 20 of the rotary chuck 5, and carries it out of the processing unit 2 (step S28). This substrate W is delivered from the transfer robot CR to the transfer robot IR and stored in the carrier C by the transfer robot IR.

[0444] <Case of peeling the processing film in the second embodiment>

[0445] Next, use Figure 30A to Figure 30C to describe in detail the case of peeling the processing film 100 from the substrate W. Figure 30A to Figure 30C is a schematic diagram for explaining the case of peeling the processing film 100 from the substrate W.

[0446] As Fig. 30A shown, the processing film 100 holds the object to be removed 103 attached to the surface layer 150 of the substrate W. The processing film 100 has a highly soluble solid 110 (highly soluble component in solid state) and a lowly soluble solid 111 (lowly soluble component in solid state). The highly soluble solid 110 and the lowly soluble solid 111 are formed by evaporation of at least a part of the solvent contained in the processing liquid.

[0447] The highly soluble solid 110 and the lowly soluble solid 111 are mixed and present in the processing film 100. Strictly speaking, the processing film 100 is not such that the highly soluble solid 110 and the lowly soluble solid 111 are uniformly distributed throughout the processing film 100. In the processing film 100, there are parts where the highly soluble solid 110 is concentrated and parts where the lowly soluble solid 111 is concentrated.

[0448] Refer to Fig. 30B, the highly soluble solid 110 is dissolved by the second stripping liquid. That is, the treatment film 100 is partially dissolved (dissolution step, partial dissolution step). By dissolving the highly soluble solid 110, through-holes 102 are formed in the part where the highly soluble solid 110 is concentrated and present in the treatment film 100 (through-hole formation step).

[0449] The through-holes 102 are particularly likely to be formed in the part where the highly soluble solid 110 extends along the thickness direction T of the treatment film 100. The through-holes 102 are, for example, several nanometers in diameter when viewed from above.

[0450] Here, when an appropriate amount of solvent remains in the treatment film 100, the second stripping liquid dissolves the treatment film 100 while dissolving into the solvent remaining on the treatment film 100. Specifically, the second stripping liquid dissolves the highly soluble solid 110 in the treatment film 100 while dissolving into the solvent remaining on the highly soluble solid 110 to form through-holes 102. Therefore, the second stripping liquid easily enters the treatment film 100 (dissolution and entry step).

[0451] The second stripping liquid passes through the through-holes 102 and reaches the upper surface of the substrate W, making the upper surface of the substrate W hydrophilic (hydrophilic treatment step). The upper surface of the substrate W is made hydrophilic, so that the contact angle of pure water on the upper surface of the substrate W is less than 41.7° (contact angle reduction step). The second stripping liquid reaching the upper surface of the substrate W acts on the interface between the treatment film 100 and the substrate W, strips the treatment film 100, and excludes the stripped treatment film 100 from the upper surface of the substrate W (stripping and exclusion step).

[0452] Specifically, the low solubility component has low solubility in the second stripping liquid, and the low soluble solid 111 is hardly dissolved by the second stripping liquid. Therefore, only the vicinity of the surface of the low soluble solid 111 is dissolved by the second stripping liquid. Therefore, the second stripping liquid reaching the vicinity of the upper surface of the substrate W via the through-holes 102 only dissolves the part of the low soluble solid 111 near the upper surface of the substrate W. Thus, as shown in the enlarged view Fig. 30B The second stripping liquid slowly dissolves the low soluble solid 111 near the upper surface of the substrate W while entering the gap G1 between the treatment film 100 and the upper surface of the substrate W (stripping liquid entry step).

[0453] Then, for example, the treatment film 100 splits starting from the periphery of the through-holes 102 and becomes membrane pieces 105. As shown in Fig. 10C The membrane pieces 105 of the treatment film 100 are stripped from the substrate W while holding the object to be removed 103 (treatment film splitting step, treatment film stripping step).

[0454] Then, the second stripping liquid is continuously supplied, whereby the processing film 100 that has become the film sheet 105 is washed away while maintaining the object to be removed 103. In other words, the film sheet 105 holding the object to be removed 103 is pushed out of the substrate W and excluded from the upper surface of the substrate W (processing film exclusion step, object to be removed exclusion step). Thereby, the upper surface of the substrate W can be cleaned well.

[0455] <Summary of the Second Embodiment>

[0456] In summary, according to the second embodiment, by solidifying or hardening the processing liquid supplied to the upper surface of the substrate W, the processing film 100 holding the object to be removed 103 is formed. Then, the second stripping liquid is supplied to the upper surface of the substrate W. By supplying the second stripping liquid, through-holes 102 are formed in the processing film 100, the upper surface of the substrate W is hydrophilized, and the processing film 100 holding the object to be removed 103 is peeled off from the upper surface of the substrate W. That is, the formation of the through-holes 102, the hydrophilization of the substrate W, and the peeling of the processing film 100 are all caused by the supply of a single second stripping liquid.

[0457] According to the second embodiment, the second stripping liquid is a mixed liquid of an organic solvent and water. The processing film 100 is more soluble in the organic solvent than in water or ammonia water. Therefore, the second stripping liquid, which is a mixed liquid of an organic solvent and water, is less likely to dissolve the processing film 100 than the organic solvent. Therefore, the second stripping liquid partially dissolves the processing film 100. Thereby, through-holes 102 (gaps, spaces) are formed in the processing film 100. The second stripping liquid can pass through the through-holes 102 and reach the upper surface of the substrate W. The second stripping liquid reaching the upper surface of the substrate W acts on the interface between the processing film 100 and the substrate W.

[0458] Therefore, compared with the method of not forming gaps such as through-holes 102 in the processing film 100 but allowing the stripping liquid to penetrate into the processing film 100 to reach the interface between the processing film 100 and the substrate W, a large amount of the second stripping liquid can quickly reach the interface between the processing film 100 and the substrate W.

[0459] The stripping liquid is a diluted organic solvent. Since the processing film 100 is more soluble in the organic solvent than in water or ammonia water, the diluted organic solvent has a higher solubility in the processing film 100 than water or ammonia water. Although the processing film 100 is partially dissolved by the second stripping liquid to form the through-holes 102, the remaining part will maintain a solid state. Therefore, through the second stripping liquid, the surface of the part (low-solubility solid 111) of the processing film 100 that maintains a solid state can be moderately dissolved, so that the processing film 100 holding the object to be removed 103 can be effectively peeled off from the upper surface of the substrate W. Therefore, compared with the method of peeling off the processing film 100 without using an organic solvent, the processing film 100 can be peeled off efficiently.

[0460] According to the second embodiment, the solubility of the highly soluble component in the second stripping liquid is higher than that of the low-soluble component in the second stripping liquid. Therefore, the highly soluble solid 110 is more easily dissolved in the second stripping liquid than the low-soluble solid 111. Therefore, the highly soluble solid 110 will dissolve in the second stripping liquid, and through holes 102 will be formed in the processing film 100. On the other hand, the low-soluble solid 111 does not dissolve in the stripping liquid and remains in a solid state.

[0461] Therefore, it is possible to dissolve the highly soluble solid 110 in the second stripping liquid and keep the low-soluble solid 111 insoluble in the stripping liquid and in a solid state. Therefore, the second stripping liquid passes through the through holes 102 formed by the dissolution of the highly soluble solid 110 and reaches the interface between the substrate W and the low-soluble solid 111. Therefore, it is possible to hold the object to be removed 103 with the low-soluble solid 111 and make the second stripping liquid act on the interface between the low-soluble solid 111 and the substrate W. As a result, it is possible to quickly peel the processing film 100 from the substrate W and effectively remove the object to be removed 103 together with the processing film 100 from the substrate W.

[0462] According to the second embodiment, the second stripping liquid enters between the upper surface of the substrate W and the processing film 100 (low-soluble solid 111). Therefore, the second stripping liquid can act on the interface between the processing film 100 and the substrate W, and the processing film 100 can be peeled off from the upper surface of the substrate W more efficiently.

[0463] When the second stripping liquid is diluted IPA, if the mass percentage concentration of IPA in the second stripping liquid is 12% or more and 33% or less, the surface of the processing film 100 can be moderately dissolved, so that the processing film 100 holding the object to be removed 103 can be peeled off from the upper surface of the substrate W.

[0464] According to the second embodiment, the residue removal liquid supplied to the upper and lower surfaces of the substrate W in the residue removal liquid supply step (step S28) is an organic solvent composed of the same substance (IPA) as the organic solvent in the second stripping liquid. That is, the organic solvent in the diluted organic solvent used as the second stripping liquid is the same organic compound as the organic solvent used as the residue removal liquid. Therefore, compared with the method in which the organic solvent in the second stripping liquid and the organic solvent used as the residue removal liquid are different substances (organic compounds), the types of liquids used can be reduced. Therefore, the cost required to remove the object to be removed 103 from the substrate W can be reduced.

[0465] The higher the hydrophilicity of the upper surface of the substrate W, the easier it is for the stripping liquid to act on the interface between the substrate W and the treatment film 100, so that the treatment film 100 can be effectively stripped from the upper surface of the substrate W. In the second embodiment, the portion of the upper surface of the substrate W exposed due to the formation of the through holes 102 is hydrophilized by the second stripping liquid. Therefore, the second stripping liquid can effectively act on the interface between the portion of the treatment film 100 surrounding the through holes 102 and the substrate W. That is to say, the second stripping liquid can quickly enter between the treatment film 100 and the substrate W. Therefore, the treatment film 100 holding the object to be removed 103 can be effectively removed from the upper surface of the substrate W.

[0466] In the second embodiment, the second stripping liquid is a diluted organic solvent, and the residue removing liquid is an organic solvent, so the residue removing liquid is compatible with the second stripping liquid. Therefore, in the substrate treatment of the second embodiment (refer to Fig.18 ), the cleaning step (step S25) can be omitted.

