Substrate processing method and substrate processing apparatus

Abstract

The invention provides a substrate processing method and a substrate processing apparatus. The substrate processing method includes: a pretreatment film forming step of forming a pretreatment film on a surface of a substrate having a surface in which a first region and a second region are exposed from different substances; a pretreatment film peeling step of peeling the pretreatment film from the surface of the substrate by using a peeling liquid; a treatment film forming step of forming a treatment film on the surface of the substrate after the pretreatment film peeling step; and a treatment film peeling step of peeling the treatment film from the surface of the substrate by using a peeling liquid. The removal force of the processing film for removing the first object to be removed present in the second region is higher than the removal force of the pretreatment film for removing the first object to be removed present in the second region. The removal force of the pretreatment film for removing the first object to be removed present in the first region is higher than the removal force of the treatment film for removing the first object to be removed present in the first region.

Description

[0001] This application corresponds to Japanese Patent Application No. 2019-217610 filed with the Japan Patent Office on November 29, 2019, and Japanese Patent Application No. 2019-217611 filed with the Japan Patent Office on November 29, 2019, and all disclosures of these applications are incorporated into this application by reference.

[0002] Related divisional applications

[0003] This application is a divisional application of the invention patent application with the invention name “Substrate processing method, substrate processing device and formula selection method” and application number 202011317720.2. The filing date of the original application is November 23, 2020. Technical Field

[0004] The present invention relates to a substrate processing method and a substrate processing device for processing a substrate, and a recipe selection method for selecting a recipe for performing the substrate processing method. The substrate to be processed includes, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for flat panel displays (FPD) such as organic electroluminescence (EL) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells. Background Art

[0005] In the process of manufacturing semiconductor devices, various contaminants adhering to a substrate, residues of a processing liquid or resist used in a previous process, various particles, etc. (hereinafter sometimes collectively referred to as "removal objects") are removed.

[0006] Specifically, deionized water (DIW) or the like is usually supplied to the substrate to remove the removal object by the physical action of DIW, or a chemical liquid that chemically reacts with the removal object is supplied to the substrate to chemically remove the removal object.

[0007] However, the concavo-convex patterns formed on substrates are becoming increasingly fine and complex, and therefore, it is becoming increasingly difficult to remove the object to be removed using DIW or a chemical liquid while suppressing damage to the concavo-convex patterns.

[0008] Therefore, the following method is proposed, namely: supplying a processing liquid to the surface of a substrate, solidifying the processing liquid on the substrate to form a retaining layer for retaining an object to be removed on the substrate, and then supplying a stripping liquid to the upper surface of the substrate to strip and remove the retaining layer together with the object to be removed from the surface of the substrate (refer to Japanese Patent Gazette No. 2019-62171). Summary of the invention

[0009] The removal force of the holding layer to remove the object to be removed from the surface of the substrate is different depending on the type of material exposed from the surface of the substrate. Therefore, in the case where there are different regions of exposed material on the surface of the substrate, it may not be possible to fully remove the object to be removed by only forming a specific holding layer on the surface of the substrate and peeling the holding layer from the surface of the substrate. It is necessary to perform appropriate treatment according to the material exposed from the surface of the substrate to remove the object to be removed.

[0010] Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus, which can efficiently remove a removal target from the surface of a substrate having a surface where regions of different substances are exposed.

[0011] Another object of the present invention is to provide a recipe selection method that can select a recipe for performing an appropriate substrate processing method according to the state of the surface of the substrate.

[0012] Still another object of the present invention is to provide a substrate processing method and a substrate processing apparatus, which can suppress the deterioration of a specific substance exposed on the surface of a substrate and efficiently remove a removal object from the substrate.

[0013] One embodiment of the present invention is a substrate processing method for processing a substrate having a surface having a first region and a second region where different substances are exposed.

[0014] The substrate processing method includes: a pretreatment liquid supplying step, supplying a pretreatment liquid to the surface of the substrate; a pretreatment film forming step, solidifying or hardening the pretreatment liquid supplied to the surface of the substrate, forming a pretreatment film on the surface of the substrate, wherein the pretreatment film maintains a first removal object on the surface of the substrate; a pretreatment film stripping step, supplying a stripping liquid to the surface of the substrate, stripping the pretreatment film maintaining the first removal object from the surface of the substrate; a treatment liquid supplying step, supplying a treatment liquid to the surface of the substrate after the pretreatment film stripping step; a treatment film forming step, solidifying or hardening the treatment liquid supplied to the surface of the substrate, forming a treatment film on the surface of the substrate, wherein the treatment film maintains the first removal object on the surface of the substrate; and a treatment film stripping step, supplying a stripping liquid to the surface of the substrate, stripping the treatment film maintaining the first removal object from the surface of the substrate.

[0015] In addition, the removal force of the treatment film to remove the first removal object existing in the second area is higher than the removal force of the pretreatment film to remove the first removal object existing in the second area, and the removal force of the pretreatment film to remove the first removal object existing in the first area is higher than the removal force of the treatment film to remove the first removal object existing in the first area.

[0016] According to the method, the first object to be removed is removed from the surface of the substrate by peeling off the pretreatment film having a high removal force for removing the first object to be removed that is present in the first region. Then, the first object to be removed is removed from the surface of the substrate by peeling off the treatment film having a high removal force for removing the first object to be removed that is present in the second region. That is, the first object to be removed is removed in two stages using the pretreatment film and the treatment film having different regions with high removal forces for removing the first object to be removed.

[0017] Therefore, even when the substrate has a surface where regions where different substances are exposed exist, the first removal object can be removed efficiently.

[0018] In one embodiment of the present invention, the removal force for removing the first removal object is composed of a holding force and a peeling property, wherein the holding force holds the first removal object existing in the first region or the second region on the treatment film or the pretreatment film, and the peeling property indicates the ease of peeling of the treatment film or the pretreatment film that maintains the first removal object, wherein in the first region, the peeling property of the pretreatment film is higher than that of the treatment film, and in the second region, the holding force of the treatment film is higher than that of the pretreatment film.

[0019] Therefore, in the first region, most of the first removal object can be removed by peeling off the pretreatment liquid film, and in the second region, most of the first removal object can be removed by peeling off the treatment film. Therefore, even in the case where the substrate has a surface where regions with different substances are exposed, the first removal object can be removed efficiently.

[0020] In one embodiment of the present invention, the first area is an exposed area where the metal is exposed, and the second area is a non-exposed area other than the exposed area. The removal force of the treatment film to remove the first removal object existing in the non-exposed area is higher than the removal force of the pretreatment film to remove the first removal object existing in the non-exposed area, and the removal force of the pretreatment film to remove the first removal object existing in the exposed area is higher than the removal force of the treatment film to remove the first removal object existing in the exposed area.

[0021] According to the method, the first removal object is removed from the surface of the substrate by peeling off the pretreatment film having a relatively high removal force for removing the first removal object present in the exposed area and peeling off the treatment film having a relatively high removal force for removing the first removal object present in the non-exposed area. Therefore, the first removal object can be efficiently removed from the substrate having a surface with the exposed area and the non-exposed area.

[0022] In one embodiment of the present invention, the substrate processing method further includes: a process film residue removal step, wherein after the process film stripping step, a removal liquid is supplied to the surface of the substrate to remove the process film residue remaining on the surface of the substrate. According to the method, even if the process film residue adheres to the surface of the substrate after the process film is stripped by the stripping liquid, the residue can be removed by the removal liquid.

[0023] In one embodiment of the present invention, the process film stripping step includes the following step: not stripping the portion of the process film covering the exposed area, but stripping the portion of the process film covering the non-exposed area. In addition, the process film residue removal step includes the following step: removing the portion of the process film covering the exposed area by dissolving it in the removal liquid.

[0024] Even if a portion of the processing film covering the exposed region is not peeled off by supplying the peeling liquid to the surface of the substrate and remains on the exposed region, the portion can be dissolved in the removing liquid and removed from the exposed region.

[0025] When the portion of the treatment film covering the exposed area is dissolved in the removal liquid, the first removal object that was held and released by the portion of the treatment film covering the exposed area may reattach to the exposed area. Therefore, if the treatment film is formed after the pretreatment film having a relatively high removal force for removing the first removal object present in the exposed area is removed from the exposed area by peeling, most of the first removal object is removed from the exposed area before the treatment film is formed.

[0026] Therefore, even if the portion of the processing film covering the exposed region is dissolved in the removing liquid and removed from the exposed region, it is possible to sufficiently suppress the first removal object from remaining in the exposed region.

[0027] In one embodiment of the present invention, the processing film forming step includes the following steps: forming the processing film having a stripping target film and a protective film on the surface of the substrate, the stripping target film retains the first removal target existing in the non-exposed area of ​​the surface of the substrate and covers the non-exposed area, and the protective film covers the exposed area to protect. In addition, the substrate processing method further includes: a cleaning step, after the processing film stripping step, supplying a cleaning liquid to the surface of the substrate, and removing the second removal target existing on the surface of the substrate with the cleaning liquid.

[0028] According to the method, the processing liquid supplied to the surface of the substrate is solidified or cured, thereby forming a peeling target film covering the non-exposed area of ​​the substrate surface and a protective film covering the exposed area of ​​the substrate surface.

[0029] By supplying a stripping liquid to the surface of the substrate on which the stripping target film and the protective film are formed, the stripping target film is stripped from the surface of the substrate while maintaining the first removal target object. Thus, the first removal target object is removed from the surface of the substrate. On the other hand, the second removal target object remains on the surface of the substrate.

[0030] Then, the second object to be removed is removed from the surface of the substrate using the cleaning liquid, and then, the protective film is removed from the surface of the substrate using the removing liquid.

[0031] When the cleaning liquid is supplied to the surface of the substrate, the exposed area of ​​the substrate where the metal is exposed is covered by the protective film. Therefore, if the cleaning liquid has the property of causing the metal exposed on the surface of the substrate to deteriorate (e.g., oxidize) the second removal object can be removed without causing the metal to deteriorate.

[0032] Therefore, it is possible to suppress the deterioration of the metal exposed on the surface of the substrate and to efficiently remove the plurality of removal objects (the first removal objects and the second removal objects) from the surface of the substrate.

[0033] In one embodiment of the present invention, the substrate processing method further includes: a process film residue removal step, wherein after the process film stripping step, a removal liquid is supplied to the surface of the substrate to remove the process film residue remaining on the surface of the substrate. In addition, the process film residue removal step includes the following step: removing the protective film as the residue.

[0034] According to the method, even if the residue of the process film adheres to the surface of the substrate after the process film is stripped by the stripping liquid, the residue can be removed by the removing liquid. The protective film remaining on the substrate without being stripped by the stripping liquid is also dissolved by the removing liquid and removed from the exposed area.

[0035] Furthermore, after the pre-treatment film having a relatively high removal force for removing the first removal object present in the exposed area is removed from the exposed area by peeling, the treatment film is formed, so that most of the first removal object is removed from the exposed area before the treatment film is formed. Therefore, even if the protective film is dissolved in the removal liquid and removed from the exposed area, the first removal object can be sufficiently suppressed from remaining in the exposed area.

[0036] In one embodiment of the present invention, the first removal object and the second removal object are residues generated by dry etching.

[0037] In the back end of the line (BEOL) process of forming a plurality of metal layers on the surface of a substrate, a dry etching process is performed so that the metal is exposed on the surface of the substrate. That is, an exposed area where the metal is exposed and a non-exposed area other than the exposed area are formed on the surface of the substrate.

[0038] CF used in dry etching x The reaction products of etching gas (e.g., carbon tetrafluoride (CF4)) and the portion of the substrate constituting the non-exposed area adhere to the surface of the substrate as residue after dry etching. The portion of the substrate surface constituting the non-exposed area includes the surface of a Low-k film (low dielectric constant interlayer insulating film), an oxide film, a metal hard mask, etc.

[0039] Specifically, film-like reaction products (film-like residues) of the etching gas and the low-k interlayer insulating film and granular reaction products (granular residues) of the etching gas and the low-k interlayer insulating film, oxide film or metal hard mask are attached to the non-exposed area on the surface of the substrate. The so-called granular shape refers to spherical, ellipsoidal, polyhedral, etc. The granular residues are also attached to the exposed area on the surface of the substrate.

[0040] The granular residue can be peeled off by physical force, but the film-like residue covers at least a part of the non-exposed region and is difficult to be peeled off from the surface of the substrate by physical force compared to the granular residue.

[0041] Therefore, if the structure is such that the granular residue as the first removal object is removed by peeling off the stripping object film, and the film-like residue as the second removal object is dissolved and removed by using a cleaning liquid, the deterioration of the metal exposed on the surface of the substrate can be suppressed, and the removal object can be efficiently removed from the substrate.

[0042] In detail, a film to be stripped and a protective film are formed on the surface of the substrate after the dry etching process, and a stripping liquid is supplied to the surface of the substrate in a state where the film to be stripped and the protective film are formed, thereby stripping the film to be stripped from the surface of the substrate while maintaining the state of granular residue. Therefore, the granular residue is removed from the surface of the substrate. On the other hand, the film residue remains in the non-exposed area on the surface of the substrate. Then, the film residue is dissolved by a cleaning liquid and removed from the surface of the substrate, and then, the protective film is removed from the surface of the substrate by a removing liquid.

[0043] When the cleaning liquid is supplied to the surface of the substrate, the exposed area of ​​the metal on the surface of the substrate is covered by the protective film. Therefore, if the cleaning liquid has the property of causing the metal exposed on the surface of the substrate to deteriorate (e.g., oxidize) the metal, the film-like residue can be removed without causing the metal to deteriorate.

[0044] In one embodiment of the present invention, the treatment liquid contains a first solute and a first solvent that dissolves the first solute. The first solute contains a first high-solubility component and a first low-solubility component that is less soluble in the stripping liquid than the first high-solubility component. In addition, the treatment film stripping step includes the following step: selectively dissolving the first high-solubility component in a solid state in the stripping liquid.

[0045] According to the method, the first highly soluble component in a solid state in the treated film is selectively dissolved by the stripping solution. The phrase "the first highly soluble component in a solid state is selectively dissolved" does not mean that only the first highly soluble component in a solid state is dissolved. The phrase "the first highly soluble component in a solid state is selectively dissolved" means that the first low soluble component in a solid state is also slightly dissolved, but most of the first highly soluble component in a solid state is dissolved.

[0046] By dissolving the first high solubility component in a solid state in the stripping liquid, the stripping liquid passes through the processing film along the trace of the first high solubility component in the solid state (the path formed by the dissolution of the first high solubility component). As a result, the stripping liquid can act on the contact interface between the processing film and the substrate. On the other hand, the first low solubility component in the processing film is not dissolved but maintained in a solid state. Therefore, the first removal object can be maintained by using the first low solubility component in a solid state, while the stripping liquid is allowed to act on the contact interface between the first low solubility component in a solid state and the substrate. As a result, the processing film can be quickly removed from the surface of the substrate, and the first removal object can be efficiently removed from the surface of the substrate together with the processing film.

[0047] In one embodiment of the present invention, the process film stripping step includes a first through-hole forming step of partially dissolving the process film in the stripping solution to form a first through-hole in the process film.

[0048] Therefore, the stripping liquid can pass through the processing film through the first through hole and quickly reach the interface between the processing film and the surface of the substrate. Therefore, the stripping liquid can act on the interface between the processing film and the substrate, so that the processing film can be efficiently stripped from the substrate. As a result, the first removal object can be efficiently removed from the surface of the substrate.

[0049] In one embodiment of the present invention, the pretreatment solution contains a second solute and a second solvent that dissolves the second solute. The second solute contains a second high solubility component and a second low solubility component that is less soluble in the stripping solution than the second high solubility component. The pretreatment film stripping step includes the following step: selectively dissolving the second high solubility component in a solid state in the stripping solution.

[0050] According to the method, the second most soluble component in a solid state in the pretreatment film is selectively dissolved by the stripping solution. The so-called "the second most soluble component in a solid state is selectively dissolved" does not mean that only the second most soluble component in a solid state is dissolved. The so-called "the second most soluble component in a solid state is selectively dissolved" means that the second least soluble component in a solid state is also slightly dissolved, but most of the second most soluble component in a solid state is dissolved.

[0051] By dissolving the second high solubility component in a solid state in the stripping liquid, the stripping liquid passes through the pretreatment film along the trace of the second high solubility component in the solid state (the path formed by the dissolution of the second high solubility component). As a result, the stripping liquid can act on the contact interface between the pretreatment film and the substrate. On the other hand, the second low solubility component in the pretreatment film does not dissolve and is maintained in a solid state. Therefore, the second low solubility component in a solid state can be used to maintain the first removal object while the stripping liquid is allowed to act on the contact interface between the second low solubility component in a solid state and the substrate. As a result, the pretreatment film can be quickly removed from the surface of the substrate, and the first removal object can be efficiently removed from the surface of the substrate together with the pretreatment film.

[0052] In one embodiment of the present invention, the pretreatment film stripping step includes a second through-hole forming step of partially dissolving the pretreatment film in the stripping solution to form a second through-hole in the pretreatment film.

[0053] Therefore, the stripping liquid can pass through the pretreatment film via the second through hole and quickly reach the vicinity of the interface between the pretreatment film and the surface of the substrate. Therefore, the stripping liquid can act on the interface between the pretreatment film and the substrate, so that the pretreatment film can be efficiently stripped from the substrate. As a result, the first removal object can be efficiently removed from the surface of the substrate.

[0054] One embodiment of the present invention provides a substrate processing apparatus for processing a substrate having a surface having a first region and a second region where different substances are exposed.

[0055] The substrate processing device includes: a processing liquid supply unit, which supplies the processing liquid to the surface of the substrate; a processing film forming unit, which solidifies or hardens the processing liquid to form a processing film on the surface of the substrate; a pre-treatment liquid supply unit, which supplies the pre-treatment liquid to the surface of the substrate; a pre-treatment film forming unit, which solidifies or hardens the pre-treatment liquid to form a pre-treatment film on the surface of the substrate; a stripping liquid supply unit, which supplies the stripping liquid to the surface of the substrate; and a controller, which controls the pre-treatment liquid supply unit, the pre-treatment film forming unit, the processing liquid supply unit, the processing film forming unit and the stripping liquid supply unit.

[0056] The controller is programmed to: supply the pretreatment liquid to the surface of the substrate from the pretreatment liquid supply unit, solidify or harden the pretreatment liquid on the surface of the substrate by the pretreatment film forming unit, form a pretreatment film on the surface of the substrate, the pretreatment film retains the removal object on the surface of the substrate, supply stripping liquid to the surface of the substrate from the stripping liquid supply unit, strip the pretreatment film retaining the removal object from the surface of the substrate, after stripping the pretreatment film, supply treatment liquid to the surface of the substrate from the treatment liquid supply unit, solidify or harden the treatment liquid on the surface of the substrate by the treatment film forming unit, form a treatment film on the surface of the substrate, the treatment film retains the removal object on the surface of the substrate, supply stripping liquid to the surface of the substrate from the stripping liquid supply unit, strip the treatment film retaining the removal object from the surface of the substrate.

[0057] In addition, the removal force of the treatment film for removing the removal object existing in the second region is higher than the removal force of the pretreatment film for removing the removal object existing in the second region. Furthermore, the removal force of the pretreatment film for removing the removal object existing in the first region is higher than the removal force of the treatment film for removing the removal object existing in the first region.

[0058] According to the above structure, the same effect as that of the above substrate processing method is achieved.

[0059] In one embodiment of the present invention, the removal force for removing the removal object is composed of a holding force and a peeling property, wherein the holding force holds the removal object existing in the first region or the second region on the treatment film or the pretreatment film, and the peeling property indicates the ease of peeling of the treatment film or the pretreatment film in a state of holding the removal object. In addition, in the first region, the peeling property of the pretreatment film is higher than that of the treatment film, and in the second region, the holding force of the treatment film is higher than that of the pretreatment film.

[0060] Therefore, in the first region, most of the removal target can be removed by peeling off the pretreatment liquid film, and in the second region, most of the removal target can be removed by peeling off the treatment film. Therefore, even in the case where the substrate has a surface where regions with different substances are exposed, the removal target can be removed efficiently.

[0061] One embodiment of the present invention provides a recipe selection method for selecting a recipe for performing a substrate processing method, wherein the substrate processing method processes a processing target substrate. The recipe selection method includes: an information acquisition step for acquiring information related to the surface of the processing target substrate; a surface determination step for determining, based on the information acquired by the information acquisition step, which of the following substrates the processing target substrate is: a substrate having a surface having both an exposed area where a specific substance is exposed and a non-exposed area where the specific substance is not exposed, and a substrate having a surface having only the non-exposed area; and a recipe selection step for selecting a first recipe for executing a first substrate processing method, wherein the first substrate processing method uses a processing liquid to remove a removal object from the processing target substrate, if the surface determination step determines that the processing target substrate has only the non-exposed area on its surface; and selecting a second recipe for executing a second substrate processing method, wherein the second substrate processing method uses a pre-treatment liquid having a higher removal force than the treatment liquid to remove the removal object from the exposed area, and then uses the treatment liquid to remove the removal object from the processing target substrate.

[0062] It is preferred that different substrate processing methods be used to process substrates on which no exposed area where a specific substance is exposed is present and on which both exposed area and non-exposed area are present. Specifically, when only non-exposed area exists on the surface of the substrate to be processed, if the first substrate processing method is performed, i.e., the removal object is removed from the substrate to be processed using a processing liquid, the removal object can be fully removed from the surface of the substrate.

[0063] On the other hand, when there are both exposed areas and non-exposed areas on the surface of the processing target substrate, if only the processing liquid is used to remove the removal object from the processing target substrate, even if the removal object can be fully removed from the non-exposed area, it may not be possible to fully remove the removal object from the exposed area.

[0064] Therefore, when there are both exposed areas and non-exposed areas on the surface of the processing object substrate, it is necessary to perform a second substrate processing method, that is, use a pretreatment liquid that has a higher removal force for removing the removal object from a specific substance than the processing liquid, remove the removal object from the substrate, and then use the processing liquid to remove the removal object from the substrate.

[0065] Therefore, when there are only non-exposed areas on the surface of the processing object substrate, the first recipe of the first substrate processing method is selected to be executed, and when there are both exposed areas and non-exposed areas on the surface of the processing object substrate, the second recipe of the second substrate processing method is selected to be executed. In this way, an appropriate substrate processing method can be executed according to the state of the surface of the substrate.

[0066] In the second substrate processing method executed when the second recipe is selected, the pretreatment liquid may also contain a first component and a second component. The second component has a higher removal force than the first component to remove the object to be removed from the specific substance. The recipe selection method also includes: a type determination step, when the surface determination step determines that both the exposed area and the non-exposed area exist on the surface of the processing object substrate, based on the information acquired by the information acquisition step, the type of the specific substance exposed from the surface of the processing object substrate is determined. In addition, the recipe selection step includes the following steps: according to the specific substance of the type determined by the type determination step, the second recipe in which the concentration of the second component in the pretreatment liquid used in the second substrate processing method is set.

[0067] According to the method, when there are both exposed areas and non-exposed areas on the surface of the processing target substrate, the second recipe suitable for removing the removal target from the exposed area can be selected according to the type of the specific substance.

[0068] Another embodiment of the present invention provides a substrate processing method for processing a substrate having a surface having an exposed area where a specific substance is exposed and a non-exposed area other than the exposed area. The substrate processing method includes: a processing liquid supplying step, supplying the processing liquid to the surface of the substrate; a film forming step, solidifying or hardening the processing liquid supplied to the surface of the substrate, forming a stripping object film and a protective film on the surface of the substrate, the stripping object film retains a first removal object existing in the non-exposed area of ​​the surface of the substrate and covers the non-exposed area, and the protective film covers the exposed area for protection; a stripping object film stripping step, supplying a stripping liquid to the surface of the substrate, stripping the stripping object film retaining the first removal object from the surface of the substrate; a cleaning step, supplying a cleaning liquid to the surface of the substrate after the stripping object film stripping step, removing a second removal object existing on the surface of the substrate by using the cleaning liquid; and a protective film removing step, supplying a removal liquid to the surface of the substrate after the cleaning step, removing the protective film from the surface of the substrate.

[0069] According to the method, by solidifying or curing the processing liquid supplied to the surface of the substrate, a stripping target film covering the non-exposed area of ​​the substrate surface and a protective film covering the exposed area of ​​the substrate surface are formed. The stripping target film retains the first removal object existing in the non-exposed area.

[0070] By supplying a stripping liquid to the surface of the substrate in a state where the stripping target film and the protective film are formed, the stripping target film, which is in a state of maintaining the first removal target object, is stripped from the surface of the substrate. Therefore, the first removal target object is removed from the non-exposed area. After the stripping target film is stripped by the stripping liquid, the second removal target object also remains on the surface of the substrate.

[0071] Then, the second object to be removed is removed from the surface of the substrate using a cleaning liquid, and then the protective film is removed from the surface of the substrate using a removing liquid. When the cleaning liquid is supplied to the surface of the substrate, the exposed area of ​​the substrate surface where the specific substance is exposed is covered by the protective film. Therefore, if the cleaning liquid has the property of deteriorating (e.g., oxidizing) the specific substance exposed on the surface of the substrate, the second object to be removed can be removed without deteriorating the specific substance.

[0072] As described above, it is possible to efficiently remove a plurality of types of removal objects (first removal objects and second removal objects) from the surface of the substrate while suppressing the deterioration of the specific substance exposed on the surface of the substrate.

[0073] In another embodiment of the present invention, the processing liquid contains a first solute and a first solvent that dissolves the first solute. The first solute contains a first high-solubility component and a first low-solubility component that is less soluble in the stripping liquid than the first high-solubility component. The protective film has: a low-solubility layer, which is arranged at a position in contact with the specific substance and contains the first low-solubility component in a solid state; and a high-solubility layer, which is arranged on the opposite side of the specific substance relative to the low-solubility layer and contains the first high-solubility component in a solid state.

[0074] Therefore, in the protective film, the high solubility layer containing the first high solubility component in a solid state is dissolved by the stripping liquid, but the low solubility layer containing the first low solubility component in a solid state is hardly dissolved by the stripping liquid. Therefore, the stripping liquid is not easy to enter between the low solubility layer and the surface of the substrate. Therefore, the protective film is not stripped by the stripping liquid and remains on the exposed area. Therefore, the cleaning liquid can be supplied to the surface of the substrate while appropriately protecting the specific substance exposed from the surface of the substrate.

[0075] As a result, the second removal object can be efficiently removed from the surface of the substrate while suppressing the deterioration of the specific substance exposed on the surface of the substrate.

[0076] In another embodiment of the present invention, the processing liquid contains a first solute and a first solvent that dissolves the first solute. The first solute contains a first high-solubility component and a first low-solubility component that is less soluble in the stripping liquid than the first high-solubility component. The stripping object film forming step includes the following steps: forming the processing film containing the first high-solubility component in a solid state and the first low-solubility component in a solid state. In addition, the stripping object film stripping step includes the following steps: selectively dissolving the first high-solubility component in a solid state in the stripping liquid.

[0077] According to the above method, the first highly soluble component in a solid state in the film to be peeled off is selectively dissolved by the peeling liquid.

[0078] By dissolving the first high solubility component in a solid state in the stripping liquid, the stripping liquid passes through the stripping target film along the trace of the first high solubility component in the solid state (the path formed by the dissolution of the first high solubility component). As a result, the stripping liquid can act on the contact interface between the stripping target film and the substrate. On the other hand, the first low solubility component in the stripping target film does not dissolve and is maintained in a solid state. Therefore, while the first removal object can be maintained by using the first low solubility component in a solid state, the stripping liquid can act on the contact interface between the first low solubility component in a solid state and the substrate. As a result, the stripping target film can be quickly removed from the surface of the substrate, and the first removal object can be efficiently removed from the surface of the substrate together with the stripping target film.

[0079] In another embodiment of the present invention, the peeling-off film peeling step includes a first through-hole forming step of partially dissolving the peeling-off film in the peeling liquid to form a first through-hole in the peeling-off film.

[0080] Therefore, the stripping liquid can pass through the processing film via the first through hole and quickly reach the vicinity of the interface between the stripping target film and the non-exposed area of ​​the surface of the substrate. Therefore, the stripping liquid can act on the interface between the stripping target film and the substrate, and the stripping target film can be efficiently stripped from the substrate. As a result, the first removal target can be efficiently removed from the surface of the substrate.

[0081] In another embodiment of the present invention, the substrate processing method further includes: a pretreatment liquid supplying process, wherein the pretreatment liquid is supplied to the surface of the substrate before the treatment liquid supplying process; a pretreatment film forming process, wherein the pretreatment liquid supplied to the surface of the substrate is solidified or hardened to form a pretreatment film on the surface of the substrate before the treatment liquid supplying process, wherein the pretreatment film maintains the first removal object present in the exposed area on the surface of the substrate; and a pretreatment film stripping process, wherein a stripping liquid is supplied to the surface of the substrate before the treatment liquid supplying process to strip the pretreatment film together with the first removal object from the exposed area on the surface of the substrate.

[0082] According to the method, the first object to be removed existing in the exposed area on the surface of the substrate can be removed before the treatment liquid is supplied to the surface of the substrate. That is, after the first object to be removed is removed from the exposed area, a protective film can be formed in the exposed area. Therefore, the state in which the first object to be removed is removed from the exposed area on the surface of the substrate can be maintained until the protective film is removed in the subsequent protective film removal process. Therefore, even in the case where the protective film is dissolved in the removal liquid, the first object to be removed can be suppressed from remaining in the exposed area after the protective film is removed.

[0083] In another embodiment of the present invention, the pretreatment solution contains a second solute and a second solvent that dissolves the second solute. The second solute contains a second high solubility component and a second low solubility component that is less soluble in the stripping solution than the second high solubility component. The pretreatment film forming step includes the following steps: forming the pretreatment film containing the second high solubility component in a solid state and the second low solubility component in a solid state. In addition, the pretreatment film stripping step includes the following steps: selectively dissolving the second high solubility component in a solid state in the pretreatment film in the stripping solution.

[0084] According to the above method, the second highly soluble component in a solid state in the pretreatment film is selectively dissolved by the stripping liquid.

[0085] By dissolving the second high solubility component in a solid state in the stripping liquid, the stripping liquid passes through the pretreatment film along the trace of the second high solubility component in the solid state (the path formed by the dissolution of the second high solubility component). As a result, the stripping liquid can act on the contact interface between the pretreatment film and the substrate. On the other hand, the second low solubility component in the pretreatment film does not dissolve and is maintained in a solid state. Therefore, the second low solubility component in a solid state can be used to maintain the first removal object while the stripping liquid is allowed to act on the contact interface between the second low solubility component in a solid state and the substrate. As a result, the pretreatment film can be quickly removed from the surface of the substrate, and the first removal object can be efficiently removed from the surface of the substrate together with the pretreatment film.

[0086] In another embodiment of the present invention, the pretreatment film stripping step includes a second through-hole forming step of partially dissolving the pretreatment film in the stripping solution to form a second through-hole in the pretreatment film.

[0087] Therefore, the stripping liquid can pass through the pretreatment film via the second through hole and quickly reach the vicinity of the interface between the pretreatment film and the surface of the substrate. Therefore, the stripping liquid can act on the interface between the pretreatment film and the substrate to efficiently strip the stripping target film from the substrate. As a result, the first removal target can be efficiently removed from the surface of the substrate.

[0088] In another embodiment of the present invention, the specific substance is a metal, and the cleaning liquid has an oxidizing power to oxidize the metal exposed on the surface of the substrate. If the exposed area of ​​the substrate where the metal is exposed is covered by a protective film when the cleaning liquid is supplied to the surface of the substrate, oxidation of the metal by the cleaning liquid can be avoided and the second removal object can be removed.

[0089] In another embodiment of the present invention, the first removal object and the second removal object are residues generated by dry etching. Therefore, if the granular residue as the first removal object is removed by stripping the stripping object film, and the film residue as the second removal object is removed by a cleaning liquid, oxidation of the metal exposed on the surface of the substrate can be suppressed, and the removal object can be removed from the substrate efficiently.

[0090] Specifically, by supplying a stripping liquid to the surface of the substrate on which the stripping target film and the protective film are formed, the stripping target film remaining with the granular residue can be stripped from the surface of the substrate. Thus, the first removal target is removed from the non-exposed region.

[0091] Then, the film-like residue is removed from the surface of the substrate using a cleaning liquid, and then the protective film is removed from the surface of the substrate using a removing liquid. When the cleaning liquid is supplied to the surface of the substrate, the exposed area of ​​the substrate where the metal is exposed is covered by the protective film. Therefore, although the cleaning liquid has the property of oxidizing the metal exposed on the surface of the substrate, the film-like residue can be removed without oxidizing the metal.

[0092] In another embodiment of the present invention, the removal liquid has a property of dissolving the protective film and the film to be stripped. Therefore, the protective film can be dissolved in the removal liquid, and the protective film can be smoothly removed from the upper surface of the substrate. Furthermore, the removal liquid can dissolve the film to be stripped. Therefore, even if the film to be stripped is stripped by the stripping liquid and the residue of the film to be stripped adheres to the surface of the substrate, the removal liquid can be used to remove the residue.

[0093] Another embodiment of the present invention provides a substrate processing device for processing a substrate having a surface having an exposed area where a specific substance is exposed and a non-exposed area other than the exposed area. The substrate processing device includes: a processing liquid supply unit for supplying processing liquid to the surface of the substrate; a film forming unit for solidifying or hardening the processing liquid to form a solid film; a stripping liquid supply unit for supplying stripping liquid to the surface of the substrate; a cleaning liquid supply unit for supplying cleaning liquid to the surface of the substrate; a removing liquid supply unit for supplying removing liquid to the surface of the substrate; and a controller for controlling the processing liquid supply unit, the film forming unit, the stripping liquid supply unit, the cleaning liquid supply unit, and the removing liquid supply unit.

[0094] In addition, the controller is programmed to supply the processing liquid from the processing liquid supply unit to the surface of the substrate, solidify or harden the processing liquid on the surface of the substrate by the film forming unit, form a stripping target film and a protective film on the surface of the substrate, the stripping target film retains the first removal target existing on the surface of the substrate and covers the non-exposed area, and the protective film covers the exposed area to protect, supply the stripping liquid from the stripping liquid supply unit to the surface of the substrate, thereby stripping the stripping target film together with the first removal target from the surface of the substrate, after stripping the stripping target film, supply cleaning liquid from the cleaning liquid supply unit to the surface of the substrate to remove the second removal target existing on the surface of the substrate, and after supplying the cleaning liquid, supply removal liquid from the removal liquid supply unit to the surface of the substrate to remove the protective film from the surface of the substrate. According to the above structure, the same effect as the substrate processing method of the other embodiment is achieved.