[0467] <Example of Variation of Substrate Treatment Apparatus of Second Embodiment>

[0468] Fig.21 It is a schematic diagram for explaining the case of the stripping liquid supply step (step S24) of the substrate treatment in the variation of the substrate treatment apparatus 1P of the second embodiment. In the substrate treatment apparatus 1P of this variation, a mixing valve 90 is connected to the upper stripping liquid pipe 45 for supplying the second stripping liquid to the third moving nozzle 11.

[0469] An organic solvent pipe 91 and a pure water pipe 92 are connected to the mixing valve 90. By opening the organic solvent valve 93A inserted in the organic solvent pipe 91, an organic solvent such as IPA is supplied to the mixing valve 90. By opening the pure water valve 94A inserted in the pure water pipe 92, pure water such as DIW is supplied to the mixing valve 90. By adjusting the opening degree of the organic solvent adjusting valve 93B inserted in the organic solvent pipe 91 and the opening degree of the pure water adjusting valve 94B inserted in the pure water pipe 92, the concentration of the organic solvent in the diluted organic solvent in the mixing valve 90 can be adjusted.

[0470] Therefore, in the stripping liquid supply step (step S24), the opening degrees of the organic solvent adjusting valve 93B and the pure water adjusting valve 94B can be adjusted during the supply of the second stripping liquid to the upper surface of the substrate W, so as to adjust the concentration of the organic solvent in the second stripping liquid supplied to the upper surface of the substrate W (organic solvent concentration adjustment step). For example, by increasing the opening degree of the organic solvent adjusting valve 93B, the concentration of the organic solvent in the second stripping liquid can be increased during the supply of the second stripping liquid to the upper surface of the substrate W.

[0471] If the concentration of the organic solvent is increased so that the second stripping liquid finally does not contain pure water, the residue on the processing film 100 can be removed from the upper surface of the substrate W. That is, the organic solvent ejected from the third moving nozzle 11 can function as a residue removal liquid. Thus, after the stripping liquid supply step, the residue removal liquid supply step can be smoothly started.

[0472] Conversely, by reducing the opening degree of the organic solvent adjustment valve 93B, the concentration of the organic solvent in the second stripping liquid can be reduced during the supply of the second stripping liquid to the upper surface of the substrate W.

[0473] <Configuration of the Substrate Processing Apparatus According to the Third Embodiment>

[0474] Fig. 22 It is a partial cross-sectional schematic view showing a schematic configuration of the processing unit 2 included in the substrate processing apparatus 1Q according to the third embodiment of the present invention.

[0475] Fig. 22 Among them, the same reference numerals as those of the Figure 1 to Figure 21 shown configuration are given to the equivalent configuration, and the related description is omitted. In the following Figure 1 , the same reference numerals as those of the Figure 23 to Figure 25D are also given, and the related description is omitted. Figure 1

[0476] The main difference between the substrate processing apparatus 1Q according to the third embodiment and the substrate processing apparatus 1P according to the second embodiment (refer to Fig.16 ) is that the processing unit 2 includes a fourth moving nozzle 14 that supplies (ejects) a dissolving liquid such as ammonia water to the upper surface of the substrate W held by the rotary chuck 5. The fourth moving nozzle 14 is an example of a dissolving liquid supply unit.

[0477] When the fourth moving nozzle 14 is located at the center position, it faces the central region of the upper surface of the substrate W. When the fourth moving nozzle 14 is in the initial position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a top view. The fourth moving nozzle 14 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0478] The fourth nozzle moving unit 38 has the same configuration as the first nozzle moving unit 35. That is, the fourth nozzle moving unit 38 may also include an arm (not shown) connected to the fourth moving nozzle 14 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending along the vertical direction, and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0479] The fourth moving nozzle 14 is connected to a dissolution liquid pipe 47 that guides the dissolution liquid to the fourth moving nozzle 14. After opening a dissolution liquid valve 57 inserted in the dissolution liquid pipe 47, the dissolution liquid is continuously ejected downward from the ejection port of the fourth moving nozzle 14 in a stream. If the dissolution liquid valve 57 is opened when the fourth moving nozzle 14 is in the central position, the dissolution liquid is supplied to the central region of the upper surface of the substrate W.

[0480] As the dissolution liquid, a liquid that can moderately dissolve the processing film on the substrate W can be used. The dissolution liquid is a liquid containing substances different from those in the stripping liquid.

[0481] Specifically, as the dissolution liquid, a liquid that can more easily dissolve the highly soluble components contained in the processing liquid than the low-soluble components contained in the processing liquid can be used. For example, the dissolution liquid is ammonia water with a mass percentage concentration of 0.4%.

[0482] The dissolution liquid can also be, for example, an alkaline aqueous solution (alkaline liquid) other than ammonia water. As specific examples of alkaline aqueous solutions other than ammonia water, an aqueous solution of TMAH (tetramethylammonium hydroxide) and an aqueous solution of choline, and any combination thereof can be cited. The dissolution liquid can be pure water (preferably DIW), or a neutral or acidic aqueous solution (non-alkaline aqueous solution).

[0483] The dissolution liquid is preferably an alkaline solution. The pH of the dissolution liquid is preferably 7 to 13. Specifically, the pH of the dissolution liquid is preferably 8 to 13, more preferably 10 to 13, and further preferably 11 to 12.5. In order to avoid the influence of the dissolution of carbon dioxide gas in the air, the measurement of the pH is preferably performed after degassing.

[0484] Most of the solvent of the dissolution liquid is pure water. The ratio of pure water in the solvent of the dissolution liquid is 50 to 100 mass% (preferably 70 to 100 mass%, more preferably 90 to 100 mass%, further preferably 95 to 100 mass%, and even further preferably 99 to 100 mass%). The so-called "mass%" refers to the ratio of the mass of a certain component in the total mass of the liquid. The mass percentage concentration of the solute of the dissolution liquid is 0.1 to 10% (preferably 0.2 to 8%, more preferably 0.3 to 6%).

[0485] As Figure 5 shown, the dissolution liquid valve 57 and the fourth nozzle moving unit 38 are controlled by the controller 3.

[0486] <Substrate processing of the third embodiment>

[0487] Fig.23 is a flowchart showing an example of processing a substrate by the substrate processing apparatus 1Q of the third embodiment. The substrate processing performed by the substrate processing apparatus 1Q is the same as the substrate processing performed by the substrate processing apparatus 1P of the second embodiment (refer to Fig.18) The main difference is that between the film formation step (step S23) and the stripping liquid supply step (step S24), a dissolution liquid supply step (step S30) and a cleaning step (step S31) are sequentially performed. Hereinafter, the substrate processing performed by the substrate processing apparatus 1Q will be described centering on the dissolution liquid supply step (step S30) and the cleaning step (step S31).

[0488] In addition, the configuration of the substrate W to be processed by the substrate processing apparatus 1Q is the same as that of the substrate to be processed by the substrate processing apparatus 1. That is, a substrate W having a surface exposing at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C can be used.

[0489] Fig.24A It is a schematic diagram for explaining the case of the dissolution liquid supply step (step S30). Fig. 24B It is a schematic diagram for explaining the case of the cleaning step (step S31). After the film formation step (step S23) ends, the dissolution liquid supply step (step S30) is performed as described below.

[0490] First, the heat medium valve 88 is closed. Thereby, the supply of the heat medium to the lower surface of the substrate W is stopped. In addition, the gas valve 53 is closed. Thereby, 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.

[0491] Then, the opposing member lifting unit 61 moves the opposing member 6 to the retracted position. In a state where the opposing member 6 is in the upper position, the fourth nozzle moving unit 38 moves the fourth moving nozzle 14 to the processing position. The processing position of the fourth moving nozzle 14 is, for example, the central position.

[0492] Then, with the fourth moving nozzle 14 in the processing position, the dissolution liquid valve 57 is opened. Thereby, as Fig.24A shown, the dissolution liquid (dissolution liquid supply step, dissolution liquid ejection step) is supplied (ejected) from the fourth moving nozzle 14 to the central region of the upper surface of the rotating substrate W. The dissolution liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, a part of the processing film 100 on the upper surface of the substrate W is dissolved in the dissolution liquid, and the components dissolved in the dissolution liquid are discharged out of the substrate W together with the dissolution liquid.

[0493] The supply of the dissolution liquid to the upper surface of the substrate W continues for a specified time, for example, 60 seconds. In the dissolution liquid supply step, the substrate W rotates at a specified dissolution rotation speed, for example, 800 rpm.

[0494] After the dissolution liquid supply step (step S30), the cleaning step (step S31) described below is performed. In this cleaning step, the dissolution liquid is flushed from the substrate W with the cleaning liquid. Since the dissolution liquid is discharged out of the substrate W with the cleaning liquid, the cleaning step (step S31) is also referred to as the dissolution liquid discharge step.

[0495] In the cleaning step (step S31), first, the dissolution liquid valve 57 is closed. Thereby, the supply of the dissolution liquid to the upper surface of the substrate W is stopped. Then, the fourth nozzle moving unit 38 moves the fourth moving nozzle 14 to the initial position. Then, as Fig. 24B shown, the opposing member lifting unit 61 moves the opposing member 6 to the processing position.

[0496] Then, with the opposing member 6 in the processing position, the upper side cleaning liquid valve 51 is opened. Thereby, as Fig. 24B shown, the cleaning liquid is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (upper side cleaning liquid supply step, upper side cleaning liquid spraying step). The cleaning liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, the dissolution liquid attached to the upper surface of the substrate W is discharged out of the substrate W together with the cleaning liquid, and the dissolution liquid is replaced with the cleaning liquid (dissolution liquid discharge step).