[0095] The above and other objects, features and effects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0096] Figure 1 It is a schematic plan view showing the layout of a substrate processing apparatus according to the first embodiment of the present invention.

[0097] Figure 2 This is an example of a cross-sectional view of a surface layer of a substrate processed by the substrate processing apparatus.

[0098] Figure 3 It is a schematic partial cross-sectional view showing the general structure of a processing unit included in the substrate processing apparatus.

[0099] Figure 4 The following is a block diagram showing the hardware of a controller included in the substrate processing apparatus.

[0100] Figure 5 It is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus.

[0101] Fig. 6A It is a schematic diagram for explaining the state of the process (step S2) of supplying the pre-treatment liquid to the substrate treatment.

[0102] Figure 6B It is a schematic diagram for explaining the state of the pre-treatment film formation process (step S3) of the above-mentioned substrate processing.

[0103] Figure 6C It is a schematic diagram for explaining the state of the said pre-treatment film formation process (step S3).

[0104] Fig.6D It is a schematic diagram for explaining the state of the pre-treatment film peeling process (step S4) of the said substrate processing.

[0105] Fig. 6E It is a schematic diagram for explaining the state of the stripping liquid removal process (step S5) of the above-mentioned substrate processing.

[0106] Fig. 6F It is a schematic diagram for explaining the state of the pre-treatment film residue removal process (step S6) of the above-mentioned substrate processing.

[0107] Figure 6G It is a schematic diagram for explaining the state of the process (step S7) of supplying the processing liquid to the said substrate processing.

[0108] Figure 6HIt is a schematic diagram for explaining the state of the processing film forming step (step S8) of the above-mentioned substrate processing.

[0109] Fig.6I It is a schematic diagram for explaining the state of the said process film forming process (step S8).

[0110] Figure 6J It is a schematic diagram for explaining the state of the process film peeling process (step S9) of the said substrate processing.

[0111] Figure 6K It is a schematic diagram for explaining the state of the stripping liquid removal process (step S10) of the above-mentioned substrate processing.

[0112] Figure 6L It is a schematic diagram for explaining the process of removing the processing film residue (step S11) of the substrate processing.

[0113] Figure 6M It is a schematic diagram for explaining the state of the spin drying process (step S12) of the above-mentioned substrate processing.

[0114] Fig. 7A It is a schematic diagram for explaining the state near the surface of the substrate in a state where the pretreatment film is formed by performing the pretreatment film forming step (step S3 ).

[0115] Figure 7B It is a schematic diagram for explaining the state near the surface of the substrate during the execution of the pretreatment film peeling step (step S4).

[0116] Figure 7C It is a schematic diagram for explaining the state near the surface of the substrate in a state where the processing film is formed by performing the processing film forming step (step S8).

[0117] Fig.7D It is a schematic diagram for explaining the state near the surface of the substrate during the execution of the processing film peeling step (step S9).

[0118] Fig. 7E It is a schematic diagram for explaining the state near the surface of the substrate in a state where the residue of the process film is removed by performing the process film residue removing step (step S11).

[0119] Figure 8A to Figure 8C This is a schematic diagram for explaining a state where a pretreatment film is peeled off from a substrate.

[0120] Figures 9A to 9C This is a schematic diagram for explaining a state where a processed film is peeled off from a substrate.

[0121] Figures 10A to 10C It is a schematic diagram for explaining a state where an exposed region covering portion covering an exposed region where a metal film is exposed on a surface of a substrate is removed from a substrate.

[0122] Fig.11 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit included in a substrate processing apparatus according to a second embodiment of the present invention.

[0123] Fig.12 This is an example of a cross-sectional view of a surface layer of a substrate processed by the substrate processing apparatus according to the second embodiment.

[0124] Fig.13 This is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus according to the second embodiment.

[0125] Fig.14A It is a schematic diagram for explaining the state of the cleaning process (step S20) of the substrate processing according to the second embodiment.

[0126] Fig. 14B It is a schematic diagram for explaining the state of the cleaning liquid removing process (step S21) of the substrate processing of the second embodiment.

[0127] Fig.15A This is a schematic diagram for explaining the state near the surface of the substrate in which the pretreatment film is formed by performing the pretreatment film forming step (step S3) of the substrate treatment according to the second embodiment.

[0128] Fig. 15B This is a schematic diagram for explaining the state near the surface of the substrate during the execution of the pretreatment film peeling step (step S4) of the substrate treatment according to the second embodiment.

[0129] Fig. 15C This is a schematic diagram for explaining the state near the surface of the substrate in which the processed film is formed by performing the processed film forming step (step S12) of the substrate processing according to the second embodiment.

[0130] Fig.15D This is a schematic diagram for explaining the state near the surface of the substrate during the execution of the processing film peeling step (step S13) of the substrate processing according to the second embodiment.

[0131] Fig.15E It is a schematic diagram for explaining the state near the surface of the substrate during the execution of the cleaning step (step S20) of the substrate processing according to the second embodiment.

[0132] Fig.16This table is a table for explaining the results of an experiment for verifying the change in the particle removal force from a copper film caused by changing the ratio of the first component and the second component of the highly soluble component in the polymer-containing solution used as the treatment liquid and the pretreatment liquid.

[0133] Fig.17 The diagram is a schematic diagram of a first movable nozzle and a third movable nozzle of a processing unit included in a substrate processing apparatus according to a third embodiment of the present invention and their peripheral components.

[0134] Fig.18 This is a flowchart for explaining an example of a recipe selection process executed to select a recipe in the substrate processing apparatus according to the third embodiment.

[0135] Fig.19 This is a flowchart for explaining another example of the recipe selection process in the substrate processing apparatus according to the third embodiment.

[0136] Fig. 20 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit included in a substrate processing apparatus according to a fourth embodiment.

[0137] Fig.21 This is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus according to the fourth embodiment.

[0138] Fig.22A This is a schematic diagram for explaining the state near the surface of the substrate in which the processed film is formed by performing the processed film forming step (step S8) of the substrate processing according to the fourth embodiment.

[0139] Fig. 22B This is a schematic diagram for explaining the state near the surface of the substrate during the execution of the processing film peeling step (step S9) of the substrate processing according to the fourth embodiment.

[0140] Fig. 22C It is a schematic diagram for explaining the state near the surface of the substrate during the execution of the cleaning step (step S20) of the substrate processing according to the fourth embodiment.

[0141] Fig.22D This is a schematic diagram for explaining the state near the surface of the substrate during the execution of the process film residue removing step (step S11) of the substrate processing according to the fourth embodiment.

[0142] Figures 23A to 23C This is a schematic diagram for explaining a state in which a film to be peeled off is peeled off from a substrate in substrate processing according to the fourth embodiment.

[0143] Figures 24A to 24DThis is a schematic diagram for explaining a state in which a protective film is removed from a substrate in substrate processing according to the fourth embodiment.

[0144] Explanation of symbols

[0145] 1. 1P, 1Q, 1R: Substrate processing equipment

[0146] 2: Processing Unit

[0147] 3: Controller

[0148] 3A: Input Devices

[0149] 3B: Display device

[0150] 3C: Alarm Device

[0151] 3a: Computer Body

[0152] 3b: CPU

[0153] 3c: Primary storage device

[0154] 3d: Peripheral devices

[0155] 3e: Auxiliary storage device

[0156] 3f: Reading device

[0157] 3g: communication device

[0158] 4: Chamber

[0159] 5: Rotating chuck

[0160] 6: Opposite components

[0161] 6a: Facing surface

[0162] 6b: Connecting hole

[0163] 7: Processing cup

[0164] 9: First moving nozzle

[0165] 10: Second moving nozzle

[0166] 11: The third moving nozzle

[0167] 12: Central nozzle

[0168] 12a, 13a: Spout

[0169] 13: Lower surface nozzle

[0170] 14: The fourth moving nozzle

[0171] 20: Chuck pin

[0172] 21: Rotating base

[0173] 21a, 102, 202: Through hole

[0174] 22: Rotation axis

[0175] 23: Rotary motor

[0176] 30: Casing

[0177] 31: First Tube

[0178] 32: Second tube

[0179] 33: The third tube

[0180] 35: First nozzle moving unit

[0181] 36: Second nozzle moving unit

[0182] 37: Third nozzle moving unit

[0183] 38: Fourth nozzle moving unit

[0184] 40: Processing liquid piping

[0185] 41: Upper stripping liquid pipe

[0186] 42: Pretreatment liquid piping

[0187] 43: Upper eluent piping

[0188] 44: Removal liquid piping

[0189] 45: Gas piping

[0190] 46: Cleaning fluid piping

[0191] 50: Processing liquid valve

[0192] 51: Upper stripping liquid valve

[0193] 52: Pretreatment liquid valve

[0194] 53: Upper eluent valve

[0195] 54: Remove liquid valve

[0196] 55: Gas valve

[0197] 56: Cleaning fluid valve

[0198] 60: Hollow shaft

[0199] 60a: Inner Space

[0200] 61: Facing member lifting unit

[0201] 71: Guard

[0202] 71A: First guard plate

[0203] 71B: Second guard plate

[0204] 72: Cup

[0205] 72A: First Cup

[0206] 72B: Second Cup

[0207] 73: External wall components

[0208] 74: Guard plate lifting unit

[0209] 80: Common piping

[0210] 81: Lower eluent piping

[0211] 82: Lower stripping liquid pipe

[0212] 83: Heat medium piping

[0213] 86: Lower eluent valve

[0214] 87: Lower stripping liquid valve

[0215] 88: Heat transfer valve

[0216] 100: Processing film

[0217] 100A: Peel off the target film

[0218] 100B: Protective film

[0219] 101, 201: Liquid film

[0220] 103: Remove the object

[0221] 105, 205: Diaphragm

[0222] 110, 210: Highly soluble solids

[0223] 111, 211: Low soluble solids

[0224] 130: Exposed area covering part

[0225] 131: Non-exposed area covered part

[0226] 140, 142: Low-soluble component liquid piping

[0227] 141, 143: First component liquid piping

[0228] 144: Second component liquid piping

[0229] 150, 152: Low-soluble component liquid valve

[0230] 151, 153: First component liquid valve

[0231] 154: Second component liquid valve

[0232] 160: Concave and convex pattern

[0233] 161: Structure

[0234] 161A: Etching stop film

[0235] 161B: Low dielectric constant interlayer insulation film

[0236] 161C: Oxide film

[0237] 161D: Metal Hard Mask

[0238] 162: Concave

[0239] 163: Metal film

[0240] 165: Patterned surface

[0241] 170: Exposed area

[0242] 171: Non-exposed area

[0243] 180: Low solubility layer

[0244] 181: High solubility layer

[0245] 200: Pretreatment film

[0246] 203: First object to be removed

[0247] 204: Second object to be removed

[0248] A1: Rotation axis

[0249] C: Carrier

[0250] CR, IR: handling robots

[0251] G1, G2: Clearance

[0252] LP: Loading port

[0253] P: Program

[0254] R: Recipe

[0255] R1: First Formula

[0256] R2: Second recipe

[0257] RM: Removable Media

[0258] S1~S13, S20, S21, S30~S34: Steps

[0259] T: Normal direction

[0260] W: substrate DETAILED DESCRIPTION

[0261] <First embodiment>

[0262] Figure 1 It is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment of the present invention.

[0263] The substrate processing apparatus 1 is a single-wafer type apparatus that processes each substrate W such as a silicon wafer. In the present embodiment, the substrate W is a disk-shaped substrate.

[0264] The substrate processing device 1 includes: multiple processing units 2, which use fluid to process the substrate W; a loading port LP, which carries a carrier C, and the carrier C contains multiple substrates W to be processed in the processing unit 2; a transport robot IR and a transport robot CR, which transport the substrate W between the loading port LP and the processing unit 2; and a controller 3, which controls the substrate processing device 1.

[0265] The transport robot IR transports the substrate W between the carrier C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing unit 2. The plurality of processing units 2 have, for example, the same structure. The details will be described below, but the processing fluid supplied to the substrate W in the processing unit 2 includes a rinse liquid, a processing liquid, a pre-processing liquid, a stripping liquid, a cleaning liquid, a removal liquid, a heat medium, an inactive gas (gas), and the like.

[0266] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and a substrate W is processed in the processing cup 7. The chamber 4 is provided with an entrance (not shown) for carrying in or carrying out the substrate W by the transport robot CR. The chamber 4 includes a shutter unit (not shown) for opening and closing the entrance.

[0267] Figure 2 FIG. 1 is an example of a cross-sectional view of the surface layer of the substrate W processed by the substrate processing apparatus 1. The surface layer of the substrate W is a portion of the substrate W near the surface.

[0268] A fine concavo-convex pattern 160 is formed on the surface of the unprocessed substrate W before being processed by the processing unit 2. The concavo-convex pattern 160 includes fine convex structures 161 formed on the surface of the substrate W, and concave portions (grooves) 162 formed between adjacent structures 161. The structures 161 include an etching stopper film 161A, a low dielectric constant interlayer insulating film 161B, an oxide film 161C, a metal hard mask 161D, and the like.

[0269] The surface of the concavo-convex pattern 160, that is, the surface of the structure 161 (convex part) and the surface of the concave part 162, forms a pattern surface 165 having concavo-convexity. The pattern surface 165 is included in the surface of the substrate W. On the pattern surface 165 of the substrate W, there are regions where various substances are exposed. Figure 2 In the example shown, a metal film 163 such as a copper film is exposed from the bottom of the recess 162. The pattern surface 165 includes an exposed region 170 where the surface of the metal film 163 is exposed, and a non-exposed region 171 where the metal film 163 is not exposed. The non-exposed region 171 is a region of the pattern surface 165 of the substrate W other than the exposed region 170.

[0270] In this embodiment, metal such as copper is an example of the specific substance. In addition, the exposed region 170 corresponds to the first region, and the non-exposed region 171 corresponds to the second region.

[0271] Removal object 103 is attached to both non-exposed region 171 and exposed region 170. Removal object 103 is, for example, granular. The granular shape includes spherical, ellipsoidal, polyhedral, etc. Removal object 103 is an example of a first removal object.

[0272] Figure 3 1 is a schematic diagram for explaining a structural example of the processing unit 2. The processing unit 2 includes a spin chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11, a central nozzle 12, and a lower surface nozzle 13.

[0273] The spin chuck 5 rotates the substrate W around a vertical rotation axis A1 (vertical axis) passing through the center of the substrate W while holding the substrate W horizontally. The spin chuck 5 includes a plurality of chuck pins 20 , a rotating base 21 , a rotating shaft 22 , and a rotating motor 23 .

[0274] The rotating base 21 has a disk shape along the horizontal direction. On the upper surface of the rotating base 21, a plurality of chuck pins 20 for holding the periphery of the substrate W are arranged at intervals in the circumferential direction of the rotating base 21. The rotating base 21 and the plurality of chuck pins 20 constitute a substrate holding unit for holding the substrate W in a horizontal position. The substrate holding unit is also called a substrate holder.

[0275] The rotating shaft 22 extends in the vertical direction along the rotating axis A1. The upper end of the rotating shaft 22 is coupled to the center of the lower surface of the rotating base 21. The rotating motor 23 applies a rotating force to the rotating shaft 22. By rotating the rotating shaft 22 by the rotating motor 23, the rotating base 21 rotates. As a result, the substrate W rotates around the rotating axis A1. The rotating motor 23 is an example of a substrate rotating unit that rotates the substrate W around the rotating axis A1.

[0276] The facing member 6 faces the substrate W held on the rotating chuck 5 from above. The facing member 6 is formed into a disk shape having a diameter substantially the same as or larger than that of the substrate W. The facing member 6 has a facing surface 6a facing the upper surface of the substrate W. The facing surface 6a is arranged along a substantially horizontal plane above the rotating chuck 5. In addition, the so-called upper surface of the substrate W refers to the surface on the upper side of the substrate W, and the so-called lower surface of the substrate W refers to the surface on the lower side of the substrate W.

[0277] A hollow shaft 60 is fixed to the opposite side of the facing member 6 from the facing surface 6a. A communicating hole 6b is formed in the portion of the facing member 6 overlapping the rotation axis A1 in a plan view, penetrating the facing member 6 vertically. The communicating hole 6b communicates with the internal space 60a of the hollow shaft 60.

[0278] The facing member 6 blocks the gas environment in the space between the facing surface 6 a and the upper surface of the substrate W from the gas environment outside the space. Therefore, the facing member 6 is also called a shielding plate.

[0279] The processing unit 2 further includes an opposing member lifting unit 61, which drives the lifting of the opposing member 6. The opposing member lifting unit 61 can make the opposing member 6 be located at any position (height) from the lower position to the upper position in the vertical direction. The so-called 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 so-called 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 located at the upper position, the transport robot CR can access the rotary chuck 5 to carry in and out the substrate W.

[0280] The opposing member lifting unit 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) supporting the hollow shaft 60, and an electric motor (not shown) for applying a driving force to the ball screw mechanism. The opposing member lifting unit 61 is also called an opposing member lifter (shielding plate lifter).

[0281] The processing cup 7 includes: a plurality of guards 71 ​​for catching liquid flying outward from the substrate W held on the spin chuck 5; a plurality of cups 72 for catching liquid guided downward by the plurality of guards 71; and a cylindrical outer wall member 73 surrounding the plurality of guards 71 ​​and the plurality of cups 72.

[0282] In the present embodiment, an example is shown in which two guard plates 71 (a first guard plate 71A and a second guard plate 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided.

[0283] The first cup 72A and the second cup 72B each have a shape of an annular groove that is open upward.

[0284] The first guard plate 71A is disposed so as to surround the rotating base 21. The second guard plate 71B is disposed on the outer side in the rotation radial direction of the substrate W than the first guard plate 71A so as to surround the rotating base 21.

[0285] The first guard plate 71A and the second guard plate 71B each have a substantially cylindrical shape. The upper end of each guard plate 71 is inclined inwardly so as to face the rotating base 21 .

[0286] The first cup 72A receives the liquid guided downward by the first guard plate 71A. The second cup 72B is formed integrally with the first guard plate 71A, and receives the liquid guided downward by the second guard plate 71B.

[0287] The processing unit 2 includes a guard plate lifting unit 74, which lifts the first guard plate 71A and the second guard plate 71B in the vertical direction. The guard plate lifting unit 74 lifts the first guard plate 71A between the lower position and the upper position. The guard plate lifting unit 74 lifts the second guard plate 71B between the lower position and the upper position.

[0288] When the first guard plate 71A and the second guard plate 71B are both in the upper position, the liquid scattered from the substrate W is received by the first guard plate 71A. When the first guard plate 71A is in the lower position and the second guard plate 71B is in the upper position, the liquid scattered from the substrate W is received by the second guard plate 71B. When the first guard plate 71A and the second guard plate 71B are both in the lower position, the transfer robot CR can access the spin chuck 5 to carry the substrate W in and out.

[0289] The guard plate lifting unit 74 includes, for example: a first ball screw mechanism (not shown) coupled to the first guard plate 71A; a first motor (not shown) providing a driving force to the first ball screw mechanism; a second ball screw mechanism (not shown) coupled to the second guard plate 71B; and a second motor (not shown) providing a driving force to the second ball screw mechanism. The guard plate lifting unit 74 is also called a guard plate lifter.

[0290] The first movable nozzle 9 is an example of a processing liquid nozzle (processing liquid supplying unit) that supplies (discharges) the processing liquid onto the upper surface of the substrate W held by the spin chuck 5 .

[0291] The first movable nozzle 9 is moved in the horizontal direction and the vertical direction by the first nozzle moving unit 35. The first movable nozzle 9 can be moved in the horizontal direction between the center position and the home position (retracted position). When the first movable nozzle 9 is located at the center position, it faces the rotation center of the upper surface of the substrate W. The so-called rotation center of the upper surface of the substrate W is the intersection position of the upper surface of the substrate W with the rotation axis A1.

[0292] When located at the home position, the first movable nozzle 9 is not facing the upper surface of the substrate W but is located outside the processing cup 7 in a plan view. The first movable nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0293] The first nozzle moving unit 35 includes, for example: an arm (not shown), which is connected to the first moving nozzle 9 and extends horizontally; a rotation axis (not shown), which is connected to the arm and extends in the vertical direction; and a rotation axis driving unit (not shown) that raises, lowers or rotates the rotation axis.

[0294] The rotation axis driving unit causes the arm to swing by rotating the rotation axis around a vertical rotation axis. Furthermore, the rotation axis driving unit causes the arm to move up and down by raising and lowering the rotation axis in the vertical direction. According to the swinging and raising and lowering of the arm, the first movable nozzle 9 moves in the horizontal direction and the vertical direction.

[0295] The first moving nozzle 9 is connected to a process liquid pipe 40 for guiding the process liquid. When a process liquid valve 50 inserted in the process liquid pipe 40 is opened, the process liquid is ejected downward from the first moving nozzle 9 in the form of a continuous flow.

[0296] The processing liquid ejected from the first movable nozzle 9 contains a solute and a solvent. The processing liquid solidifies or hardens by at least a portion of the solvent volatilizing (evaporating). The processing liquid solidifies or hardens on the substrate W to form a solid processing film, and the solid processing film maintains the removal object 103 on the substrate W.

[0297] Here, "solidification" means, for example, that the solute solidifies due to the force acting between molecules or atoms as the solvent evaporates. "Hardening" means, for example, that the solute solidifies due to chemical changes such as polymerization or cross-linking. Therefore, "solidification or hardening" means that the solute "solidifies" due to various reasons.

[0298] The solute contained in the processing liquid ejected from the first moving nozzle 9 includes a low-solubility component and a high-solubility component.

[0299] When metal is exposed on the surface of the substrate W, it is preferable that the solute contained in the processing liquid ejected from the first moving nozzle 9 contains an anti-corrosion component. The details will be described later, and the anti-corrosion component is, for example, benzotriazole (BTA).

[0300] As the low-soluble component and the high-soluble component contained in the treatment liquid ejected from the first moving nozzle 9, substances having different solubility in the stripping liquid can be used. The low-soluble component contained in the treatment liquid ejected from the first moving nozzle 9 is, for example, novolac. The high-soluble component contained in the treatment liquid ejected from the first moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane. The treatment liquid is also referred to as a polymer-containing solution, and the treatment film is also referred to as a polymer film.

[0301] The solvent contained in the processing liquid ejected from the first moving nozzle 9 may be a liquid that dissolves the low-soluble component and the high-soluble component. The solvent contained in the processing liquid is preferably a liquid that is compatible (miscible) with the stripping liquid.

[0302] The solvent contained in the treatment liquid is referred to as the first solvent, the solute contained in the treatment liquid is referred to as the first solute, the low-soluble component contained in the treatment liquid is referred to as the first low-soluble component, and the high-soluble component contained in the treatment liquid is referred to as the first high-soluble component.

[0303] The details of the solvent, the low-soluble component, the high-soluble component, and the anti-corrosion component contained in the processing liquid ejected from the first moving nozzle 9 will be described later.

[0304] The second movable nozzle 10 is an example of a stripping liquid nozzle (stripping liquid supply unit) that supplies (sprays) a stripping liquid such as ammonia water in a continuous flow to the upper surface of the substrate W held on the spin chuck 5. The stripping liquid is a liquid for stripping the processing film that holds the removal object 103 from the upper surface of the substrate W. Specifically, only the portion of the processing film that covers the non-exposed region 171 is stripped from the substrate W by the stripping liquid.

[0305] The second movable nozzle 10 is moved in the horizontal direction and the vertical direction by the second nozzle moving unit 36. The second movable nozzle 10 is movable in the horizontal direction between a center position and an original position (retracted position).

[0306] When the second movable nozzle 10 is located at the center position, it faces the rotation center of the upper surface of the substrate W. When the second movable nozzle 10 is located at the home position, it does not face the upper surface of the substrate W, but is located outside the processing cup 7 in a plan view. The second movable nozzle 10 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0307] The second nozzle moving unit 36 ​​has the same structure as the first nozzle moving unit 35. That is, the second nozzle moving unit 36 ​​includes, for example: an arm (not shown) coupled to the second moving nozzle 10 and extending horizontally; a rotation shaft (not shown) coupled to the arm and extending in the vertical direction; and a rotation shaft driving unit (not shown) that raises and lowers or rotates the rotation shaft.

[0308] The stripping liquid ejected from the second moving nozzle 10 may be a liquid that dissolves highly soluble components contained in the solute of the processing liquid more easily than low soluble components contained in the solute of the processing liquid. The stripping liquid ejected from the second moving nozzle 10 is not limited to ammonia water.

[0309] The stripping liquid ejected from the second moving nozzle 10 may be an alkaline aqueous solution (alkaline liquid) other than ammonia water. Specific examples of alkaline aqueous solutions other than ammonia water include tetramethylammonium hydroxide (TMAH) aqueous solution, choline aqueous solution, and any combination thereof.

[0310] The stripping liquid ejected from the second moving nozzle 10 may be pure water (preferably DIW) or a neutral or acidic aqueous solution (non-alkaline aqueous solution).

[0311] The second moving nozzle 10 is connected to an upper stripping liquid pipe 41 that guides the stripping liquid to the second moving nozzle 10. When the upper stripping liquid valve 51 inserted in the upper stripping liquid pipe 41 is opened, the stripping liquid is ejected downward from the ejection port of the second moving nozzle 10 in a continuous flow.

[0312] The third movable nozzle 11 is an example of a pre-processing liquid nozzle (pre-processing liquid supplying unit) that supplies (discharges) the pre-processing liquid onto the upper surface of the substrate W held by the spin chuck 5 .

[0313] The third movable nozzle 11 is moved in the horizontal direction and the vertical direction by the third nozzle moving unit 37. The third movable nozzle 11 is movable in the horizontal direction between a center position and an original position (retracted position).

[0314] When the third movable nozzle 11 is located at the center position, it faces the rotation center of the upper surface of the substrate W. When the third movable nozzle 11 is located at the home position, it does not face the upper surface of the substrate W, but is located outside the processing cup 7 in a plan view. The third movable nozzle 11 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.

[0315] The third nozzle moving unit 37 has the same structure as the first nozzle moving unit 35. That is, the third nozzle moving unit 37 includes, for example, an arm (not shown) coupled to the third moving nozzle 11 and extending horizontally, a rotation shaft (not shown) coupled to the arm and extending in the vertical direction, and a rotation shaft driving unit (not shown) for lifting or rotating the rotation shaft.

[0316] The pretreatment liquid ejected from the third moving nozzle 11 contains a solute and a solvent. The pretreatment liquid solidifies or hardens by at least a portion of the solvent volatilizing (evaporating). The pretreatment liquid solidifies or hardens on the substrate W to form a pretreatment film, which maintains the removal object 103 on the substrate W.

[0317] The solute contained in the pretreatment liquid ejected from the third moving nozzle 11 includes a low-solubility component and a high-solubility component.

[0318] When metal is exposed on the surface of the substrate W, it is preferable that the solute contained in the pretreatment liquid ejected from the third moving nozzle 11 contains an anticorrosive component. The details will be described later, but the anticorrosive component is, for example, BTA.

[0319] The low-soluble component and the high-soluble component contained in the pretreatment liquid can use substances with different solubility in the stripping liquid. The low-soluble component contained in the pretreatment liquid ejected from the third moving nozzle 11 is, for example, phenolic varnish. The high-soluble component contained in the pretreatment liquid ejected from the third moving nozzle 11 includes 2,2-bis(4-hydroxyphenyl)propane (first component) and 3,6-dimethyl-4-octyne-3,6-diol (second component). The pretreatment liquid is also called a polymer-containing solution, and the pretreatment film is also called a polymer film.

[0320] The solvent contained in the pretreatment liquid ejected from the third moving nozzle 11 may be any liquid that dissolves the low-soluble component and the high-soluble component. The solvent contained in the pretreatment liquid is preferably a liquid that is compatible (miscible) with the stripping liquid.

[0321] The solvent contained in the pretreatment liquid is referred to as the second solvent, the solute contained in the pretreatment liquid is referred to as the second solute, the low-soluble component contained in the treatment liquid is referred to as the second low-soluble component, and the high-soluble component contained in the treatment liquid is referred to as the second high-soluble component.

[0322] The details of the solvent, the low-soluble component, the high-soluble component, and the anti-corrosion component contained in the pre-treatment liquid ejected from the third moving nozzle 11 will be described later.

[0323] In the pretreatment film, both the portion covering the exposed region 170 and the portion covering the non-exposed region 171 are peeled off from the substrate W by the peeling liquid.

[0324] The removal force of the polymer film such as the treatment film or the pretreatment film to remove the removal object 103 is significantly different when the removal object 103 is removed from the exposed area 170 and when the removal object 103 is removed from the non-exposed area 171 .

[0325] The removal force of the polymer film to remove the object 103 is composed of the object retention force and the peeling property. The so-called object retention force is the ability to keep the object 103 present in the target area (exposed area 170 or non-exposed area 171) in at least one of the film and the surface of the polymer film. The so-called peeling property is the property of the ease of peeling when the polymer film that keeps the object 103 is peeled by the peeling liquid. The so-called high peeling property means that it is easy to peel by the peeling liquid. The so-called removal force of the polymer film is the ability to remove the object 103 from the target area when the polymer film is peeled by the peeling liquid while keeping the object 103 present in the target area.

[0326] The pretreatment film exhibits a high force to retain objects to be removed in both the non-exposed area 171 and the exposed area 170, but the treatment film exhibits a higher force to retain objects to be removed than the pretreatment film in both the non-exposed area 171 and the exposed area 170. On the other hand, the pretreatment film has higher peelability than the treatment film in the exposed area 170. Therefore, in the exposed area 170, the pretreatment film exhibits a higher force to retain objects to be removed than the treatment film, and in the non-exposed area 171, the treatment film exhibits a higher force to retain objects to be removed than the pretreatment film.

[0327] Specifically, the removal force of the treatment film to remove the removal object 103 present in the non-exposed area 171 is higher than the removal force of the pre-treatment film to remove the removal object 103 present in the non-exposed area 171. The removal force of the pre-treatment film to remove the removal object 103 present in the exposed area 170 is higher than the removal force of the treatment film to remove the removal object 103 present in the exposed area 170.

[0328] The third moving nozzle 11 is connected to a pretreatment liquid pipe 42 that guides the pretreatment liquid to the third moving nozzle 11. When the pretreatment liquid valve 52 inserted in the pretreatment liquid pipe 42 is opened, the pretreatment liquid is ejected downward from the ejection port of the third moving nozzle 11 as a continuous flow.

[0329] The central nozzle 12 is accommodated in the internal space 60a of the hollow shaft 60 of the facing member 6. The ejection port 12a provided at the front end of the central nozzle 12 faces the central area of ​​the upper surface of the substrate W from above. The central area of ​​the upper surface of the substrate W refers to the area on the upper surface of the substrate W including the rotation center of the substrate W and its surroundings.

[0330] The central nozzle 12 includes a plurality of tubes (a first tube 31, a second tube 32, and a third tube 33) for ejecting fluid downward, and a cylindrical casing 30 surrounding the plurality of tubes. The plurality of tubes and the casing 30 extend in the vertical direction along the rotation axis A1. The ejection port 12a of the central nozzle 12 is also 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.

[0331] The first tube 31 (central nozzle 12) is an example of a rinse liquid supply unit that supplies a rinse liquid such as DIW to the upper surface of the substrate W. The second tube 32 (central nozzle 12) is an example of a removal liquid supply unit that supplies a removal liquid such as isopropyl alcohol (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) between the upper surface of the substrate W and the facing surface 6a of the facing member 6. The central nozzle 12 is also a rinse liquid nozzle, a removal liquid nozzle, and a gas nozzle.

[0332] The first tube 31 is connected to the upper eluent piping 43 that guides the eluent to the first tube 31. When the upper eluent valve 53 inserted in the upper eluent piping 43 is opened, the eluent is ejected from the first tube 31 (central nozzle 12) toward the central area of ​​the upper surface of the substrate W in the form of a continuous flow.

[0333] Examples of the eluent include DIW, carbonated water, electrolytic ion water, diluted hydrochloric acid water (eg, about 1 ppm to 100 ppm), diluted ammonia water (eg, about 1 ppm to 100 ppm), and reduced water (hydrogen water).

[0334] The second tube 32 is connected to a removal liquid pipe 44 that guides the removal liquid to the second tube 32. When a removal liquid valve 54 inserted in the removal liquid pipe 44 is opened, the removal liquid is ejected from the second tube 32 (central nozzle 12) toward the central area of ​​the upper surface of the substrate W in the form of a continuous flow.

[0335] The removal liquid sprayed from the second tube 32 is a liquid used to remove the portion of the treated film that has not been peeled off from the upper surface of the substrate W by the stripping liquid, or the portion of the pre-treated film that has not been peeled off from the upper surface of the substrate W by the stripping liquid. The removal liquid is preferably a liquid with higher volatility than the rinsing liquid. The removal liquid sprayed from the second tube 32 is preferably compatible with the rinsing liquid.

[0336] The removal liquid ejected from the second pipe 32 is, for example, an organic solvent. Examples of the organic solvent ejected from the second pipe 32 include a solution containing at least one of IPA, hydrofluoroether (HFE), methanol, ethanol, acetone, propylene glycol monoethyl ether (PGEE), and trans-1,2-dichloroethylene.

[0337] Furthermore, the organic solvent ejected from the second pipe 32 does not need to contain only the monomer component, but may be a liquid mixed with other components. For example, it may be a mixed liquid of IPA and DIW, or a mixed liquid of IPA and HFE.

[0338] The third tube 33 is connected to a gas pipe 45 that guides the gas to the third tube 33. When a gas valve 55 inserted in the gas pipe 45 is opened, the gas is ejected downward from the third tube 33 (central nozzle 12) as a continuous flow.

[0339] 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 inert gas is not limited to nitrogen, and is a gas that is resistant to the upper surface of the substrate W or the concave-convex pattern 160 (see FIG. 1 ) formed on the upper surface of the substrate W. Figure 2 ) is an inert gas. Examples of inert gases include nitrogen and other rare gases such as argon.

[0340] The lower surface nozzle 13 is inserted into the through hole 21a opened in the center of the upper surface of the rotating base 21. The ejection port 13a of the lower surface nozzle 13 is exposed from the upper surface of the rotating base 21. The ejection port 13a of the lower surface nozzle 13 faces the central area of ​​the lower surface (the lower surface) of the substrate W from below. The central area of ​​the lower surface of the substrate W is an area of ​​the lower surface of the substrate W that includes the rotation center of the substrate W.

[0341] The lower surface nozzle 13 is connected to one end of a common pipe 80 that guides the rinsing liquid, the stripping liquid, and the heat medium to the lower surface nozzle 13. The other end of the common pipe 80 is connected to a lower rinsing liquid pipe 81 that guides the rinsing 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.