[0497] In addition, while the upper side cleaning liquid valve 51 is opened, the lower side cleaning liquid valve 86 is opened. Thereby, as Fig. 24B shown, the cleaning liquid is supplied (sprayed) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W (lower side cleaning liquid supply step, lower side cleaning liquid spraying step). Thereby, even if the dissolution liquid attached to the upper surface of the substrate W moves from the upper surface of the substrate W to the lower surface of the substrate W along the peripheral portion of the substrate W, causing the lower surface of the substrate W to be attached with the dissolution liquid, the dissolution liquid on the lower surface of the substrate W is flushed with the cleaning liquid.

[0498] The supply of the cleaning liquid to the upper surface and the lower surface of the substrate W continues for a specified time, for example, 30 seconds. In the cleaning step (step S31), the substrate W rotates at a specified dissolution liquid discharge rotation speed, for example, 800 rpm.

[0499] As Fig.23 shown, after the cleaning step (step S31), the stripping liquid supply step (step S24) is performed. Also refer to Fig.19D ). Then, the cleaning step (step S25) - substrate unloading step (step S28) are performed in sequence.

[0500] <The stripping situation of the processing film in the third embodiment>

[0501] Next, use Figures 25A to 25D, the case of peeling the processing film 100 from the substrate W in the substrate processing of the third embodiment will be described in detail. Figures 25A to 25D It is a schematic diagram for explaining the case of peeling the processing film 100 from the substrate W in the substrate processing of the third embodiment.

[0502] As Fig.25A shown, the processing film 100 has the same configuration as the substrate processing of the second embodiment. That is, as Fig.25A shown, the processing film 100 holds the object to be removed 103 attached to the surface layer 150 of the substrate W and has a highly soluble solid 110 and a low soluble solid 111.

[0503] In the substrate processing of the third embodiment, referring to Fig.25B , a dissolution liquid is supplied to the upper surface of the substrate W in a state where the processing film 100 is formed (dissolution liquid supply step). The highly soluble solid 110 is dissolved by the dissolution liquid supplied to the upper surface of the substrate W. That is, the processing film 100 is partially dissolved (dissolution step, partial dissolution step).

[0504] By dissolving the highly soluble solid 110, through holes 102 are formed in the part where the highly soluble solid 110 is concentrated and present in the processing film 100 (through hole formation step). Through holes 102 are formed by the dissolution liquid, but the processing film 100 is not peeled off.

[0505] Here, when an appropriate amount of solvent remains in the processing film 100, the dissolution liquid dissolves the processing film 100 partially while dissolving into the solvent remaining on the processing film 100. Specifically, the dissolution liquid dissolves into the solvent remaining on the highly soluble solid 110 and dissolves the highly soluble solid 110 in the processing film 100 to form through holes 102. Therefore, the dissolution liquid easily enters the processing film 100 (dissolution liquid entry step).

[0506] Then, after removing the dissolution liquid with a cleaning liquid, a second stripping liquid is supplied to the upper surface of the substrate W (stripping liquid supply step). As Fig.25C shown, the second stripping liquid passes through the through holes 102 formed by the dissolution liquid and reaches the upper surface of the substrate W. Thereby, the part of the upper surface of the substrate W exposed due to the formation of the through holes 102 is hydrophilized (hydrophilization step). The upper surface of the substrate W is hydrophilized, so that the contact angle of pure water on the upper surface of the substrate W is less than 41.7° (contact angle reduction step).

[0507] The second stripping liquid reaching the upper surface of the substrate W acts on the interface between the processing film 100 and the substrate W, peels off the processing film 100, and excludes the peeled processing film 100 from the upper surface of the substrate W (peeling and exclusion step).

[0508] Specifically, the low-solubility components have low solubility in the second stripping liquid, and the low-solubility solid 111 is hardly dissolved by the second stripping liquid. Therefore, only the vicinity of the surface of the low-solubility solid 111 is dissolved by the second stripping liquid. Thus, the second stripping liquid that reaches the vicinity of the upper surface of the substrate W through the through-hole 102 dissolves only the portion of the low-solubility solid 111 that is near the upper surface of the substrate W. Thereby, as magnified Fig.25C as shown, while slowly dissolving the low-solubility solid 111 near the upper surface of the substrate W, the second stripping liquid enters the gap G1 between the processing film 100 and the upper surface of the substrate W (stripping liquid entry step).

[0509] During the process of the stripping liquid entering the gap G1, the processing film 100 splits starting from the periphery of the through-hole 102 and becomes the film pieces 105. As Fig.25D shown, the film pieces 105 of the processing film 100 are peeled off from the substrate W while maintaining the state of holding the object to be removed 103 (processing film splitting step, processing film peeling step).

[0510] After the processing film 100 starts to peel off, the second stripping liquid continues to be supplied. Thus, the processing film 100 that has become the film pieces 105 is washed away while maintaining the state of holding the object to be removed 103 by the second stripping liquid. In other words, the film pieces 105 holding the object to be removed 103 are pushed out beyond the substrate W and excluded from the upper surface of the substrate W (processing film exclusion step, object to be removed exclusion step). Thereby, the upper surface of the substrate W can be washed well.

[0511] In summary, according to the third embodiment, a dissolving liquid and a second stripping liquid are respectively supplied to the upper surface of the substrate W on which the processing film 100 is formed. By supplying the dissolving liquid, through-holes 102 are formed in the processing film 100. Then, by supplying the second stripping liquid, the upper surface of the substrate W is hydrophilized, and the processing film 100 is peeled off from the upper surface of the substrate W. That is, the formation of the through-holes 102 and the hydrophilization of the substrate W and the peeling of the processing film 100 are caused by the supply of different liquids.

[0512] <Summary of the Third Embodiment>

[0513] According to the third embodiment, the same effects as those of the second embodiment can be obtained. However, in the third embodiment, different from the second embodiment, a dissolving liquid is supplied to the substrate W after the processing film 100 is formed and before the second stripping liquid is supplied to the substrate W.

[0514] In the third embodiment, if a liquid (e.g., an alkaline liquid such as ammonia water) with a greater difference in solubility between the highly soluble solid 110 and the low-soluble solid 111 than that of the second stripping liquid is used as the dissolving liquid, then after selectively dissolving the highly soluble solid 110 to form the through holes 102, the low-soluble solid 111 can be stripped from the substrate W by the second stripping liquid. That is, it is possible to suppress the loss of the dissolving liquid to the low-soluble solid 111 and to suppress the detachment of the object to be removed from the low-soluble solid 111. Therefore, the processing film 100 holding the object to be removed 103 can be effectively stripped.

[0515] In addition, since it is not necessary to consider the solubility of the highly soluble solid 110 in the second stripping liquid when selecting the second stripping liquid, the degree of freedom in selecting the second stripping liquid is increased.

[0516] <Configuration of the substrate processing apparatus according to the fourth embodiment>

[0517] Fig.26 FIG. is a partial cross-sectional schematic view showing a schematic configuration of the processing unit 2 included in the substrate processing apparatus 1R according to the fourth embodiment of the present invention.

[0518] Fig.26 In, for the configuration equivalent to the configuration shown in Figure 1 to Figure 25D the same reference numerals as Figure 1 etc. are given, and the related description is omitted. In the following Figure 26 to Figure 32C the same reference numerals as Figure 1 etc. are also given, and the related description is omitted.

[0519] The main difference between the substrate processing apparatus 1R according to the fourth embodiment and the substrate processing apparatus 1Q according to the third embodiment (see Fig. 22 ) is that the processing unit 2 includes a first moving nozzle 9, and the hydrophilic liquid ejected from the first moving nozzle 9 is a second hydrophilic liquid such as SC1 (ammonia hydrogen peroxide water mixture).

[0520] The second hydrophilic liquid is a liquid that can moderately hydrophilize (improve hydrophilicity) the surface of the substrate W. The second hydrophilic liquid is a liquid containing substances different from those of the dissolving liquid and the stripping liquid. The second hydrophilic liquid is, for example, an oxidizing liquid such as SC1. The oxidizing liquid is a liquid containing a substance (oxidizing agent) having oxidizing power. As the oxidizing liquid, in addition to SC1, hydrochloric acid hydrogen peroxide water mixed aqueous solution (HPM: hydrochloric hydrogen peroxide mixed water solution), hydrogen peroxide water, ozone water, etc. can also be cited. HPM is also called SC2 (Standard Clean 2, standard cleaning liquid 2).

[0521] SC1, SC2, and hydrogen peroxide water contain hydrogen peroxide (H2O2) as an oxidizing agent. Ozone water contains ozone (O3) as an oxidizing agent.

[0522] As described below Fig.31 As in the case of substrate treatment shown below, when supplying the second hydrophilic liquid to the substrate W whose upper surface does not have a treatment film formed thereon, a liquid with a relatively high solubility in the treatment film can be used as the second hydrophilic liquid. As such a liquid, hydrofluoric acid (HF), diluted hydrofluoric acid (DHF), sulfuric acid hydrogen peroxide water mixture (SPM), organic solvents, etc. can be cited.

[0523] Hydrofluoric acid and diluted hydrofluoric acid contain hydrogen fluoride as an oxidizing agent. SPM contains persulfuric acid as an oxidizing agent. As an organic solvent that can be used as a hydrophilic liquid for the substrate W whose upper surface does not have a treatment film formed thereon, IPA etc. can be cited.

[0524] Fig. 27 It is a schematic diagram for explaining the case where the surface of the substrate W is hydrophilized by the second hydrophilic liquid.