[0342] When the lower eluent valve 86 inserted in the lower eluent pipe 81 is opened, the eluent is ejected from the lower surface nozzle 13 to the central area of ​​the lower surface of the substrate W in the form of a continuous flow. When the lower stripping liquid valve 87 inserted in the lower stripping liquid pipe 82 is opened, the stripping liquid is ejected from the lower surface nozzle 13 to the central area of ​​the lower surface of the substrate W in the form of a continuous flow. When the heat medium valve 88 inserted in the heat medium pipe 83 is opened, the heat medium is ejected from the lower surface nozzle 13 to the central area of ​​the lower surface of the substrate W in the form of a continuous flow.

[0343] The lower surface nozzle 13 is an example of a lower side rinse liquid supply unit that supplies rinse liquid to the lower surface of the substrate W. Furthermore, the lower surface nozzle 13 is an example of a lower side stripping liquid supply unit that supplies stripping liquid to the lower surface of the substrate W. Furthermore, the lower surface 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 surface nozzle 13 is also a substrate heating unit that heats the substrate W.

[0344] The heat medium ejected from the lower surface nozzle 13 is, for example, high-temperature DIW having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the treatment liquid. When the solvent contained in the treatment liquid is IPA, the heat medium may be, for example, DIW at 60°C to 80°C. The heat medium ejected from the lower surface nozzle 13 is not limited to high-temperature DIW, but may also be a high-temperature gas such as a high-temperature inert gas or high-temperature air having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the treatment liquid.

[0345] Figure 4 : is a block diagram showing the hardware of the controller 3. The controller 3 is a computer including a computer body 3a and a peripheral device 3d connected to the computer body 3a. The computer body 3a includes a central processing unit 3b (CPU) for executing various commands and a main storage device 3c for storing information. The peripheral device 3d includes an auxiliary storage device 3e for storing information such as a program P, a reading device 3f for reading information from a removable media RM, and a communication device 3g for communicating with other devices such as a host computer.

[0346] The controller 3 is connected to an input device 3A, a display device 3B and an alarm device 3C. The input device 3A is operated by an operator such as a user or a maintenance person in charge when inputting information to the substrate processing device 1. The information is displayed on the screen of the display device 3B. The input device 3A can be any one of a keyboard, a pointing device and a touch panel, or a device other than these. A touch screen display that also serves as the input device 3A and the display device 3B can also be provided in the substrate processing device 1. The alarm device 3C uses one or more of light, sound, text and graphics to issue an alarm. When the input device 3A is a touch screen display, the input device 3A can also serve as the alarm device 3C.

[0347] The CPU 3b executes the program P stored in the auxiliary storage device 3e. The program P in the auxiliary storage device 3e may be pre-installed in the controller 3, or may be sent to the auxiliary storage device 3e from the removable medium RM via the reading device 3f, or may be sent to the auxiliary storage device 3e from an external device such as a host computer via the communication device 3g.

[0348] The auxiliary storage device 3e and the removable medium RM are non-volatile memories that retain storage even when power is not supplied. The auxiliary storage device 3e is, for example, a magnetic storage device such as a hard disk drive. The removable medium RM is, for example, an optical disk such as a compact disc or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a non-temporary tangible recording medium.

[0349] The auxiliary storage device 3e stores a plurality of recipes R. The recipe R is information that defines the processing content, processing conditions, and processing order of the substrate W. The plurality of recipes R differ from each other in at least one of the processing content, processing conditions, and processing order of the substrate W.

[0350] The controller 3 controls the substrate processing apparatus 1 so as to process the substrate W according to the recipe R set in the main storage device 3c. The following steps are executed by controlling the substrate processing apparatus 1 by the controller 3. In other words, the controller 3 is programmed to execute the following steps.

[0351] Figure 5 It is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1 . Figure 5 In the figure, the processing realized by the controller 3 executing the program is mainly shown. Figure 6A to Figure 6M It is a schematic diagram for explaining the conditions of each step of the substrate processing.

[0352] In the substrate processing performed by the substrate processing apparatus 1, for example, Figure 5 As shown, the substrate carrying-in process (step S1), the pretreatment liquid supplying process (step S2), the pretreatment film forming process (step S3), the pretreatment film stripping process (step S4), the stripping liquid removing process (step S5), the pretreatment film residue removing process (step S6), the treatment liquid supplying process (step S7), the treatment film forming process (step S8), the treatment film stripping process (step S9), the stripping liquid removing process (step S10), the treatment film residue removing process (step S11), the spin drying process (step S12) and the substrate carrying-out process (step S13) are performed in sequence.

[0353] First, an unprocessed substrate W is carried by a transfer robot IR and a transfer robot CR (see Figure 1 ) is carried from the carrier C to the processing unit 2 and handed over to the spin chuck 5 (step S1). Thus, the substrate W is held horizontally by the spin chuck 5 (substrate holding process). The substrate W is held on the spin chuck 5 in such a way that the pattern surface 165 becomes the upper surface. When the substrate W is carried in, the facing member 6 retreats to the upper position.

[0354] The spin chuck 5 continues to hold the substrate W until the spin drying process (step S12) is completed. The guard plate lifting unit 74 adjusts the height positions of the first guard plate 71A and the second guard plate 71B so that at least one guard plate 71 is located in the upper position during the period from the start of the substrate holding process to the end of the spin drying process (step S12).

[0355] Next, after the transfer robot CR retreats outside the processing unit 2, the pre-processing liquid supply process is started (step S2). In the pre-processing liquid supply process, first, the rotary motor 23 rotates the rotary base 21. Thus, the substrate W held horizontally is rotated (substrate rotating process).

[0356] When the facing member 6 is in the upper 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. Next, the pre-processing liquid valve 52 is started. Fig. 6A As shown, the pretreatment liquid is supplied (discharged) from the third movable nozzle 11 to the central area of ​​the upper surface of the rotating substrate W (pretreatment liquid supplying step, pretreatment liquid discharging step). Thus, a liquid film 201 (pretreatment liquid film) of the pretreatment liquid is formed on the substrate W (pretreatment liquid film forming step).

[0357] The supply of the pre-processing liquid from the third movable nozzle 11 is continued for a predetermined time, for example, 2 to 4 seconds. In the pre-processing liquid supplying step, the substrate W is rotated at a predetermined pre-processing liquid rotation speed, for example, 10 to 1500 rpm.

[0358] Next, a pre-treatment film forming step is performed (step S3). In the pre-treatment film forming step, the pre-treatment liquid on the substrate W is solidified or hardened to form a pre-treatment film 200 on the upper surface of the substrate W (see the following description). Fig. 7A ), the pre-treatment film 200 maintains the removal object 103 present on the substrate W.

[0359] In the pre-treatment film forming process, first, a pre-treatment liquid thinning process (pre-treatment liquid spin-off process) is performed, that is, the thickness of the pre-treatment liquid film 201 on the substrate W is reduced. Specifically, the pre-treatment liquid valve 52 is closed. Thus, the supply of the pre-treatment liquid to the substrate W is stopped. Next, the third nozzle moving unit 37 moves the third movable nozzle 11 to the original position.

[0360] like Figure 6B As shown, in the pretreatment liquid thin film forming step, a portion of the pretreatment liquid is removed from the upper surface of the substrate W by using centrifugal force while stopping the supply of the pretreatment liquid to the upper surface of the substrate W so that the thickness of the liquid film 201 on the substrate W becomes an appropriate thickness.

[0361] After the third moving nozzle 11 moves to the original position, the facing member 6 is also maintained at the upper position.

[0362] In the pre-treatment liquid thin film process, the rotary motor 23 changes the rotation speed of the substrate W to a predetermined pre-treatment liquid thin film speed. The pre-treatment liquid thin film speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept constant 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 pre-treatment liquid thin film process. The pre-treatment liquid thin film process is performed for a predetermined time, for example, 30 seconds.

[0363] In the pretreatment film forming step, after the pretreatment liquid thin film forming step, the pretreatment liquid solvent evaporation step is performed, that is, a part of the solvent is evaporated (volatized) from the pretreatment liquid film 201. In the pretreatment liquid solvent evaporation step, in order to evaporate a part of the solvent of the pretreatment liquid on the substrate W, the liquid film 201 on the substrate W is heated.

[0364] Specifically, if Figure 6C As shown, the facing member lifting unit 61 moves the facing member 6 to a close position between the upper position and the lower position. The close position may also be the lower position. The close position is a position where the distance from the upper surface of the substrate W to the facing surface 6a is, for example, 1 mm.

[0365] Next, the gas valve 55 is opened to thereby supply gas to the upper surface of the substrate W (the upper surface of the liquid film 201 ) and the space between the opposing surface 6 a of the opposing member 6 (gas supplying step).

[0366] By spraying gas onto the liquid film 201 on the substrate W, the evaporation (volatization) of the solvent in the liquid film 201 is promoted (pretreatment liquid solvent evaporation step, pretreatment liquid solvent evaporation promotion step). Therefore, the time for forming the pretreatment film 201 (see Fig. 7A The central nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the pretreatment liquid.

[0367] Next, the heat medium valve 88 is opened. As a result, the heat medium is supplied (ejected) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (heat medium supply process, heat medium ejection process). The heat medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W is radially expanded by the centrifugal force and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W continues for a predetermined time, for example, for 60 seconds. In the pre-treatment liquid solvent evaporation process, the substrate W is rotated at a predetermined evaporation rotation speed, for example, at 1000 rpm.

[0368] By supplying a heat medium to the lower surface of the substrate W, the liquid film 201 on the substrate W is heated through the substrate W. Thus, the evaporation (volatization) of the solvent in the liquid film 201 is promoted (pretreatment liquid solvent evaporation step, pretreatment liquid solvent evaporation promotion step). Therefore, the time required to form the pretreatment film 200 (see Fig. 7A The lower surface nozzle 13 functions as an evaporation unit (evaporation promotion unit) for evaporating (volatizing) the solvent in the pretreatment liquid.

[0369] By performing the pre-treatment liquid film thinning step and the pre-treatment liquid film solvent evaporation step, the pre-treatment liquid is solidified or hardened to form a pre-treatment film 200 on the substrate W (see Fig. 7A ). In this way, the substrate rotating unit (rotation motor 23), the central nozzle 12 and the lower surface nozzle 13 constitute a pretreatment film forming unit (film forming unit) that solidifies or hardens the pretreatment liquid to form a pretreatment film 200 (solid film).

[0370] In the pre-treatment liquid solvent evaporation step, the substrate W is preferably heated in such a manner that the temperature of the pre-treatment liquid on the substrate W is lower than the boiling point of the solvent. By heating the pre-treatment liquid to a temperature lower than the boiling point of the solvent, a moderate amount of solvent can be left in the pre-treatment film 200. Therefore, compared with a case where no solvent remains in the pre-treatment film 200, in the subsequent pre-treatment film stripping step (step S4), the stripping liquid is easily fused to the pre-treatment film 200.

[0371] Next, a pre-treatment film stripping step of stripping the pre-treatment film 200 is performed (step S4). Specifically, the heat medium valve 88 is closed. Thus, the supply of heat medium to the lower surface of the substrate W is stopped. Furthermore, the gas valve 55 is closed. Thus, the supply of gas to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is stopped.

[0372] Next, the facing member lifting unit 61 moves the facing member 6 to the upper position. When the facing member 6 is in the upper 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.

[0373] Next, when the second movable nozzle 10 is located at the processing position, the upper stripping liquid valve 51 is opened. Fig.6D As shown in FIG. 1 , the stripping liquid is supplied (discharged) from the second movable nozzle 10 to the central area of ​​the upper surface of the rotating substrate W (upper stripping liquid supplying process, upper stripping liquid discharging process). The stripping liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. As a result, the pre-treatment film on the upper surface of the substrate W (see FIG. 1 ) is Fig. 7A ) is peeled off and discharged together with the stripping liquid to the outside of the substrate W. In the pretreatment film stripping step, the substrate W is rotated at a predetermined pretreatment film stripping rotation speed, for example, at 800 rpm.

[0374] When the upper stripping liquid valve 51 is opened, the lower stripping liquid valve 87 is opened. Thus, the stripping liquid is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower stripping liquid supplying step, lower stripping liquid discharging step). The stripping liquid supplied to the lower surface of the substrate W spreads to the entire lower surface of the substrate W due to the centrifugal force.

[0375] Here, Fig. 6A In the pre-treatment liquid supply process (step S2) shown in FIG. 1 , the pre-treatment liquid supplied to the upper surface of the substrate W sometimes passes to the periphery of the substrate W and goes around to the lower surface of the substrate W. In addition, the pre-treatment liquid scattered from the substrate W sometimes splashes back from the guard plate 71 and adheres to the lower surface of the substrate W. Even in this case, Figure 6C As shown, in the pre-treatment film forming step, the heat medium is supplied to the lower surface of the substrate W, and thus the pre-treatment liquid can be removed from the lower surface of the substrate W by the flow of the heat medium.

[0376] Furthermore, the pre-treatment liquid attached to the lower surface of the substrate W in the pre-treatment liquid supply process (step S2) may solidify or harden to form a solid. Fig.6DAs shown, during the period when the stripping liquid is supplied to the upper surface of the substrate W in the pre-treatment film stripping step (step S4), the stripping liquid is supplied (discharged) from the lower surface nozzle 13 to the lower surface of the substrate W. Therefore, even if solids of the pre-treatment liquid are formed on the lower surface of the substrate W, the solids can be stripped and removed from the lower surface of the substrate W.

[0377] After the pretreatment film stripping step (step S4), a stripping liquid removal step (step S5) is performed to remove (rinse) the stripping liquid from the substrate W by supplying a rinse liquid. Specifically, the upper stripping liquid valve 51 and the lower stripping liquid valve 87 are closed. Thus, the supply of the stripping liquid to the upper surface and the lower surface of the substrate W is stopped. Next, the second nozzle moving unit 36 ​​moves the second movable nozzle 10 to the original position. Next, as shown in FIG. Fig. 6E As shown, the facing member lifting unit 61 moves the facing member 6 to the processing position.

[0378] Next, with the facing member 6 at the processing position, the upper eluent valve 53 is opened to supply (discharge) eluent from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (upper eluent supplying step, upper eluent discharging step).

[0379] In the stripping liquid removal process, the substrate W is rotated at a predetermined stripping liquid removal rotation speed, for example, 800 rpm. The processing position is a position that is farther upward from the upper surface of the substrate W than the closer 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.

[0380] The rinsing liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. Thus, the stripping liquid attached to the upper surface of the substrate W is washed away by the rinsing liquid (rinsing step).

[0381] Furthermore, while the upper eluent valve 53 is opened, the lower eluent valve 86 is opened. Thus, the eluent is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower eluent supplying process, lower eluent discharging process). Thus, the stripping liquid attached to the lower surface of the substrate W is washed away by the eluent. The supply of the eluent to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, for 35 seconds.

[0382] After the stripping liquid removing step (step S5 ), a pretreatment film residue removing step (step S6 ) is performed, that is, the residue of the pretreatment film 200 existing on the upper surface of the substrate W is removed by using the removing liquid.

[0383] Specifically, the upper eluent valve 53 and the lower eluent valve 86 are closed. Thus, the supply of eluent to the upper and lower surfaces of the substrate W is stopped. Next, while the facing member 6 is maintained at the processing position, the removal liquid valve 54 is opened. Fig. 6F As shown, the removal liquid is supplied (discharged) from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (removal liquid supplying step, removal liquid discharging step). The supply of the removal liquid to the upper surface of the substrate W is continued for a predetermined time, for example, for 30 seconds. In the pre-treatment film residue removal step, the substrate W is rotated at a predetermined pre-treatment film residue removal rotation speed, for example, at 300 rpm.

[0384] The removal liquid supplied to the upper surface of the substrate W is radially expanded by the centrifugal force and spreads to the entire upper surface of the substrate W. As a result, the rinse liquid on the upper surface of the substrate W is replaced by the removal liquid. The removal liquid supplied to the upper surface of the substrate W removes the pre-treatment film (see Fig. 7A ) is dissolved and then discharged from the periphery of the upper surface of the substrate W.

[0385] Next, the process liquid supply process (step S7) is performed, that is, the process liquid is supplied to the upper surface of the substrate W. Specifically, when the facing member 6 is in the upper position, the first nozzle moving unit 35 moves the first movable nozzle 9 to the process position. The process position of the first movable nozzle 9 is, for example, the central position. Next, the process liquid valve 50 is opened. As a result, Figure 6G As shown, the processing liquid is supplied (discharged) from the first movable nozzle 9 to the central area of ​​the upper surface of the rotating substrate W (processing liquid supplying step, processing liquid discharging step). As a result, a liquid film 101 (processing liquid film) of the processing liquid is formed on the substrate W (processing liquid film forming step).

[0386] The supply of the processing liquid from the first movable nozzle 9 is continued for a predetermined time, for example, 2 to 4 seconds. In the processing liquid supplying step, the substrate W is rotated at a predetermined processing liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0387] Next, a process film forming step is performed (step S8). In the process film forming step, the process liquid on the substrate W is solidified or hardened to form a process film 100 on the upper surface of the substrate W (see the following description). Figure 7C ), the processing film 100 maintains the removal object 103 present on the substrate W.

[0388] In the process film forming step, firstly, a process liquid thinning step (process liquid spin removal step) is performed, that is, the thickness of the process liquid film 101 on the substrate W is reduced. Specifically, the process liquid valve 50 is closed. Thus, the supply of the process liquid to the substrate W is stopped. Next, the first movable nozzle 9 is moved to the original position by the first nozzle moving unit 35.