[0525] When using an oxidizing liquid such as SC1 as the second hydrophilic liquid, as Fig. 27 shown, the surface of the substrate W will be oxidized and an oxide film 171 will be formed on the surface of the substrate W. Because the surface of the substrate W is oxidized, oxygen atoms will bond with the substances exposed from the surface of the substrate W. Because the oxygen atoms bond with the substances exposed from the surface of the substrate W, the hydrophilicity of the surface of the substrate W is improved.

[0526] When using an oxidizing liquid as the second hydrophilic liquid, the substrate W can be hydrophilized regardless of the presence or absence of the organic matter 170.

[0527] A substrate W having a surface exposing at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C can be hydrophilized by the second hydrophilic liquid. In particular, a substrate W having a surface exposing at least any one of Si, SiN, SiO2, W, TiN, Co, Cu, and Ru is more easily hydrophilized by the second hydrophilic liquid, and a substrate W having a surface exposing any one of Si, SiN, SiO2, W, TiN, Co, and Cu is even more easily hydrophilized by the second hydrophilic liquid.

[0528] <Substrate treatment of the fourth embodiment>

[0529] Fig.28 It is a flowchart for explaining an example of the substrate treatment by the substrate treatment apparatus 1R of the fourth embodiment. The substrate treatment performed by the substrate treatment apparatus 1R is the same as the substrate treatment performed by the substrate treatment apparatus 1Q of the third embodiment (refer to Fig.23)The main difference is that between the cleaning step (step S31) and the stripping liquid supply step (step S24), a hydrophilic liquid supply step (step S40) and a cleaning step (step S41) are sequentially performed. Below, the substrate processing performed by the substrate processing apparatus 1Q will be described centering on the hydrophilic liquid supply step (step S40) and the cleaning step (step S41).

[0530] In addition, the structure of the substrate W that is the processing object of the substrate processing apparatus 1R is the same as that of the substrate that is the processing object of the substrate processing apparatus 1P. That is, a substrate W having a surface exposing at least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C can be used.

[0531] Fig.29A It is a schematic diagram for explaining the hydrophilic liquid supply step (step S40). Fig.29B It is a schematic diagram for explaining the cleaning step (step S41).

[0532] After the cleaning step (step S31) is completed, the hydrophilic liquid supply step (step S40) is performed as described below.

[0533] First, the upper cleaning liquid valve 51 and the lower cleaning liquid valve 86 are closed. Thereby, the supply of the cleaning liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the facing member lifting unit 61 moves the facing member 6 to the retracted position. In a state where the facing member 6 is in the retracted position, the first nozzle moving unit 35 moves the first moving nozzle 9 to the processing position. The processing position of the first moving nozzle 9 is, for example, the central position.

[0534] Then, with the first moving nozzle 9 in the processing position, the hydrophilic liquid valve 50 is opened. Thereby, as Fig.29A shown, the second hydrophilic liquid is supplied (sprayed) from the first moving nozzle 9 to the central region of the upper surface of the rotating substrate W (hydrophilic liquid supply step, hydrophilic liquid spraying step). The second hydrophilic liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, the entire upper surface of the substrate W is hydrophilized by the second hydrophilic liquid. The second hydrophilic liquid is discharged outside the substrate W by centrifugal force.

[0535] The supply of the second hydrophilic liquid to the upper surface of the substrate W continues for a specified time, for example, 60 seconds. In the hydrophilic liquid supply step, the substrate W rotates at a specified hydrophilic rotation speed, for example, 800 rpm.

[0536] After the hydrophilic liquid supply step (step S40), the cleaning step (step S41) is performed as described below. In this cleaning step, the second hydrophilic liquid is flushed from the substrate W by the cleaning liquid. Since the second hydrophilic liquid is discharged out of the substrate W by the cleaning liquid, the cleaning step (step S41) is also referred to as the hydrophilic liquid discharge step.

[0537] In the cleaning step (step S41), first, the hydrophilic liquid valve 50 is closed. Thereby, the supply of the second hydrophilic liquid to the upper surface of the substrate W is stopped.

[0538] Then, the first nozzle moving unit 35 moves the first moving nozzle 9 to the initial position. Then, as Fig.29B shown, the facing member lifting unit 61 moves the facing member 6 to the processing position.

[0539] Then, with the facing member 6 in the processing position, the upper side cleaning liquid valve 51 is opened. Thereby, as Fig.29B shown, the cleaning liquid is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (upper side cleaning liquid supply step, upper side cleaning liquid spraying step). The cleaning liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thereby, the second hydrophilic liquid attached to the upper surface of the substrate W is discharged out of the substrate W together with the cleaning liquid, and the cleaning liquid is used for replacement (hydrophilic liquid discharge step).

[0540] In addition, while the upper side cleaning liquid valve 51 is opened, the lower side cleaning liquid valve 86 is opened. Thereby, as Fig.29B shown, the cleaning liquid is supplied (sprayed) from the lower nozzle 13 to the central region of the lower surface of the rotating substrate W (lower side cleaning liquid supply step, lower side cleaning liquid spraying step). Thereby, even if the hydrophilic liquid attached to the upper surface of the substrate W moves from the upper surface of the substrate W to the lower surface of the substrate W along the peripheral portion of the substrate W, causing the second hydrophilic liquid to adhere to the lower surface of the substrate W, the second hydrophilic liquid on the lower surface of the substrate W is flushed off by the cleaning liquid.

[0541] The supply of the cleaning liquid to the upper surface and the lower surface of the substrate W continues for a specified time, for example, 30 seconds. In the cleaning step (step S41), the substrate W rotates at a specified hydrophilic liquid discharge rotation speed, for example, 800 rpm.

[0542] As Fig.28 shown, after the cleaning step (step S41), the stripping liquid supply step (step S24) to the substrate unloading step (step S28) are sequentially performed.

[0543] <The stripping of the processing film in the fourth embodiment>

[0544] Next, use Figures 30A to 30E Hereinafter, a case where the treatment film 100 is peeled off from the substrate W in the substrate treatment of the fourth embodiment will be described in detail. Figures 30A to 30E FIG. is a schematic view for explaining a case where the treatment film 100 is peeled off from the substrate W in the substrate treatment of the fourth embodiment.

[0545] As Fig. 30A shown, the treatment film 100 has the same configuration as the substrate treatment of the second embodiment. That is, as Fig. 30A shown, the treatment film 100 holds the object 103 to be removed attached to the surface layer 150 of the substrate W, and has a highly soluble solid 110 and a low soluble solid 111.

[0546] In the substrate treatment of the fourth embodiment, in the same manner as the substrate treatment of the third embodiment, referring to Fig. 30B , a dissolution liquid is supplied to the upper surface of the substrate W in a state where the treatment film 100 is formed (dissolution liquid supply step). The highly soluble solid 110 is dissolved by the dissolution liquid supplied to the upper surface of the substrate W. That is, the treatment film 100 is partially dissolved (dissolution step, partial dissolution step).

[0547] By dissolving the highly soluble solid 110, through-holes 102 are formed in a portion where the highly soluble solid 110 is concentrated in the treatment film 100 (through-hole formation step). Through-holes 102 are formed by the dissolution liquid, but the treatment film 100 is not peeled off.

[0548] Here, when an appropriate amount of solvent remains in the treatment film 100, the dissolution liquid dissolves the treatment film 100 partially while dissolving into the solvent remaining on the treatment film 100. Specifically, the dissolution liquid dissolves into the solvent remaining on the highly soluble solid 110 and dissolves the highly soluble solid 110 in the treatment film 100 to form through-holes 102. Therefore, the dissolution liquid easily enters the treatment film 100 (dissolution liquid entry step).

[0549] Then, after removing the dissolution liquid with a cleaning liquid, a second hydrophilic liquid is supplied to the upper surface of the substrate W (hydrophilic liquid supply step). As Fig. 30C shown, the second hydrophilic liquid passes through the through-holes 102 formed by the dissolution liquid and reaches the upper surface of the substrate W. Thereby, the portion of the upper surface of the substrate W exposed due to the formation of the through-holes 102 is hydrophilized (hydrophilization step). The upper surface of the substrate W is hydrophilized, so that the contact angle of pure water on the upper surface of the substrate W is less than 41.7° (contact angle reduction step). The surface of the substrate W is hydrophilized by the second hydrophilic liquid, but the treatment film 100 is not peeled off.

[0550] Then, after removing the second hydrophilic liquid with the cleaning liquid, a second stripping liquid is supplied to the upper surface of the substrate W (stripping liquid supply step). As Fig.30D shown, the second stripping liquid passes through the through hole 102 and reaches the upper surface of the substrate W. The second stripping liquid that reaches the upper surface of the substrate W acts on the interface between the processing film 100 and the substrate W, strips the processing film 100, and excludes the stripped processing film 100 from the upper surface of the substrate W (stripping and exclusion step).

[0551] The portion of the upper surface of the substrate W exposed due to the formation of the through hole 102 is hydrophilized by the second hydrophilic liquid. Therefore, the second stripping liquid can effectively act on the interface between the portion of the processing film 100 surrounding the through hole 102 and the substrate W. That is, as magnified Fig.30D shown, the second stripping liquid can quickly enter the gap G1 between the processing film 100 and the substrate W (stripping liquid entry step).

[0552] Specifically, the low-solubility component has low solubility in the second stripping liquid, and the low-solubility solid 111 is hardly dissolved by the stripping liquid. Therefore, only the vicinity of the surface of the low-solubility solid 111 will be dissolved by the second stripping liquid. Therefore, the second stripping liquid reaching the vicinity of the upper surface of the substrate W via the through hole 102 only dissolves the portion of the low-solubility solid 111 near the upper surface of the substrate W. Thus, as magnified Fig.30D shown, the second stripping liquid slowly dissolves the low-solubility solid 111 near the upper surface of the substrate W while entering the gap G1 between the processing film 100 and the upper surface of the substrate W (stripping liquid entry step).

[0553] During the process of the second stripping liquid entering the gap G1, the processing film 100 splits starting from the periphery of the through hole 102 and becomes film pieces 105. As Fig.30E shown, the film pieces 105 of the processing film 100 are stripped from the substrate W while holding the object to be removed 103 (processing film splitting step, processing film stripping step).

[0554] Continue to supply the second stripping liquid, and thereby wash away the processing film 100 that has become film pieces 105 while holding the object to be removed 103 by the second stripping liquid. In other words, the film pieces 105 holding the object to be removed 103 are pushed out of the substrate W and excluded from the upper surface of the substrate W (processing film exclusion step, object to be removed exclusion step). Thus, the upper surface of the substrate W can be washed well.

[0555] As described above, according to the fourth embodiment, a dissolution liquid, a second hydrophilic liquid, and a second stripping liquid are respectively supplied to the upper surface of the substrate W on which the processing film 100 is formed. By supplying the dissolution liquid, through-holes 102 are formed in the processing film 100. By supplying the second hydrophilic liquid, the upper surface of the substrate W is hydrophilized. Then, by supplying the second stripping liquid, the processing film 100 is stripped from the upper surface of the substrate W. That is, the formation of the through-holes 102, the hydrophilization of the substrate W, and the stripping of the processing film 100 are caused by the supply of the respective liquids.

[0556] <Summary of the Fourth Embodiment>

[0557] According to the fourth embodiment, the same effects as those of the third embodiment are obtained. However, in the fourth embodiment, different from the third embodiment, the second hydrophilic liquid is supplied to the substrate W after the dissolution liquid is supplied to the substrate W and before the second stripping liquid is supplied to the substrate W.

[0558] In the fourth embodiment, the upper surface of the substrate W can be sufficiently hydrophilized by the second hydrophilic liquid. Therefore, the hydrophilic performance of the second stripping liquid does not need to be considered when selecting the second stripping liquid.

[0559] Specifically, if the mass percentage concentration of IPA in the second stripping liquid is 12% or more, the hydrophilicity of the upper surface of the substrate W can be sufficiently improved. If the mass percentage concentration of IPA in the second stripping liquid is 1% or more and 33% or less, the processing film 100 on the substrate W can be moderately dissolved and the processing film 100 can be stripped from the substrate W. Therefore, the processing film 100 can be sufficiently stripped even by using the second stripping liquid with a mass percentage concentration of IPA greater than or equal to 1% and less than 12%. Therefore, if the second hydrophilic liquid is used, the hydrophilic degree (hydrophilic force of the second stripping liquid) that the second stripping liquid can achieve does not need to be considered when selecting the second stripping liquid. Therefore, the degree of freedom in selecting the second stripping liquid is increased.

[0560] Since the hydrophilic force of the second stripping liquid does not need to be considered when selecting the second stripping liquid suitable for stripping the processing film 100, the processing film 100 holding the object to be removed 103 can be effectively stripped.

[0561] <Another Example of Substrate Processing in the Fourth Embodiment>

[0562] Using the substrate processing apparatus 1R of the fourth embodiment, the substrate processing shown in Fig.31 can also be performed. Fig.31 In the substrate processing shown in Fig.28The substrate treatment shown is different. Instead of performing the hydrophilic liquid supply step (step S40) and the cleaning step (step S41), a pre-hydrophilic treatment step (step S50), a cleaning step (step S51), and a replacement step (step S52) are performed before the treatment liquid supply step (step S22).

[0563] Figures 32A to 32C is used to illustrate Fig.31 a schematic diagram of the substrate treatment shown.

[0564] First, after the substrate loading step (step S21), the pre-hydrophilic treatment step (step S50) is performed. Specifically, as Fig.32A shown, the second hydrophilic liquid (pre-hydrophilic liquid supply step, pre-hydrophilic liquid ejection step) is supplied (ejected) from the first moving nozzle 9 toward the central region of the upper surface of the rotating substrate W. The second hydrophilic liquid supplied to the upper surface of the substrate W diffuses to the entire upper surface of the substrate W by centrifugal force. Thus, the entire upper surface of the substrate W is hydrophilized by the second hydrophilic liquid. The second hydrophilic liquid is discharged outside the substrate W by centrifugal force.

[0565] In the pre-hydrophilic treatment step (step S50), the second hydrophilic liquid is supplied to the substrate W on whose upper surface no treatment film is formed. Therefore, as described above, a liquid with a relatively high solubility in the treatment film can be used as the second hydrophilic liquid. Therefore, as the second hydrophilic liquid, the following can be used: oxidizing liquids such as SC1, SC2, hydrogen peroxide water, ozone water, SPM, and hydrofluoric acid; or organic solvents such as IPA.

[0566] Referring to Fig.32B , after the pre-hydrophilic treatment step (step S50), the same cleaning step (step S51) as the cleaning step (step S41) is performed. In this cleaning step (step S51), the hydrophilic liquid is washed off the substrate W with the cleaning liquid. Since the hydrophilic liquid is discharged outside the substrate W with the cleaning liquid, the cleaning step (step S51) is also referred to as the pre-hydrophilic liquid discharge step.

[0567] Referring to Fig.32C , after the cleaning step (step S51), a replacement step (step S52) is performed, that is, the cleaning liquid on the substrate W is replaced with a replacement liquid such as an organic solvent. In the replacement step, the cleaning liquid on the substrate W is replaced with a residue removal liquid as the replacement liquid.

[0568] Specifically, the upper cleaning liquid valve 51 and the lower cleaning liquid valve 86 are closed. Thereby, the supply of the cleaning liquid to the upper surface and the lower surface of the substrate W is stopped. The opposing member 6 is maintained at the treatment position.

[0569] While the opposing member 6 is maintained at the treatment position, the organic solvent valve 52 is opened. Thereby, as Fig.32C As shown, a replacement liquid (residue removal liquid), such as IPA, as an organic solvent, is supplied (sprayed) from the central nozzle 12 to the central region of the upper surface of the rotating substrate W (replacement liquid supply step, replacement liquid spraying step). The central nozzle 12 is an example of a replacement liquid supply unit.

[0570] The replacement liquid supplied from the central nozzle 12 to the upper surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire upper surface of the substrate W. Thereby, the cleaning liquid on the substrate W is replaced with the replacement liquid.

[0571] In the replacement step, the spraying of the replacement liquid from the central nozzle 12 continues for a specified time, for example, 10 seconds. In the replacement step, the substrate W rotates at a specified replacement rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not necessarily rotate at a fixed rotation speed in the replacement step. For example, the rotation motor 23 may also cause the substrate W to rotate at 300 rpm at the start of the supply of the replacement liquid, and while supplying the replacement liquid to the substrate W, accelerate the rotation of the substrate W until the rotation speed of the substrate W reaches 1500 rpm.

[0572] The replacement liquid such as IPA sprayed from the second tube 32 is supplied to the upper surface of the substrate W covered with the liquid film of the cleaning liquid, and the processing liquid is supplied to the upper surface of the substrate W covered with the liquid film of the replacement liquid. After the replacement liquid is supplied to the upper surface of the substrate W covered with the liquid film of the cleaning liquid, almost all of the cleaning liquid on the substrate W is pushed by the replacement liquid and discharged from the substrate W.

[0573] The remaining trace amount of cleaning liquid will dissolve in the replacement liquid and diffuse in the replacement liquid. The diffused cleaning liquid will be discharged from the substrate W together with the replacement liquid. Therefore, the cleaning liquid on the substrate W can be efficiently replaced with the replacement liquid. For the same reason, the replacement liquid on the substrate W can be efficiently replaced with the processing liquid. Thereby, the cleaning liquid contained in the processing liquid on the substrate W can be reduced.

[0574] Then, as Fig.31 shown, the processing liquid supply step (step S22) to the substrate unloading step (step S28) are sequentially executed.

[0575] Fig.31 In the substrate processing shown, the upper surface of the substrate W is hydrophilized in advance, that is, before the processing liquid is supplied to the upper surface of the substrate W. Therefore, the processing film 100 is formed on the hydrophilized upper surface of the substrate W. Therefore, the processing film 100 can be effectively peeled off from the substrate W by the second peeling liquid.

[0576] <Contact Angle Measurement Experiment Using Diluted IPA>

[0577] Next, the results of a contact angle measurement experiment for measuring the contact angle of diluted IPA on the surface of a substrate will be described.

[0578] In this experiment, an experimental substrate with exposed Ru on the surface and an experimental substrate with exposed bare silicon on the surface were used. The experimental substrate with exposed Ru on the surface is a substrate on which a Ru film is formed by CVD method. The experimental substrate used in this experiment is the same as the above-mentioned experiment, and is also a square chip substrate with a side length of 3 cm when viewed from above.

[0579] The experimental substrate with exposed Ru on the surface has been pre-treated with IPA, and the contact angle of pure water on this experimental substrate is 60°. The experimental substrate with exposed Si on the surface has been pre-treated with hydrofluoric acid with a mass percentage concentration of 0.5%, and the contact angle of pure water on this experimental substrate is 62°.

[0580] In this experiment, diluted IPA prepared at five IPA concentrations was dropped onto the experimental substrate, and the contact angle of the diluted IPA at each IPA concentration on the surface of the experimental substrate was measured. The contact angles of the diluted IPA at five IPA concentrations were measured for each experimental substrate.

[0581] Fig.33 is a graph showing the relationship between the concentration of IPA in the diluted IPA and the contact angle of the diluted IPA on the surface of the experimental substrate. Fig.33 The horizontal axis of represents the concentration of IPA in the diluted IPA (mass percentage concentration). Fig.33 The vertical axis of represents the contact angle of the diluted IPA on the surface of the experimental substrate.