[0389] like Figure 6H As shown, in the thin film forming step of the processing liquid, a portion of the processing liquid is removed from the upper surface of the substrate W by centrifugal force in a state where the supply of the processing liquid to the upper surface of the substrate W is stopped so that the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness. After the first movable nozzle 9 moves to the original position, the facing member 6 is also maintained in the upper position.

[0390] In the process of thinning the processing liquid into a thin film, the rotary motor 23 changes the rotation speed of the substrate W to a predetermined speed of thinning the processing liquid into a thin film. The speed of thinning the processing liquid into a thin film is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept constant 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 process of thinning the processing liquid into a thin film. The process of thinning the processing liquid into a thin film is performed for a predetermined time, for example, 30 seconds.

[0391] In the process film forming step, after the process liquid thin film forming step, the process liquid solvent evaporation step is performed, that is, a part of the solvent is evaporated (volatized) from the process liquid film 101. In the process liquid solvent evaporation step, in order to evaporate a part of the solvent of the process liquid on the substrate W, the liquid film 101 on the substrate W is heated.

[0392] Specifically, if Fig.6I As shown, the opposing member lifting unit 61 moves the opposing member 6 to the approach position.

[0393] In addition, the gas valve 55 is opened to thereby supply gas to the upper surface of the substrate W (the upper surface of the liquid film 101 ) and the space between the opposing surface 6 a of the opposing member 6 (gas supplying step).

[0394] By spraying gas onto the liquid film 101 on the substrate W, the evaporation (volatization) of the solvent in the liquid film 101 is promoted (process liquid solvent evaporation step, process liquid solvent evaporation promotion step). Therefore, the time for forming the process film 100 (see Figure 7C In the process film forming step, the central nozzle 12 also functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the process liquid.

[0395] Then, the heat medium valve 88 is opened. Thus, the heat medium is supplied (ejected) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (heat medium supply process, heat medium ejection process). The heat medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W is radially expanded by the centrifugal force and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W continues for a predetermined time, for example, for 60 seconds. In the process of evaporating the processing liquid solvent, the substrate W is rotated at a predetermined evaporation rotation speed, for example, at 1000 rpm.

[0396] By supplying a heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated through the substrate W. As a result, the evaporation (volatization) of the solvent in the liquid film 101 is promoted (process liquid solvent evaporation step, process liquid solvent evaporation promotion step). Therefore, the time required to form the process film 100 (see Figure 7C In the process film forming step, the lower surface nozzle 13 also functions as an evaporation unit (evaporation promotion unit) for evaporating (volatizing) the solvent in the process liquid.

[0397] The process liquid is solidified or hardened by performing the process liquid thin film forming step and the process liquid solvent evaporation step. Thus, a process film 100 holding the removal object 103 is formed on the entire upper surface of the substrate W. In this way, the substrate rotating unit (rotation motor 23), the central nozzle 12 and the lower surface nozzle 13 constitute a process film forming unit (film forming unit) that solidifies or hardens the process liquid to form the process film 100 (solid film).

[0398] In the process liquid solvent evaporation step, the substrate W is preferably heated so that the temperature of the process liquid on the substrate W is lower than the boiling point of the solvent. By heating the process liquid to a temperature lower than the boiling point of the solvent, the solvent can be left appropriately in the process film 100. Thus, in the subsequent process film stripping step (step S9), the stripping liquid is easily fused to the process film 100, compared with a case where no solvent remains in the process film 100.

[0399] Next, a process film stripping step (step S9) is performed, that is, the process film 100 is stripped using a stripping liquid. Specifically, the heat medium valve 88 is closed. Thus, the supply of heat medium to the lower surface of the substrate W is stopped. Furthermore, the gas valve 55 is closed. Thus, the supply of gas to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is stopped.

[0400] Next, the facing member lifting unit 61 moves the facing member 6 to the upper position. In a state where the facing member 6 is located at the upper position, the second nozzle moving unit 36 ​​moves the second moving nozzle 10 to the processing position.

[0401] Next, when the second movable nozzle 10 is located at the processing position, the upper stripping liquid valve 51 is opened. Figure 6J As shown in FIG. 1 , the stripping liquid is supplied (discharged) from the second movable nozzle 10 to the central area of ​​the upper surface of the rotating substrate W (upper stripping liquid supplying process, upper stripping liquid discharging process). The stripping liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. As a result, the pre-treatment film on the upper surface of the substrate W is stripped and discharged to the outside of the substrate W together with the stripping liquid. In the process film stripping process, the substrate W is rotated at a predetermined process film stripping rotation speed, for example, 800 rpm.

[0402] When the upper stripping liquid valve 51 is opened, the lower stripping liquid valve 87 is opened. Thus, the stripping liquid is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower stripping liquid supplying step, lower stripping liquid discharging step). The stripping liquid supplied to the lower surface of the substrate W spreads to the entire lower surface of the substrate W due to the centrifugal force.

[0403] Here, due to Fig. 6A The same reason as the pretreatment liquid supply process shown in the figure may Figure 6G In the process liquid supply process (step S7) shown in FIG. Fig.6I As shown, the processing liquid can be removed from the lower surface of the substrate W by the flow of the heat medium supplied to the lower surface of the substrate W.

[0404] Furthermore, similarly to the pre-treatment liquid, the treatment liquid attached to the lower surface of the substrate W in the treatment liquid supply process (step S7) may become solid. Figure 6J As shown, the stripping liquid is supplied (discharged) to the lower surface of the substrate W, so that the solid can be stripped and removed from the lower surface of the substrate W.

[0405] Next, after the film stripping step (step S9), a stripping liquid removal step (step S10) is performed, that is, the stripping liquid is removed (rinsed) from the substrate W by supplying a rinse liquid. Specifically, the upper stripping liquid valve 51 and the lower stripping liquid valve 87 are closed. Thus, the supply of the stripping liquid to the upper surface and the lower surface of the substrate W is stopped. Next, the second nozzle moving unit 36 ​​moves the second movable nozzle 10 to the original position. Next, as shown in FIG. Figure 6K As shown, the facing member lifting unit 61 moves the facing member 6 to the processing position.

[0406] Next, with the facing member 6 at the processing position, the upper eluent valve 53 is opened to supply (discharge) eluent from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (upper eluent supplying step, upper eluent discharging step).

[0407] In the stripping liquid removal process, the substrate W is rotated at a predetermined stripping liquid removal rotation speed, for example, 800 rpm. The processing position is a position that is further upward from the upper surface of the substrate W than the approach position. The rinsing liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. As a result, the stripping liquid attached to the upper surface of the substrate W is rinsed by the rinsing liquid (rinsing process).

[0408] Furthermore, while the upper eluent valve 53 is opened, the lower eluent valve 86 is opened. Thus, the eluent is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower eluent supplying process, lower eluent discharging process). Thus, the stripping liquid attached to the lower surface of the substrate W is washed away by the eluent. The supply of the eluent to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, for 35 seconds.

[0409] Next, after the stripping liquid removal step (step S10), a process film residue removal step (step S11) is performed, that is, the residue of the process film 100 existing on the upper surface of the substrate W is removed by using the removal liquid. Specifically, the upper side rinsing liquid valve 53 and the lower side rinsing liquid valve 86 are closed. Thus, the supply of the rinsing liquid to the upper surface and the lower surface of the substrate W is stopped.

[0410] Next, with the facing member 6 in the processing position, the removal liquid valve 54 is opened. Figure 6L As shown, the removal liquid is supplied (discharged) from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (removal liquid supplying step, removal liquid discharging step). The supply of the removal liquid to the upper surface of the substrate W is continued for a predetermined time, for example, for 30 seconds. In the process film residue removal step, the substrate W is rotated at a predetermined process film residue removal rotation speed, for example, at 300 rpm.

[0411] The removal liquid supplied to the upper surface of the substrate W is radially expanded by the centrifugal force to the entire upper surface of the substrate W. Thus, the rinse liquid on the upper surface of the substrate W is replaced by the removal liquid. The removal liquid supplied to the upper surface of the substrate W dissolves the residue of the processing film 100 remaining on the upper surface of the substrate W and is discharged from the periphery of the upper surface of the substrate W.

[0412] Next, a spin drying process (step S12) is performed, that is, the substrate W is rotated at a high speed to dry the upper surface of the substrate W. Specifically, the removal liquid valve 54 is closed. Thus, the supply of the removal liquid to the upper surface of the substrate W is stopped. Figure 6MAs shown in FIG. 1 , the facing member lifting unit 61 moves the facing member 6 to a drying position below the processing position. When the facing member 6 is located at 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. Next, the gas valve 55 is opened. Thus, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

[0413] Next, the rotary motor 23 accelerates the rotation of the substrate W, so that the substrate W rotates at a high speed. The substrate W in the spin drying process rotates at a drying speed, for example, at 1500 rpm. The spin drying process is performed for a predetermined time, for example, for a period of 30 seconds. As a result, a large centrifugal force acts on the removal liquid on the substrate W, and the removal liquid on the substrate W is spun off to the periphery of the substrate W. In the spin drying process, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6 to promote the evaporation of the removal liquid.

[0414] Next, the rotary motor 23 stops the rotation of the substrate W. The shield lifting unit 74 moves the first shield 71A and the second shield 71B to the lower position. The gas valve 55 is closed. In addition, the opposing member lifting unit 61 moves the opposing member 6 to the upper position.

[0415] The transfer robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S13). The substrate W is handed over by the transfer robot CR to the transfer robot IR, which stores it on the carrier C.

[0416] In the spin drying process of the substrate treatment, the upper surface of the substrate W is not dried by spinning off the rinsing liquid such as DIW on the substrate W, but the upper surface of the substrate W is dried by spinning off the removing liquid on the substrate W after the rinsing liquid on the substrate W is replaced by a removing liquid such as IPA. That is, the spin drying process is performed after the rinsing liquid is replaced by IPA having a lower surface tension than DIW, so that the concave-convex pattern 160 (see FIG. 1 ) acting on the upper surface of the substrate W when the upper surface of the substrate W is dried can be reduced. Figure 2 )'s surface tension.

[0417] Next, the state of the vicinity of the upper surface of the substrate W during substrate processing will be described. Figure 7A to Figure 7E It is a schematic diagram for explaining the state near the upper surface of the substrate W during substrate processing.

[0418] Fig. 7A 1 is a schematic diagram for explaining the state of the upper surface and the vicinity of the substrate W in a state where the pre-treatment film 200 is formed by performing the pre-treatment film forming step (step S3). Fig. 7A As shown, the pretreatment film 200 holds the removal object 103 .

[0419] If a stripping liquid is supplied to the upper surface of the substrate W on which the pre-treatment film 200 is formed, Figure 7B As shown, due to the peeling action of the peeling liquid, the pre-processing film 200 is peeled off from the upper surface of the substrate W together with the removal object 103. When peeling off from the upper surface of the substrate W, the pre-processing film 200 is split into film pieces 205.

[0420] Next, after the pretreatment film 200 is peeled off, the stripping liquid is continuously supplied to the upper surface of the substrate W, so that the film pieces 205 of the split pretreatment film 200 are discharged to the outside of the substrate W together with the stripping liquid. Thus, the film pieces 205 of the pretreatment film 200 are removed from the upper surface of the substrate W while the removal object 103 is maintained.

[0421] As described above, the pre-treatment film 200 has a relatively high removal force (compared with the treatment film 100) for removing the removal object 103 present in the exposed area 170. Figure 7B As shown in FIG. 1 , most of the removal objects 103 can be removed from the exposed area 170 by the pretreatment film peeling step (step S4). On the other hand, the removal force of the pretreatment film 200 to remove the removal objects 103 present in the non-exposed area 171 is relatively low (compared to the treatment film 100). Therefore, in the non-exposed area 171, the removal objects 103 that cannot be removed by the pretreatment film 200 may remain.

[0422] Then, if Figure 7C As shown in FIG. 1 , the processing film 100 that holds the removal object 103 is formed. Compared with the pre-processing film 200, the processing film 100 has a higher object holding force for holding the removal object 103 present in the non-exposed area 171, and thus can hold the removal object 103. If a stripping liquid is supplied to the upper surface of the substrate W on which the processing film 100 is formed, as shown in FIG. Fig.7D As shown, due to the peeling action of the peeling liquid, the processing film 100 is peeled off from the upper surface of the substrate W together with the removal object 103. When the processing film 100 is peeled off from the upper surface of the substrate W, it is split into film pieces 105.

[0423] The removal force of the treatment film 100 to remove the removal object 103 present in the non-exposed area 171 is high. Therefore, even in the pre-treatment film peeling step (step S4), if the removal object 103 that cannot be removed by the pre-treatment film 200 exists on the non-exposed area 171 (refer to Figure 7B ), the removal object 103 may be removed from the substrate W by performing a treatment film peeling step (step S9).

[0424] After the processing film 100 is peeled off by using a stripping liquid in the processing film stripping step (step S9), Fig.7DAs shown in FIG. 1 , the portion of the process film 100 covering the exposed region 170 (the exposed region covering portion 130) remains as residue on the exposed region 170. The exposed region covering portion 130 is dissolved by the removal liquid supplied to the upper surface of the substrate W in the subsequent process film residue removal step (step S11). Fig. 7E It is removed from the upper surface of the substrate W as shown.

[0425] Next, use Figure 8A to Figure 8C The peeling state of the pretreatment film 200 will be described.

[0426] like Fig. 8A As shown, the pretreatment film 200 holds the removal object 103. Specifically, the pretreatment film 200 contains a high-solubility solid 210 (the second high-solubility component in a solid state) and a low-solubility solid 211 (the second low-solubility component in a solid state). The high-solubility solid 210 and the low-solubility solid 211 are formed by evaporating at least a portion of the solvent contained in the pretreatment solution.

[0427] In the pretreatment film 200, the high-soluble solids 210 and the low-soluble solids 211 are mixed in a single layer. Strictly speaking, in the pretreatment film 200, the high-soluble solids 210 and the low-soluble solids 211 are not uniformly distributed in the pretreatment film 200, but there are parts where the high-soluble solids 210 are unevenly distributed and parts where the low-soluble solids 211 are unevenly distributed.

[0428] The pretreatment film 200 is a structure that is mixed in a single layer regardless of the region (position) where the pretreatment film 200 is formed on the upper surface of the substrate W. In other words, the pretreatment film 200 is a structure that is mixed in a single layer in any region of the exposed region 170 and the non-exposed region 171.

[0429] Reference Figure 8B The highly soluble solid 210 is dissolved by supplying the stripping liquid. That is, the pretreatment film 200 is partially dissolved. As the highly soluble solid 210 is dissolved, the through-holes 202 are formed in the portion of the pretreatment film 200 where the highly soluble solid 210 is unevenly distributed.

[0430] The through hole 202 is particularly likely to be formed in a portion where the high-soluble solid 210 extends in the normal direction T (also the thickness direction of the pretreatment film 200) of the pattern surface 165. The through hole 202 has a diameter of, for example, several nanometers (nm) in a plan view.

[0431] The low-soluble component has low solubility in the stripping liquid, and the low-soluble solid 211 is hardly dissolved by the stripping liquid. Therefore, the low-soluble solid 211 is slightly dissolved only near the surface by the stripping liquid. Therefore, the stripping liquid that reaches the upper surface (pattern surface 165) of the substrate W through the through hole 202 slightly dissolves the portion of the low-soluble solid 211 near the upper surface of the substrate W. As a result, Figure 8B As shown in the enlarged view of , the stripping liquid gradually enters the gap G2 between the pretreatment film 200 and the upper surface of the substrate W while slowly dissolving the low-soluble solid 211 near the upper surface of the substrate W (stripping liquid entering step).

[0432] Next, for example, the pre-treatment film 200 is split into film pieces 205 with the periphery of the through hole 202 as a starting point. Figure 8C As shown, the film piece 205 of the pre-treatment film 200 is peeled off from the substrate W while maintaining the removal object 103 (pre-treatment film splitting step, peeling step). Next, by continuously supplying the peeling liquid, the pre-treatment film 200 that has become the film piece 205 is rinsed (pushed out of the substrate W) while maintaining the removal object 103, and is removed from the upper surface of the substrate W (removal object removal step).

[0433] use Figures 9A to 9C , the peeling condition of the processing film 100 is described in detail. Figures 9A to 9C This is a schematic diagram for explaining a state in which a portion (non-exposed region covering portion 131 ) of the processing film 100 covering the non-exposed region 171 is peeled off from the non-exposed region 171 .

[0434] like Fig.9A As shown, the treatment film 100 holds the removal object 103. Specifically, the portion of the treatment film 100 covering the non-exposed region 171 contains a high-soluble solid 110 (a first high-soluble component in a solid state) and a low-soluble solid 111 (a first low-soluble component in a solid state). The high-soluble solid 110 and the low-soluble solid 111 are formed by evaporation of at least a portion of the solvent contained in the treatment liquid.

[0435] In the non-exposed area coating 131, the high-soluble solid 110 and the low-soluble solid 111 are mixed in a single layer. Strictly speaking, the non-exposed area coating 131 is not a region where the high-soluble solid 110 and the low-soluble solid 111 are evenly distributed throughout the treatment film 100, but a region where the high-soluble solid 110 and the low-soluble solid 111 are unevenly distributed.