[0582] As Fig.33 shown, for both the experimental substrate with exposed Ru and the experimental substrate with exposed Si on the surface, the higher the IPA concentration in the diluted IPA, the lower the contact angle. From this experiment, the following results were obtained: in the experimental substrate with exposed Ru on the surface, if the IPA concentration is about 12% or more, the contact angle is less than 41.7°. The following result was also obtained: in the experimental substrate with exposed bare silicon on the surface, if the IPA concentration is about 15% or more, the contact angle is less than 41.7°. Therefore, through this experiment, the possibility that the surface of the substrate can be sufficiently hydrophilized if the IPA concentration is about 12% or more was revealed.

[0583] <Treatment film stripping experiment using diluted IPA>

[0584] Next, the results of a treatment film stripping experiment for stripping the treatment film using diluted IPA will be described.

[0585] In this experiment, a substrate with Si exposed on the surface was used as the experimental substrate. The experimental substrate used in this experiment is the same as that in the above experiment, and is also a small square substrate with a side length of 3 cm when viewed from above. The experimental substrate has been pre-treated with IPA, and the contact angle of pure water on the experimental substrate is 23°.

[0586] In this experiment, a treatment liquid was dropped onto the surface of an experimental substrate to form a treatment film, and then diluted IPA was dropped onto the surface of the experimental substrate having the treatment film formed thereon, and the removal of the treatment film was observed using a microscope.

[0587] Fig.34 This is a microscope image used to explain the state of the surface of the experimental substrate when diluted IPA is dripped onto the experimental substrate having a treated film formed on the surface. Fig.34 As shown, when the mass percentage concentration of IPA in the diluted IPA is 1%, 25% and 33%, the process film is peeled off by the diluted IPA. Specifically, when the mass percentage concentration of IPA in the diluted IPA is 1%, 25% and 33%, the diluted IPA enters between the process film and the experimental substrate, causing wrinkles 400 on the process film. On the other hand, when the mass percentage concentration of IPA in the diluted IPA is 50%, the process film is dissolved by the diluted IPA. Therefore, it is known from this experiment that if the concentration of IPA is greater than 1% and less than 33%, the process film can be peeled off from the surface of the substrate.

[0588] It was also found that if the IPA concentration was 50% or more, the treated film was dissolved to a level that was insufficient for peeling. From this, it was inferred that the treated film had the property of being more soluble in organic solvents such as IPA than in water.

[0589] <Details of treatment fluid>

[0590] Next, each component in the processing liquid used in the above-described embodiment will be described.

[0591] In the following, “C x～y "C x ~C y ” and “C x " etc. indicate 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).

[0592] When a polymer has multiple repeating units, these repeating units may copolymerize. Unless otherwise specified, their copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of the above copolymerization forms. When a polymer or resin is represented by a structural formula, n or m, etc., indicated together with brackets, indicates the number of repetitions.

[0593] <Low solubility component>

[0594] (A) The low solubility component contains at least one of phenolic aldehyde, polyhydroxystyrene, polystyrene, polyacrylate derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylate derivatives, and copolymers of combinations thereof. Preferably, (A) the low solubility component may also contain at least one of phenolic aldehyde, polyhydroxystyrene, polyacrylate derivatives, polycarbonate, polymethacrylate derivatives, and copolymers of combinations thereof. More preferably, (A) the low solubility component may also contain at least one of phenolic aldehyde, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. The phenolic aldehyde may be phenolic phenolic aldehyde.

[0595] The treatment liquid may also contain one or a combination of two or more of the above-mentioned examples as (A) the low solubility component. For example, (A) the low solubility component may contain both phenolic aldehyde and polyhydroxystyrene.

[0596] In a preferred embodiment, (A) the low solubility component is formed into a film by drying, and most of the film is not dissolved by the stripping liquid, but peels off while maintaining the object to be removed. In addition, an embodiment in which a very small part of (A) the low solubility component is dissolved by the stripping liquid is also allowed.

[0597] Preferably, (A) the low solubility component does not contain fluorine and / or silicon, and more preferably does not contain both.

[0598] The copolymerization is preferably random copolymerization or block copolymerization.

[0599] As specific examples of (A) the low solubility component, the compounds shown in the following Chemical Formula 1 to Chemical Formula 7 can be cited, but the scope of rights is not limited thereto.

[0600] [Chemical Formula 1]

[0601] [Chemical Formula 1]

[0602]

[0603] [Chemical Formula 2]

[0604] [Chemical Formula 2]

[0605]

[0606] [Chemical Formula 3]

[0607] [Chemical Formula 3]

[0608]

[0609] (The asterisk * indicates the bond with the adjacent constitutional unit)

[0610] [Chemical Formula 4]

[0611] [Chemical formula 4]

[0612]

[0613] (R represents a substituent such as C1-C4 alkyl. The asterisk * represents a bond to an adjacent structural unit)

[0614] [Chemical formula 5]

[0615] [Chemical formula 5]

[0616]

[0617] [Chemical formula 6]

[0618] [Chemical formula 6]

[0619]

[0620] [Chemical formula 7]

[0621] [Chemical formula 7]

[0622]

[0623] (Me represents methyl. The asterisk * represents a bond to an adjacent structural unit)

[0624] (A) The weight average molecular weight (Mw) of the low solubility component is preferably 150 - 500,000, more preferably 300 - 300,000, still more preferably 500 - 100,000, and even more preferably 1,000 - 50,000.

[0625] (A) The low solubility component can be obtained by synthesis. In addition, it can also be purchased. If you want to purchase, the following examples can be cited as suppliers. (A) polymers can also be synthesized by the supplier.

[0626] Phenol formaldehyde: Showa Denko K.K., Asahi Organic Chemicals Co., Ltd., Gun Ei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0627] Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.

[0628] Polyacrylic acid derivatives: Nippon Shokubai Co., Ltd.

[0629] Polycarbonate: Sigma - Aldrich

[0630] Polymethacrylic acid derivatives: Sigma - Aldrich

[0631] With respect to the total mass of the treatment liquid, component (A), the poorly soluble component, is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass. That is, assuming the total mass of the treatment liquid is 100% by mass, based on this, component (A), the poorly soluble component, is 0.1 to 50% by mass. That is, "with respect to..." can also be expressed as "based on...". Unless otherwise specified, the same applies hereinafter.

[0632] <Highly soluble component>

[0633] (B) The highly soluble component is (B') the cleavage promoting component. (B') The cleavage promoting component contains a hydrocarbon and also contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). When (B') the cleavage promoting component is a polymer, each unit of one kind of constituent unit contains a hydrocarbon and also contains a hydroxyl group and / or a carbonyl group. As the carbonyl group, carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and ketene can be exemplified, and carboxylic acid is preferred.

[0634] When the treatment liquid is dried to form a treatment film on the substrate and the treatment film is peeled off using a stripping liquid, it can be expected that component (B), the highly soluble component, will create a portion that becomes the starting point for the peeling of the treatment film; this is not intended to limit the scope of the claims and is not bound by theory. Therefore, component (B), the highly soluble component, is preferably a component that is more soluble in the stripping liquid than component (A), the poorly soluble component. Regarding the aspect in which (B') the cleavage promoting component contains a ketone as the carbonyl group, cyclic hydrocarbons can be exemplified. As specific examples, 1,2-cyclohexanedione or 1,3-cyclohexanedione can be exemplified.

[0635] As a more specific aspect, component (B), the highly soluble component, is represented by at least any one of the following (B-1), (B-2), and (B-3).

[0636] (B-1) is a compound containing 1 to 6 of the following Chemical Formula 8 as constituent units (preferably 1 to 4), and each constituent unit is bonded by a linking group (linker L1). Here, linker L1 can be a single bond or an alkylene. 1～6 The alkylene links the constituent units as a linker, and it is not limited to a divalent group. A divalent to tetravalent group is preferred. The alkylene 1～6 can be linear or branched. 1～6 The alkylene can be linear or branched.

[0637] [Chemical Formula 8]

[0638] [Chemical Formula 8]

[0639]

[0640] Cy1 is C5 to 30a hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. As a preferred embodiment, the linker L1 connects a plurality of Cy1s.

[0641] R1 is independently C 1～5 alkyl, preferably methyl, ethyl, propyl or butyl. The C 1～5 alkyl can be straight-chain or branched-chain.

[0642] n b1 is 1, 2 or 3, preferably 1 or 2, more preferably 1. n b1 ' is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0643] The following Chemical Formula 9 is a chemical formula representing the structural unit described in Chemical Formula 8 using the linker L9. The linker L9 is preferably a single bond, methylene, ethylene or propylene.

[0644] [Chemical Formula 9]

[0645] [Chemical Formula 9]

[0646]

[0647] Examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxydiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, but the scope of the claims is not limited thereto. They can also be obtained by polymerization or condensation.

[0648] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following Chemical Formula 10 will be described. This compound has 3 structural units of Chemical Formula 8 in (B-1), and the structural units are bonded by the linker L1 (methylene). n b1 = n b1 ' = 1, and R1 is methyl.

[0649] [Chemical Formula 10]

[0650] [Chemical Formula 10]

[0651]

[0652] (B-2) is represented by the following Chemical Formula 11.

[0653] [Chemical Formula 11]

[0654] [Chemical Formula 11]

[0655]

[0656] R 21 , R 22 , R 23 and R 24 are independently hydrogen or C 1～5 The alkyl group is preferably hydrogen, methyl, ethyl, t-butyl or isopropyl, more preferably hydrogen, methyl or ethyl, further preferably methyl or ethyl.