[0436] Reference Fig. 9B, the highly soluble solid 110 is dissolved by supplying the stripping liquid. That is, the non-exposed region coating portion 131 is partially dissolved. As the highly soluble solid 110 is dissolved, the through hole 102 is formed in the portion where the highly soluble solid 110 is unevenly distributed in the non-exposed region coating portion 131 (through hole forming step).

[0437] The through hole 102 is particularly likely to be formed in a portion where the high-soluble solid 110 extends in the normal direction T (also the thickness direction of the processing film 100) of the pattern surface 165. The through hole 102 has a diameter of, for example, several nanometers in plan view.

[0438] The low-soluble component has low solubility in the stripping liquid, and the low-soluble solid 111 is hardly dissolved by the stripping liquid. Therefore, only the surface of the low-soluble solid 111 is slightly dissolved by the stripping liquid. Therefore, the stripping liquid that reaches the upper surface of the substrate W through the through hole 102 slightly dissolves the portion of the low-soluble solid 111 near the upper surface of the substrate W. As a result, Fig. 9B As shown in the enlarged view of , the stripping liquid slowly dissolves the low-soluble solid 111 near the upper surface of the substrate W while gradually entering the gap G1 between the non-exposed region covering portion 131 and the upper surface of the substrate W (stripping liquid entering step).

[0439] Next, for example, the covering portion 131 is split into the membrane 105 with the periphery of the through hole 102 as the starting point instead of the exposed area. Fig. 9C As shown, the film 105 of the non-exposed region covering portion 131 is peeled off from the substrate W while retaining the removal object 103 (processing film splitting step, peeling step). Next, by continuously supplying the peeling liquid, the non-exposed region covering portion 131 of the film 105 is rinsed (pushed out of the substrate W) while retaining the removal object 103, and is removed from the upper surface of the substrate W (removal object removing step).

[0440] Reference Figures 9A to 9C The process of partially dissolving the non-exposed region covering portion 131 of the processing film 100 to form the through hole 102 is an example of the first through hole forming process, and the through hole 102 formed thereby is an example of the first through hole. Figure 8A to Figure 8C The process of partially dissolving the pretreatment film 200 to form the through hole 202 is an example of the second through hole forming process, and the through hole 202 formed in this way is an example of the second through hole.

[0441] Next, use Figures 10A to 10C , the removal of the exposed region covering portion 130 covering the exposed region 170 will be described in detail. Figures 10A to 10C This is a schematic diagram for explaining a state in which the exposed region covering portion 130 is removed from the upper surface of the substrate W.

[0442] As described above, most of the removal objects 103 are removed from the exposed region 170 by the pretreatment film peeling step (step S4 ). However, some of the removal objects 103 may exist in the exposed region 170 when the treatment film 100 is formed.

[0443] The exposed region covering portion 130 includes a high-soluble solid 110 (a first high-soluble component in a solid state) and a low-soluble solid 111 (a first low-soluble component in a solid state). The high-soluble solid 110 and the low-soluble solid 111 are formed by evaporating at least a portion of the solvent included in the treatment liquid.

[0444] The exposed region covering portion 130 includes: a low solubility layer 180, which is disposed at a position in contact with the metal film 163 and includes a low solubility solid 111; and a high solubility layer 181, which is disposed on the opposite side of the metal film 163 relative to the low solubility layer 180 and includes a high solubility solid 110. That is, the low solubility layer 180 is located between the metal film 163 and the high solubility layer 181.

[0445] The high-soluble solid 110 dissolves in the stripping liquid, but the low-soluble solid 111 hardly dissolves in the stripping liquid. Therefore, if the stripping liquid is supplied to the upper surface of the substrate W in the process film stripping step (step S9), Fig. 10B As shown in FIG. 1 , the high solubility layer 181 is dissolved by the stripping liquid. On the other hand, although the surface of the low solubility layer 180 is slightly dissolved, the metal film 163 is not exposed, and the exposed area 170 is kept covered. Therefore, the stripping liquid is not easy to enter between the low solubility layer 180 and the upper surface of the substrate W. Therefore, the low solubility layer 180 of the protective film 100B is not stripped by the stripping liquid, and remains on the exposed area 170. Therefore, the stripping property of the treatment film 100 in the exposed area 170 is lower than that of the pre-treatment film 200.

[0446] The removal object 103 attached to the exposed region 170 is peeled off from the exposed region 170 when the process film 100 is formed. In the process film residue removal step (step S8), the exposed region covering portion 130 is dissolved in the removal liquid. Fig. 10C As shown, the removal objects 103 float in the removal liquid in a state of being peeled off from the exposed region 170. Therefore, by continuing to supply the removal liquid, the removal objects 103 floating in the removal liquid are removed from the upper surface of the substrate W together with the removal liquid.

[0447] According to the first embodiment, the removal object 103 is removed from the upper surface of the substrate W by peeling off the pretreatment film 200 having a high removal force for removing the removal object 103 present in the exposed area 170 (first area). Then, the removal object 103 is removed from the upper surface of the substrate W by peeling off the treatment film 100 having a high removal force for removing the removal object 103 present in the non-exposed area 171 (second area). That is, both the peeling off of the pretreatment film 200 having a relatively high removal force for removing the removal object 103 present in the exposed area 170 and the peeling off of the treatment film 100 having a relatively high removal force for removing the removal object 103 present in the non-exposed area 171 are performed. To put it more directly, the removal of the removal object 103 is performed in two stages using the pretreatment film 200 and the treatment film 100 having different areas having a high removal force for removing the removal object 103.

[0448] Therefore, the removal object 103 can be efficiently removed from the substrate W having a surface including the exposed region 170 where the metal film 163 is exposed and the other non-exposed region 171 .

[0449] Furthermore, according to the first embodiment, after the process film stripping step (step S9), a process film residue removing step (step S11) is performed, that is, a removal liquid is supplied to the upper surface of the substrate W to remove the residue of the process film 100 remaining on the upper surface of the substrate W. Therefore, even if the residue of the process film 100 adheres to the exposed area 170 and the non-exposed area 171 after the process film 100 is stripped by the stripping liquid, the residue can be removed by the removal liquid.

[0450] According to the first embodiment, in the process film peeling step, the exposed region covering portion 130 is not peeled off, but the non-exposed region covering portion 131 is peeled off. Next, in the process film residue removing step, the exposed region covering portion 130 is removed as residue of the process film 100 .

[0451] Therefore, even if the exposed region covering portion 130 is not peeled off by supplying the peeling liquid to the upper surface of the substrate W and remains on the exposed region 170 , the exposed region covering portion 130 can be dissolved in the removing liquid and removed from the exposed region 170 .

[0452] When the exposed region covering portion 130 of the processing film 100 is dissolved in the removal liquid, the removal object 103 held by the exposed region covering portion 130 and released may reattach to the exposed region 170. According to the first embodiment, the processing film 100 is formed after the pre-processing film 200 having a relatively high removal force for removing the removal object 103 present in the exposed region 170 is removed from the exposed region 170 by peeling. Therefore, most of the removal object 103 is removed from the exposed region 170 before the processing film 100 is formed.

[0453] Therefore, even in a configuration in which the exposed region covering portion 130 is dissolved in the removal liquid and the exposed region covering portion 130 is removed from the exposed region 170 , it is possible to sufficiently suppress the removal target 103 from remaining in the exposed region 170 .

[0454] According to the first embodiment, the high-soluble solid 110 and the low-soluble solid 111 are mixed in a single layer in the non-exposed region coating portion 131 of the process film 100. In addition, in the process film stripping step (step S9), the high-soluble solid 110 is selectively dissolved in the stripping solution.

[0455] By dissolving the highly soluble solid 110 in the stripping liquid, the stripping liquid passes through the non-exposed region coating portion 131 of the processing film 100 along the trace (through hole 102) of the highly soluble solid 110. Thus, the stripping liquid can quickly reach the vicinity of the interface between the processing film 100 and the non-exposed region 171 on the surface of the substrate W.

[0456] On the other hand, the low-soluble solid 111 in the non-exposed region covering portion 131 does not dissolve but remains in a solid state. Therefore, the removal object 103 can be held by the low-soluble solid 111 while the stripping liquid acts on the contact interface between the low-soluble solid 111 and the substrate W. As a result, the non-exposed region covering portion 131 can be quickly removed from the upper surface of the substrate W, and the removal object 103 can be efficiently removed from the upper surface of the substrate W together with the non-exposed region covering portion 131 of the processing film 100.

[0457] Furthermore, according to the first embodiment, the high-soluble solid 210 and the low-soluble solid 211 are mixed in the pretreatment film 200. The high-soluble solid 210 in the pretreatment film 200 is selectively dissolved in the stripping liquid. By dissolving the high-soluble solid 210 in the stripping liquid, the stripping liquid passes through the pretreatment film 200 along the trace (through hole 202) where the high-soluble solid 210 exists. As a result, the pretreatment film 200 can quickly reach the vicinity of the interface between the upper surface of the substrate W.

[0458] On the other hand, the low-soluble solid 211 in the pretreatment film 200 does not dissolve but remains in a solid state. Therefore, while the removal object 103 can be held by the low-soluble solid 211, the stripping liquid can act on the contact interface between the low-soluble solid 211 and the substrate W. As a result, the pretreatment film 200 can be quickly removed from the upper surface of the substrate W, and the removal object 103 can be removed from the upper surface of the substrate W together with the pretreatment film 200 efficiently.

[0459] The phrase “highly soluble solids 110 and 210 are selectively dissolved” does not mean that only the highly soluble solids 110 and 210 are dissolved. The phrase “highly soluble solids 110 and 210 are selectively dissolved” means that the low soluble solids 111 and 211 are also slightly dissolved, but most of the highly soluble solids 110 and 210 are dissolved.

[0460] Furthermore, the metal film 163 exposed on the surface of the exposed region 170 is not limited to a copper film. The metal film 163 may be, for example, an aluminum film, a cobalt film, a ruthenium film, a molybdenum film, a tungsten film, or the like. Furthermore, the film exposed on the surface of the exposed region 170 may not be the metal film 163, but may be, for example, a nitride film such as a silicon nitride film or a titanium nitride film. Even when the substrate treatment of the above embodiment is performed on a substrate in which the specific substance exposed in the exposed region 170 is a metal or a nitride other than copper, the same effect as that of the above embodiment is exerted.

[0461] <Second embodiment>

[0462] Fig.11 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit 2 included in a substrate processing apparatus 1P according to the second embodiment. Fig.11 Regarding the Figure 1 to Figure 10C The same structure as shown is marked with Figure 1 The same reference numerals as above are used and their description is omitted. Figure 12 to Figure 15E In the same way, Figure 1 The same reference numerals are used and their descriptions are omitted.

[0463] Reference Fig.11 The substrate processing apparatus 1P of the second embodiment is different from the substrate processing apparatus 1 of the first embodiment (see Figure 3 ) The main difference is that in the substrate processing apparatus 1P of the second embodiment, substrate processing is performed on the substrate W that has been subjected to dry etching processing.

[0464] Fig.121 is an example of a cross-sectional view of the surface layer of a substrate W processed by the substrate processing apparatus 1P. In the substrate W, a first removal object 203 is attached to both the non-exposed area 171 and the exposed area 170. The first removal object 203 is a residue generated by the dry etching process in the previous step. The first removal object 203 is a granular residue (granular residue). The CF used in the dry etching process x The reaction product of the etching gas (such as carbon tetrafluoride (CF4)) and the structure 161.

[0465] Second removal object 204 is attached to non-exposed region 171. Second removal object 204 is also a residue of dry etching. Second removal object 204 is a film-like residue (film-like residue) covering at least a portion of non-exposed region 171. Fig.12 In the example of FIG. 1 , the second removal object 204 covers the surface of the low dielectric constant interlayer insulating film 161B. The second removal object 204 is a reaction product between the etching gas and the low dielectric constant interlayer insulating film 161B.

[0466] Reference Fig.11 The processing unit 2 of the second embodiment includes a fourth movable nozzle 14. The fourth movable nozzle 14 is an example of a cleaning liquid nozzle (cleaning liquid supply unit) that supplies (sprays) a cleaning liquid such as SC1 (ammonia-hydrogen peroxide aqueous solution) in a continuous flow to the upper surface of the substrate W held on the spin chuck 5. The cleaning liquid is a liquid used to dissolve the second removal object 204 that cannot be removed from the upper surface of the substrate W by the stripping liquid and remove it from the upper surface of the substrate W.

[0467] The fourth movable nozzle 14 is moved in the horizontal direction and the vertical direction by the fourth nozzle moving unit 38. The fourth movable nozzle 14 is movable between a center position and an original position (retracted position) in the horizontal direction.

[0468] When the fourth movable nozzle 14 is located at the center position, it faces the rotation center of the upper surface of the substrate W. When the fourth movable nozzle 14 is located at the home position, it does not face the upper surface of the substrate W, but is located outside the processing cup 7 in a plan view. The fourth movable nozzle 14 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0469] The fourth nozzle moving unit 38 has the same structure as the first nozzle moving unit 35. That is, the fourth nozzle moving unit 38 includes, for example, an arm (not shown) coupled to the fourth moving nozzle 14 and extending horizontally, a rotation shaft (not shown) coupled to the arm and extending in the vertical direction, and a rotation shaft driving unit (not shown) that lifts or rotates the rotation shaft.

[0470] The fourth moving nozzle 14 is connected to a cleaning liquid pipe 46 that guides cleaning liquid to the fourth moving nozzle 14. When a cleaning liquid valve 56 inserted in the cleaning liquid pipe 46 is opened, the cleaning liquid is ejected downward from the ejection port of the fourth moving nozzle 14 in a continuous flow.

[0471] The cleaning liquid ejected from the fourth moving nozzle 14 preferably has a higher oxidizing power than the stripping liquid. The cleaning liquid ejected from the fourth moving nozzle 14 is not limited to SC1, and may be hydrofluoric acid or diluted ammonia (dNH4OH).

[0472] Fig.13 It is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1P according to the second embodiment. Fig.14A and Fig. 14B The schematic diagram for explaining the state of each process of the substrate processing performed by the substrate processing apparatus 1P.

[0473] In the substrate processing performed by the substrate processing apparatus 1P, a substrate W that has been subjected to dry etching is used. Fig.13 As shown, the substrate processing performed by the substrate processing apparatus 1P is different from the substrate processing performed by the substrate processing apparatus 1 (see Figure 5 ), a cleaning step (step S20) and a cleaning liquid removal step (step S21) are performed between the stripping liquid removal step (step S10) and the treated film residue removal step (step S11).

[0474] The cleaning process (step S20) is a process for removing the second removal object 204 attached to the upper surface of the substrate W and cleaning the upper surface of the substrate W. The cleaning liquid removal process (step S21) is a process for removing (rinsing) the cleaning liquid from the upper surface of the substrate W by supplying the rinse liquid.

[0475] Hereinafter, the cleaning step (step S20 ) and the cleaning liquid removing step (step S21 ) will be described in detail.

[0476] After the upper eluent valve 53 and the lower eluent valve 86 are closed to stop the supply of the eluent in the stripping liquid removal process (step S10), the opposing member lifting unit 61 moves the opposing member 6 to the upper position. When the opposing member 6 is in the upper position, the fourth nozzle moving unit 38 moves the fourth movable nozzle 14 to the processing position. The processing position of the fourth movable nozzle 14 is, for example, the central position.

[0477] Next, when the fourth movable nozzle 14 is located at the processing position, the cleaning liquid valve 56 is opened. Fig.14AAs shown, the cleaning liquid is supplied (discharged) from the fourth movable nozzle 14 to the central area of ​​the upper surface of the rotating substrate W (cleaning liquid supplying process, cleaning liquid discharging process). The cleaning liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. In the cleaning process, the substrate W is rotated at a predetermined cleaning rotation speed. The cleaning rotation speed is, for example, a speed in the range of 10 rpm to 1000 rpm. The cleaning rotation speed is preferably 800 rpm.

[0478] The cleaning liquid supplied to the upper surface of the substrate W is radially spread by the centrifugal force and spreads to the entire upper surface of the substrate W. Thus, the rinse liquid on the upper surface of the substrate W is replaced by the cleaning liquid.

[0479] After the cleaning process (step S20), a cleaning liquid removal process (step S21) is performed. Specifically, the cleaning liquid valve 56 is closed. Thus, the supply of cleaning liquid to the upper surface of the substrate W is stopped. In addition, the fourth nozzle moving unit 38 moves the fourth movable nozzle 14 to the original position. In addition, as Fig. 14B As shown, the facing member lifting unit 61 moves the facing member 6 to the processing position.

[0480] Next, when the facing member 6 is located at the processing position, the upper eluent valve 53 is opened. Thus, the eluent is supplied (discharged) from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (upper eluent supplying step, upper eluent discharging step). In the cleaning liquid removing step, the substrate W is rotated at a predetermined cleaning liquid removing rotation speed, for example, 800 rpm.

[0481] The eluent supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. Thus, the cleaning liquid attached to the upper surface of the substrate W is washed away by the eluent.

[0482] Furthermore, while the upper eluent valve 53 is opened, the lower eluent valve 86 is opened. Thus, the eluent is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower eluent supplying process, lower eluent discharging process). Thus, even if the cleaning liquid flows from the upper surface of the substrate W to the lower surface of the substrate W and adheres to the lower surface of the substrate W, the cleaning liquid adhered to the lower surface of the substrate W is rinsed by the eluent. The supply of the eluent to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, for 35 seconds.

[0483] Figures 15A to 15E 1P is a schematic diagram for explaining a state near the upper surface of a substrate W during substrate processing by the substrate processing apparatus 1P.