[0657] Linker L 21 and linker L 22 Each is independent of C 1～20 Alkylene, C 1～20 Cycloalkane, C 2～4 Alkenyl, C 2～4 Alkyne, or C 6～20 These groups can also be C 1～5 Here, the so-called alkenylene group means a divalent hydrocarbon group having one or more double bonds, and the so-called alkynylene group means a divalent hydrocarbon group having one or more triple bonds. 21 and linker L 22 Preferably, C2-4 alkylene, acetylene (C2 alkynylene) or phenylene is used, and C 2～4 alkylene or acetylene, and acetylene is preferred.

[0658] n b2 It is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

[0659] As suitable examples of (B-2), 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol can be cited. As another embodiment, 3-hexyne-2,5-diol, 1,4-butyne diol, 2,4-hexadiyne-1,6-diol, 1,4-butane diol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol can also be cited as suitable examples of (B-2). However, this is not intended to limit the scope of the rights.

[0660] (B-3) is a polymer having a weight average molecular weight (Mw) of 500 to 10,000 and including a structural unit represented by the following Chemical Formula 12. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

[0661] [Chemistry 12]

[0662] [Chemistry 12]

[0663]

[0664] Here, R 25is -H, -CH3 or -COOH, preferably -H or -COOH. It is also allowed that one (B-3) polymer contains two or more constitutional units represented by Chemical Formula 12 respectively.

[0665] As suitable examples of the (B-3) polymer, polymers of acrylic acid, maleic acid, or combinations thereof can be cited. Polyacrylic acid and maleic acid-acrylic acid copolymer are more preferable examples. However, the scope of rights is not to be limited thereto.

[0666] If it is a copolymerization, random copolymerization or block copolymerization is appropriate, and random copolymerization is more preferable.

[0667] As an example, the maleic acid-acrylic acid copolymer shown in the following Chemical Formula 13 is cited for illustration. This copolymer is included in (B-3), has two constitutional units represented by Chemical Formula 12, and in one constitutional unit, R 25 is -H, and in the other constitutional unit, R 25 is -COOH.

[0668] [Chemical Formula 13]

[0669] [Chemical Formula 13]

[0670]

[0671] Of course, the treatment liquid may also contain one or a combination of two or more of the above-mentioned suitable examples as the (B) highly soluble component. For example, the (B) highly soluble component may also contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0672] The (B) highly soluble component may also have a molecular weight of 80 to 10,000. The highly soluble component preferably has a molecular weight of 90 to 5000, and more preferably 100 to 3000. When the (B) highly soluble component is a resin, polymer or copolymer, the molecular weight is represented by the weight average molecular weight (Mw).

[0673] The (B) highly soluble component can be obtained by synthesis or by purchase. As suppliers, Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai can be cited.

[0674] In the treatment liquid, the mass of the (B) highly soluble component relative to the mass of the (A) low soluble component is preferably 1 to 100% by mass, more preferably 1 to 50% by mass. In the treatment liquid, the mass of the (B) highly soluble component relative to the mass of the (A) low soluble component is further preferably 1 to 30% by mass.

[0675] <Solvent>

[0676] (C) The solvent preferably contains an organic solvent. (C) The solvent may also be volatile. By being volatile, it means that the volatility is higher than that of water. For example, the boiling point of (C) the solvent under 1 atmospheric pressure is preferably 50 to 250 °C. The boiling point of the solvent under 1 atmospheric pressure is more preferably 50 to 200 °C, and still more preferably 60 to 170 °C. The boiling point of the solvent under 1 atmospheric pressure is still further more preferably 70 to 150 °C. It is also allowed for (C) the solvent to contain a small amount of pure water. The pure water contained in (C) the solvent is preferably 30 mass% or less with respect to the whole of (C) the solvent. The pure water contained in the solvent is more preferably 20 mass% or less, and still more preferably 10 mass% or less. The pure water contained in the solvent is still further more preferably 5 mass% or less. It is also a preferred embodiment that the solvent does not contain pure water (0 mass%). The so-called pure water is preferably DIW.

[0677] Examples of the organic solvent include: alcohols such as isopropyl alcohol (IPA); ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE); propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; lactate esters such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone; amides such as N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone; and the like. These organic solvents can be used alone or in combination of two or more.

[0678] As a preferred aspect, the organic solvent contained in (C) the solvent can be selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. In the case of a combination of two organic solvents, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

[0679] With respect to the total mass of the treatment liquid, (C) the solvent is 0.1 to 99.9 mass%. With respect to the total mass of the treatment liquid, (C) the solvent is preferably 50 to 99.9 mass%, and more preferably 75 to 99.5 mass%. With respect to the total mass of the treatment liquid, (C) the solvent is still more preferably 80 to 99 mass%, and still further more preferably 85 to 99 mass%.

[0680] <Other Additives>

[0681] The treatment liquid of the present invention may also further contain (D) other additives. As an aspect of the present invention, (D) the other additives include surfactants, acids, bases, antibacterial agents, fungicides, preservatives, or antifungal agents (preferably surfactants), and may also include any combination thereof.

[0682] As an aspect of the present invention, with respect to the mass of the (A) low-solubility component in the treatment liquid, the (D) other additives (if there are multiple types, then their sum) is 0 to 100 mass% (preferably 0 to 10 mass%, more preferably 0 to 5 mass%, still more preferably 0 to 3 mass%, and still more preferably 0 to 1 mass%). The treatment liquid not containing the (D) other additives (0 mass%) is also one aspect of the present invention.

[0683] <Anticorrosion component>

[0684] As the (F) anticorrosion component, in addition to BTA, examples include uric acid, caffeine, purine, adenine, glyoxylic acid, glucose, fructose, mannose, and the like.

[0685] <Other embodiments>

[0686] The present invention is not limited to the embodiments described above and can be implemented in other ways.

[0687] For example, the hydrophilization of the upper surface of the substrate W in the first embodiment can also be performed by methods such as UV irradiation, plasma treatment, oxygen ashing, etc., that is, methods other than the first hydrophilization liquid treatment.

[0688] In addition, in the first embodiment, the same organic solvent is used as the replacement liquid and the residue removal liquid. However, if a nozzle for ejecting the organic solvent as the replacement liquid and a nozzle for ejecting the residue removal liquid are separately provided, the organic solvents used as the replacement liquid and the residue removal liquid can be different from each other. For example, methanol can be used as the replacement liquid and IPA can be used as the residue removal liquid.

[0689] In addition, in the first embodiment, the treatment film 100 is partially dissolved by the stripping liquid to form the through hole 102, and thus the stripping liquid reaches the interface between the treatment film 100 and the substrate W through the through hole 102. However, it is not necessary to form a visible through hole 102, and it can also pass through the gap formed in the treatment film 100 by dissolving the highly soluble solid 110 in the treatment film 100 with the stripping liquid and reach the interface between the treatment film 100 and the substrate W.

[0690] The nozzles for ejecting the respective treatment fluids in the first embodiment are not limited to those described above. For example, in the embodiment, the treatment liquid, the hydrophilization liquid, and the stripping liquid are ejected from the moving nozzle onto the upper surface of the substrate W, and the cleaning liquid, the organic solvent, and the gas are ejected from the fixed nozzle (central nozzle 12) onto the upper surface of the substrate W. However, it can also be configured such that the cleaning liquid, the organic solvent, and the gas are ejected from the moving nozzle, and it can also be configured such that, in addition to the cleaning liquid, the organic solvent, and the gas, the treatment liquid, the hydrophilization liquid, and the stripping liquid are also ejected from the central nozzle 12.

[0691] In addition, in the fourth embodiment, the hydrophilization of the upper surface of the substrate W in the pre-hydrophilization step (step S51) may also be performed by a method other than the treatment with the second hydrophilization liquid such as UV irradiation, plasma treatment, and oxygen ashing.

[0692] In addition, Fig.31 In the substrate treatment shown, the same organic solvent is used as the replacement liquid and the residue removal liquid. However, if nozzles for ejecting the organic solvent as the replacement liquid and nozzles for ejecting the residue removal liquid are provided separately, the organic solvent used as the replacement liquid and the organic solvent used as the residue removal liquid may be different from each other. For example, methanol may be used as the replacement liquid and IPA may be used as the residue removal liquid.

[0693] The same applies to the second to fourth embodiments. The nozzles for ejecting each processing fluid (processing liquid, stripping liquid, cleaning liquid, residue removal liquid, dissolving liquid, hydrophilization liquid, heat medium, inert gas, replacement liquid) are not necessarily in the form shown in the above embodiments. For example, in the fourth embodiment, the first moving nozzle 9 may not be provided, and the fourth moving nozzle 14 may be configured to eject the second hydrophilization liquid and the dissolving liquid.

[0694] For example, when the second hydrophilization liquid is SC1 and the dissolving liquid is ammonia water, the second hydrophilization liquid can be prepared by mixing hydrogen peroxide water in the dissolving liquid. Therefore, by supplying only ammonia water to the fourth moving nozzle 14, the dissolving liquid can be ejected from the fourth moving nozzle 14, and by supplying ammonia water and hydrogen peroxide water to the fourth moving nozzle 14, SC1 can be ejected from the fourth moving nozzle 14.

[0695] If all the processing fluids are ejected from the moving nozzle or all the processing fluids are ejected from the fixed nozzle arranged outside the substrate W in a plan view, the facing member 6 may not be provided.

[0696] The same applies to the second to fourth embodiments. It is not necessary to form a visually visible through hole 102 in the processing film 100. Instead, gaps may be formed in the processing film 100 by dissolving highly soluble solids 110, and the hydrophilization liquid or the stripping liquid may pass through these gaps to reach the interface between the substrate W and the processing film 100.

[0697] Fig.21The modification example of the second embodiment can also be applied to the substrate processing apparatus 1Q of the third embodiment and the substrate processing apparatus 1R of the fourth embodiment. That is to say, similarly in the stripping liquid supply step (step S24) of the substrate processing of the third embodiment and the stripping liquid supply step (step S24) of the substrate processing of the fourth embodiment, during the supply of the second stripping liquid to the upper surface of the substrate W, the opening degrees of the organic solvent adjustment valve 93B and the pure water adjustment valve 94B can be adjusted, so as to adjust the concentration of the organic solvent in the second stripping liquid supplied to the upper surface of the substrate W (organic solvent concentration adjustment step).

[0698] In addition, Fig.28 and Fig.31 in the substrate processing shown, the dissolution liquid supply step (step S30) and the cleaning step (step S31) can be omitted.

[0699] In addition, Fig.18 、 Fig.23 and Fig.28 in the substrate processing shown, the pre-hydrophilic treatment step (step S50), the cleaning step (step S51) and the replacement step (step S52) can also be performed.

[0700] Specifically, Fig.18 in the substrate processing, after the substrate loading step (step S21), the pre-hydrophilic treatment step (step S50), the cleaning step (step S51) and the replacement step (step S52) can also be performed, and then, the treatment liquid supply step (step S22), the treatment film formation step (step S23), the stripping liquid supply step (step S24), the cleaning step (step S25), the residue removal liquid supply step (step S26), the spin drying step (step S27) and the substrate unloading step (step S28) are performed in sequence.

[0701] Similarly, Fig.23 in the substrate processing, after the substrate loading step (step S21), the pre-hydrophilic treatment step (step S50), the cleaning step (step S51) and the replacement step (step S52) can also be performed, and then, the treatment liquid supply step (step S22), the treatment film formation step (step S23), the dissolution liquid supply step (step S30), the cleaning step (step S31), the stripping liquid supply step (step S24), the cleaning step (step S25), the residue removal liquid supply step (step S26), the spin drying step (step S27) and the substrate unloading step (step S28) are performed in sequence.

[0702] Similarly, Fig.28In the substrate treatment, after the substrate loading step (step S21), a pre-hydrophilic treatment step (step S50), a cleaning step (step S51), and a replacement step (step S52) may be performed. Then, a treatment liquid supply step (step S22), a treatment film formation step (step S23), a dissolution liquid supply step (step S30), a cleaning step (step S31), a hydrophilic liquid supply step (step S40), a cleaning step (step S41), a stripping liquid supply step (step S24), a cleaning step (step S25), a residue removal liquid supply step (step S26), a spin drying step (step S27), and a substrate unloading step (step S28) are sequentially performed.

[0703] In addition, Fig.28 In the substrate treatment shown, when the hydrophilic liquid and the dissolution liquid are compatible, the cleaning step (step S31) can be omitted. When the hydrophilic liquid and the stripping liquid are compatible, the cleaning step (step S41) can be omitted. Fig.23 and Fig.31 In the substrate treatment shown, when the dissolution liquid and the stripping liquid are compatible, the cleaning step (step S31) can be omitted.

[0704] In this specification, when a numerical range is represented by "~" or "-", as long as there is no special limitation, the numerical values at both ends of these two symbols are included, and the units are common.

[0705] The embodiments of the present invention have been described in detail above, but they are merely specific examples used to clarify the technical content of the present invention. The present invention should not be construed as being limited to these specific examples, and the scope of the present invention is only limited by the appended claims.

Claims

1. A substrate processing method, comprising: A hydrophilization step of hydrophilizing the surface of the substrate; A processing liquid supply step of supplying a processing liquid to the surface of the hydrophilized substrate; A processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate; And A stripping step of supplying a stripping liquid to the surface of the substrate to strip the processing film holding the object to be removed from the surface of the substrate; and The stripping step includes a through-hole formation step of partially dissolving the processing film in the stripping liquid to form a through-hole in the processing film, The hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water on the surface of the substrate so that the contact angle is less than 41.7°, The contact angle of pure water on the processing film is greater than 52° and less than 61°.

2. The substrate processing method according to claim 1, wherein The stripping step includes a stripping liquid entry step of allowing the stripping liquid to enter between the surface of the substrate and the processing film.

3. The substrate processing method according to claim 1 or 2, wherein The hydrophilization step includes a step of hydrophilizing the surface of the substrate by supplying a hydrophilizing liquid to the surface of the substrate.

4. The substrate processing method according to claim 3, wherein The hydrophilizing liquid is an oxidizing liquid or an organic solvent.

5. The substrate processing method according to claim 1 or 2, wherein At least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate.

6. The substrate processing method according to claim 3, wherein The surface layer of the substrate includes a TiN layer exposed from the surface of the substrate, and The hydrophilizing liquid is an oxidizing liquid.

7. The substrate processing method according to claim 1 or 2, wherein The processing liquid contains a solvent and a solute, The solute has a highly soluble component and a low-soluble component whose solubility in the stripping liquid is lower than that of the highly soluble component, The processing film formation step includes a step of forming the processing film, which has a highly soluble solid formed by the highly soluble component and a low-soluble solid formed by the low-soluble component, The stripping step is to dissolve the highly soluble solid in the stripping liquid to strip the processing film holding the object to be removed from the surface of the substrate.

8. A substrate processing method, comprising: A hydrophilization step of hydrophilizing the surface of the substrate; A processing liquid supply step of supplying a processing liquid to the surface of the hydrophilized substrate; A processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate; And A stripping step of supplying a stripping liquid to the surface of the substrate to strip the processing film holding the object to be removed from the surface of the substrate; and The hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water on the surface of the substrate so that the contact angle is less than 41.7°. The contact angle of pure water on the treatment film is greater than 52° and less than 61°.

9. A substrate processing method, comprising: A hydrophilization step of hydrophilizing the surface of the substrate; A treatment liquid supply step of supplying a treatment liquid to the surface of the hydrophilized substrate; A treatment film formation step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that holds a removal object existing on the surface of the substrate; And A peeling step of supplying a peeling liquid to the surface of the substrate to peel the treatment film holding the removal object from the surface of the substrate; and The treatment liquid contains a solvent and a solute, The solute has a highly soluble component and a low soluble component with lower solubility in the peeling liquid than the highly soluble component, The treatment film formation step includes a step of forming the treatment film, which has a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component, In the peeling step, the highly soluble solid is dissolved in the peeling liquid to peel the treatment film holding the removal object from the surface of the substrate, The hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water on the surface of the substrate so that the contact angle is less than 41.7°. The contact angle of pure water on the treatment film is greater than 52° and less than 61°.

10. The substrate processing method according to claim 9, wherein At least any one of Si, SiN, SiO2, SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate.

11. A substrate processing apparatus, comprising: A hydrophilization liquid supply unit that supplies a hydrophilization liquid for hydrophilizing the surface of the substrate to the surface of the substrate; A treatment liquid supply unit that supplies a treatment liquid to the surface of the substrate; A treatment film formation unit that solidifies or hardens the treatment liquid in contact with the surface of the substrate to form a treatment film; A peeling liquid supply unit that supplies a peeling liquid for peeling the treatment film formed on the surface of the substrate to the surface of the substrate; And A controller that controls the hydrophilization liquid supply unit, the treatment liquid supply unit, the treatment film formation unit, and the peeling liquid supply unit; and The controller is programmed as follows: Hydrophilize the surface of the substrate by supplying a hydrophilization liquid from the hydrophilization liquid supply unit to the surface of the substrate; Supply a treatment liquid from the treatment liquid supply unit to the surface of the hydrophilized substrate; Solidify or harden the treatment liquid supplied to the surface of the substrate through the treatment film formation unit to form a treatment film on the surface of the substrate that holds a removal object existing on the surface of the substrate; Supply a peeling liquid from the peeling liquid supply unit to the surface of the substrate to peel the treatment film holding the removal object from the surface of the substrate; and The treatment film is partially dissolved by the stripping liquid, and through-holes are formed in the treatment film. The hydrophilic treatment reduces the contact angle of pure water on the surface of the substrate, making the contact angle less than 41.7°. The contact angle of pure water on the treatment film is greater than 52° and less than 61°.

12. A substrate treatment apparatus, comprising: A hydrophilic liquid supply unit that supplies a hydrophilic liquid for hydrophilizing the surface of the substrate to the surface of the substrate; A treatment liquid supply unit that supplies a treatment liquid to the surface of the substrate; A treatment film forming unit that cures or hardens the treatment liquid in contact with the surface of the substrate to form a treatment film; A stripping liquid supply unit that supplies a stripping liquid for stripping the treatment film formed on the surface of the substrate to the surface of the substrate; And A controller that controls the hydrophilic liquid supply unit, the treatment liquid supply unit, the treatment film forming unit, and the stripping liquid supply unit; and The treatment liquid contains a solvent and a solute, The solute has a highly soluble component and a poorly soluble component whose solubility in the stripping liquid is lower than that of the highly soluble component, The treatment film formed on the surface of the substrate has a highly soluble solid formed by the highly soluble component and a poorly soluble solid formed by the poorly soluble component, The controller is programmed as follows: The surface of the substrate is hydrophilized by supplying a hydrophilic liquid from the hydrophilic liquid supply unit to the surface of the substrate; A treatment liquid is supplied from the treatment liquid supply unit to the surface of the hydrophilized substrate; The treatment liquid supplied to the surface of the substrate is cured or hardened by the treatment film forming unit to form a treatment film on the surface of the substrate that holds the object to be removed present on the surface of the substrate; And A stripping liquid is supplied from the stripping liquid supply unit to the surface of the substrate to dissolve the highly soluble solid in the stripping liquid and strip the treatment film holding the object to be removed from the surface of the substrate, The hydrophilic treatment reduces the contact angle of pure water on the surface of the substrate, making the contact angle less than 41.7°. The contact angle of pure water on the treatment film is greater than 52° and less than 61°.

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