[0484] Fig.15A1 is a schematic diagram for explaining the state of the upper surface and the vicinity of the substrate W in a state where the pre-treatment film 200 is formed by performing the pre-treatment film forming step (step S3). Fig.15A As shown, the pretreatment film 200 holds the first removal object 203 .

[0485] If a stripping liquid is supplied to the upper surface of the substrate W on which the pre-treatment film 200 is formed, Fig. 15B As shown, due to the peeling action of the peeling liquid, the pre-processing film 200 is peeled off from the upper surface of the substrate W together with the first removal object 203. When the pre-processing film 200 is peeled off from the upper surface of the substrate W, it is split into film pieces 205.

[0486] Next, after the pre-treatment film 200 is peeled off, the stripping liquid is continuously supplied to the upper surface of the substrate W, so that the film pieces 205 of the split pre-treatment film 200 are discharged to the outside of the substrate W together with the stripping liquid. Thus, the film pieces 205 of the pre-treatment film 200 that retain the first removal object 203 are removed from the upper surface of the substrate W.

[0487] The removal force, removal object retention force, and peelability of the polymer film related to the first removal object 203 present in the target area (exposed area 170 or non-exposed area 171) are respectively the same as the removal force, removal object retention force, and peelability of the polymer film related to the removal object 103 described in the first embodiment.

[0488] Therefore, the pretreatment film 200 exhibits a high removal object retention force in both the non-exposed area 171 and the exposed area 170, but the treatment film 100 exhibits a higher removal object retention force than the pretreatment film 200 in both the non-exposed area 171 and the exposed area 170. On the other hand, the pretreatment film 200 has higher peelability than the treatment film 100 in the exposed area 170.

[0489] Therefore, the removal force of the treatment film 100 for removing the first removal object 203 existing in the non-exposed area 171 is higher than the removal force of the pre-treatment film 200 for removing the first removal object 203 existing in the non-exposed area 171. The removal force of the pre-treatment film 200 for removing the first removal object 203 existing in the exposed area 170 is higher than the removal force of the treatment film 100 for removing the first removal object 203 existing in the exposed area 170.

[0490] Therefore, if Fig. 15BAs shown in FIG. 1 , most of the first removal objects 203 can be removed from the exposed area 170 by the pretreatment film stripping step (step S4). On the other hand, the removal force of the pretreatment film 200 to remove the first removal objects 203 existing in the non-exposed area 171 is relatively low (compared with the treatment film 100). Therefore, in the non-exposed area 171, the first removal objects 203 that cannot be retained by the pretreatment film 200 with sufficient removal object retention force may remain. The second removal objects 204 are not stripped together with the pretreatment film 200 and are not dissolved by the stripping liquid, so they remain in the non-exposed area 171 on the upper surface of the substrate W.

[0491] Then, if Fig. 15C As shown in FIG. 1 , the processing film 100 that holds the first removal object 203 is formed. Compared with the pre-processing film 200, the processing film 100 has a higher object holding force for holding the first removal object 203 present in the non-exposed area 171, and thus can hold the first removal object 203. If a stripping liquid is supplied to the upper surface of the substrate W on which the processing film 100 is formed, as shown in FIG. Fig.15D As shown, due to the peeling action of the peeling liquid, the processing film 100 is peeled off from the upper surface of the substrate W together with the first removal object 203. When the processing film 100 is peeled off from the upper surface of the substrate W, it is split into film pieces 105.

[0492] In the treatment film 100, the non-exposed area covering portion 131 covering the non-exposed area 171 is peeled off by the peeling liquid. Fig.15D As shown, the exposed region covering portion 130 remains as residue on the exposed region 170. That is, the non-exposed region covering portion 131 functions as a peeling target film that is peeled off with a peeling liquid.

[0493] The removal force of the pretreatment film 100 to remove the first removal object 203 present in the non-exposed area 171 is high. Therefore, even if the first removal object 203 that cannot be removed by the pretreatment film 200 in the pretreatment film peeling step (step S4) exists on the non-exposed area 171 (see Fig. 15B ), the first removal object 203 may be removed from the substrate W by performing a treatment film stripping step (step S9). The second removal object 204 is not stripped together with the pretreatment film 200 and is not dissolved by the stripping liquid, so it remains in the non-exposed area 171 on the upper surface of the substrate W.

[0494] In the subsequent cleaning process (step S20), the cleaning liquid is supplied to the upper surface of the substrate W, thereby Fig.15E As shown in FIG. 1 , the second removal object 204 is dissolved. Since the metal film 163 is covered by the exposed region covering portion 130, during the period when the cleaning liquid is supplied to the upper surface of the substrate W, Fig.15E As shown, the metal film 163 is not exposed to the cleaning liquid but is protected. That is, the exposed region covering portion 130 functions as a protective film for protecting the metal film 163. In this way, the cleaning liquid can be supplied to the upper surface of the substrate W while the metal film 163 exposed from the upper surface of the substrate W is appropriately protected, and the second removal object 204 can be removed from the substrate W.

[0495] The exposed region covering portion 130 of the processing film 100 can be dissolved in the removing liquid by the subsequent processing film residue removing step (step S11 ), and the exposed region covering portion 130 can be removed from the upper surface of the substrate W smoothly.

[0496] According to the second embodiment, the same effects as those of the first embodiment are achieved.

[0497] Furthermore, according to the second embodiment, the following effects are also achieved.

[0498] By supplying the stripping liquid to the upper surface of the substrate W on which the processing film 100 is formed, the non-exposed region covering portion 131 (stripping target film) is stripped from the upper surface of the substrate W while retaining the first removal target 203. Thus, the first removal target 203 is removed from the upper surface of the substrate W. On the other hand, the second removal target 204 remains on the upper surface of the substrate W.

[0499] Then, the second removal object 204 is removed from the upper surface of the substrate W using the cleaning liquid, and then, the exposed region covering portion 130 (protective film) is removed from the upper surface of the substrate W using the removing liquid.

[0500] When the cleaning liquid is supplied to the upper surface of the substrate W, the exposed region 170 of the upper surface of the substrate W where the metal film 163 is exposed is covered by the exposed region covering portion 130. Therefore, although the cleaning liquid used to remove the second removal object 204 has the property of oxidizing the metal film 163, the second removal object 204 can be removed without oxidizing the metal film 163.

[0501] Therefore, the oxidation of the metal film 163 is suppressed, and the plurality of removal objects (the first removal objects 203 and the second removal objects 204 ) can be removed from the upper surface of the substrate W efficiently.

[0502] When the exposed region covering portion 130 of the processing film 100 is dissolved in the removal liquid, the first removal objects 203 held by the exposed region covering portion 130 and released may reattach to the exposed region 170. According to the second embodiment, the pre-processing film 200 having a relatively high removal force for removing the first removal objects 203 present in the exposed region 170 is removed from the exposed region 170 by peeling, and then the processing film 100 is formed. Therefore, most of the first removal objects 203 are removed from the exposed region 170 before the processing film 100 is formed.

[0503] Therefore, even if the exposed region covering portion 130 is dissolved in the removal liquid and removed from the exposed region 170 , it is possible to sufficiently suppress the first removal object 203 from remaining in the exposed region 170 .

[0504] As in the first embodiment, when the substrate processing of the second embodiment is performed on a substrate in which the specific substance exposed in the exposed region 170 is a metal other than copper or a nitride, the same effects as those of the second embodiment are achieved.

[0505] <Details of treatment fluid>

[0506] Hereinafter, each component in the treatment liquid used in the above-described embodiment will be described.

[0507] Below, "C x～y ”, “C x～ C y ” and “C x " refers to the number of carbon atoms in a molecule or a substituent. For example, C 1～6 The alkyl group refers to an alkyl chain having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0508] When the polymer has multiple repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerizations, random copolymerizations, block copolymerizations, graft copolymerizations, or any of the mixtures thereof. When a polymer or resin is represented by a structural formula, n or m, etc., which are recorded together in brackets, represent the number of repetitions.

[0509] <Low Solubility Ingredients>

[0510] (A) The low solubility component contains at least one of novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonates, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, (A) the low solubility component may contain at least one of novolac, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonates, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, (A) the low solubility component may contain at least one of novolac, polyhydroxystyrene, polycarbonates, and copolymers of combinations thereof. Novolac may also be phenol novolac.

[0511] The treatment liquid may contain one of the above-mentioned suitable examples or a combination of two or more of the above-mentioned suitable examples as the (A) low-soluble component. For example, the (A) low-soluble component may contain both novolac and polyhydroxystyrene.

[0512] Regarding the low-solubility component (A), a suitable form is to form a film by drying, and the film is mostly not dissolved by the stripping solution, but peeled off while retaining the object to be removed. In addition, a form in which a very small part of the low-solubility component (A) is dissolved by the stripping solution is also acceptable.

[0513] The (A) low-solubility component preferably contains no fluorine and / or silicon, and more preferably contains no both.

[0514] The copolymerization is preferably random copolymerization or block copolymerization.

[0515] Although not intending to limit the scope of the claims, specific examples of the (A) low-solubility component include compounds represented by the following Chemical Formulas 1 to 7.

[0516] [Chemistry 1]

[0517]

[0518] [Chemistry 2]

[0519]

[0520] [Chemistry 3]

[0521]

[0522] (Asterisk * indicates bonding to adjacent structural units)

[0523] [Chemistry 4]

[0524]

[0525] (R refers to C 1～4 The asterisk * indicates a bond to an adjacent structural unit)

[0526] [Chemistry 5]

[0527]

[0528] [Chemistry 6]

[0529]

[0530] [Chemistry 7]

[0531]

[0532] (Me means methyl. The asterisk * indicates a bond to an adjacent structural unit)

[0533] The weight average molecular weight (Mw) of the low-soluble component (A) is preferably 150 to 500,000, more preferably 300 to 300,000, further preferably 500 to 100,000, further more preferably 1,000 to 50,000.

[0534] (A) The low-solubility component can be obtained by synthesis. Alternatively, it can be purchased. In the case of purchase, the following suppliers are provided as examples. The supplier can also synthesize the (A) polymer.

[0535] Phenolic varnish: Showa Chemical Industry Co., Ltd., Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0536] Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.

[0537] Polyacrylic acid derivatives: Nippon Shokubai

[0538] Polycarbonate: Sigma-Aldrich

[0539] Polymethacrylic acid derivatives: Sigma-Aldrich

[0540] Compared with the total mass of the treatment liquid, the low-soluble component (A) is 0.1% to 50% by mass, preferably 0.5% to 30% by mass, more preferably 1% to 20% by mass, and further preferably 1% to 10% by mass. That is, the total mass of the treatment liquid is set to 100% by mass, and the low-soluble component (A) is 0.1% to 50% by mass based on this. That is, "compared with..." can be replaced by "taking..." as a reference. Unless otherwise specified, the same applies below.

[0541] Solubility can be evaluated using well-known methods. For example, the (A) or (B) described later can be added to 5.0 mass % ammonia water in a flask at 100 ppm under the conditions of 20°C to 35°C (more preferably 25°C ± 2°C), covered and shaken with an oscillator for 3 hours, and the solution can be obtained based on whether (A) or (B) is dissolved. Oscillation can also be stirring. Dissolution can also be judged by visual inspection. If it is not dissolved, it is considered to have a solubility of less than 100 ppm, and if it is dissolved, it is considered to have a solubility of more than 100 ppm. When the solubility is less than 100 ppm, it is considered to be insoluble or poorly soluble, and when the solubility is more than 100 ppm, it is considered to be soluble. In a broad sense, soluble includes slightly soluble. Among insoluble, poorly soluble, and soluble, insoluble means the lowest solubility, and poorly soluble means the second lowest solubility. In a narrow sense, slightly soluble is lower in solubility than soluble, and higher in solubility than poorly soluble.

[0542] <Highly soluble ingredients>

[0543] (B) The highly soluble component is (B') a crack promoting component. (B') The crack promoting component contains hydrocarbons and also contains hydroxyl groups (-OH) and / or carbonyl groups (-C(=O)-). When (B') The crack promoting component is a polymer, each unit of a structural unit contains hydrocarbons and further has hydroxyl groups and / or carbonyl groups. The carbonyl group includes carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, and carboxylic acids are preferred.

[0544] It is not intended to limit the scope of the rights, and there is no limitation in theory, but it can be considered that when the treatment liquid is dried to form a treatment film on the substrate, and the stripping liquid strips the treatment film, the (B) high solubility component produces a portion that becomes the starting point for the treatment film to peel off. Therefore, the (B) high solubility component preferably has higher solubility in the stripping liquid than the (A) low solubility component. As a form in which the (B') crack-promoting component contains a ketone as a carbonyl group, a cyclic hydrocarbon can be cited. Specific examples include 1,2-cyclohexanedione or 1,3-cyclohexanedione.

[0545] As a more specific embodiment, the highly soluble component (B) is a compound containing one to six (preferably one to four) structural units of the following chemical formula 8, and each structural unit is bonded via a linker (linker) L1. Here, the linker L1 may be a single bond or a C 1～6 Alkylene. 1～6 The alkylene group is used as a linker to link the structural units and is not limited to a divalent group. A divalent to tetravalent group is preferred. 1～6 The alkylene group may be linear or branched.

[0546] [Chemistry 8]

[0547]

[0548] Cy1 is C5～30 The hydrocarbon ring is preferably a phenyl group, a cyclohexane group or a naphthyl group, and more preferably a phenyl group. As a suitable embodiment, the linker L1 links a plurality of Cy1 groups.

[0549] R1 is independently C 1～5 Alkyl, preferably methyl, ethyl, propyl or butyl. 1～5 The alkyl group may be linear or branched.

[0550] n b1 is 1, 2 or 3, preferably 1 or 2, more preferably 1. b1' is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0551] The following Chemical Formula 9 is a chemical formula in which a linker L9 is used to represent the structural unit described in Chemical Formula 8. The linker L9 is preferably a single bond, a methylene group, an ethylene group, or a propylene group.

[0552] [Chemistry 9]

[0553]

[0554] Although not intended to limit the scope of the invention, suitable examples of the highly soluble component (B) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalene diol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These compounds can also be obtained by polymerization or condensation.

[0555] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following chemical formula 10 is used for explanation. This compound has three structural units of the chemical formula 8 in (B), and the structural units are bonded via a linker L1 (methylene). b1 =n b1' =1, R1 is methyl.

[0556] [Chemistry 10]

[0557]

[0558] (B) The highly soluble component may have a molecular weight of 80 to 10,000. The highly soluble component preferably has a molecular weight of 90 to 5000, more preferably 100 to 3000. When (B) the highly soluble component is a resin, a polymer or a polymer, the molecular weight is expressed as a weight average molecular weight (Mw).

[0559] (B) The highly soluble component can be synthesized or purchased. Examples of suppliers include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

[0560] In the treatment liquid, the amount of the high-soluble component (B) is preferably 1% to 100% by mass, more preferably 1% to 50% by mass, compared to the mass of the low-soluble component (A). In the treatment liquid, the amount of the high-soluble component (B) is further preferably 1% to 30% by mass, compared to the mass of the low-soluble component (A).

[0561] <Solvent>

[0562] The (C) solvent preferably contains an organic solvent. The (C) solvent may also be volatile. Volatile means that it is more volatile than water. For example, the boiling point of the (C) solvent at one atmosphere is preferably 50°C to 250°C. The boiling point of the solvent at one atmosphere is more preferably 50°C to 200°C, and more preferably 60°C to 170°C. The boiling point of the solvent at one atmosphere is more preferably 70°C to 150°C. The (C) solvent is also allowed to contain a small amount of pure water. Compared with the (C) solvent as a whole, the pure water contained in the (C) solvent is preferably 30% by mass or less. The pure water contained in the solvent is more preferably 20% by mass or less, and more preferably 10% by mass or less. The pure water contained in the solvent is more preferably 5% by mass or less. A suitable form is also a solvent that does not contain pure water (0% by mass). As for the so-called pure water, DIW is suitable.

[0563] 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; lactic acid esters such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone; amides such as N,N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone, etc. These organic solvents may be used alone or in combination of two or more.

[0564] As a preferred embodiment, the organic solvent contained in the solvent (C) can be selected from IPA, PGME, PGEE, EL, PGMEA, or any combination thereof. When the organic solvent is a combination of two, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

[0565] The (C) solvent is 0.1% to 99.9% by mass compared to the total mass of the treatment liquid. The (C) solvent is preferably 50% to 99.9% by mass, more preferably 75% to 99.5% by mass, compared to the total mass of the treatment liquid. The (C) solvent is further preferably 80% to 99% by mass, further more preferably 85% to 99% by mass, compared to the total mass of the treatment liquid.

[0566] <Other additives>

[0567] The treatment liquid of the present invention may also contain (D) other additives. As one embodiment of the present invention, (D) other additives include surfactants, acids, bases, antibacterial agents, bactericides, preservatives or antifungal agents (preferably surfactants), and may also contain any combination of these.

[0568] As one embodiment of the present invention, compared with the mass of the low-soluble component (A) in the treatment liquid, (D) other additives (the sum of them in the case of multiple types) is 0 to 100 mass% (preferably 0 to 10 mass%, more preferably 0 to 5 mass%, further preferably 0 to 3 mass%, further more preferably 0 to 1 mass%). It is also one embodiment of the present invention that the treatment liquid does not contain (D) other additives (0 mass%).

[0569] <Anti-corrosion ingredients>

[0570] (E) The anticorrosive component includes, in addition to BTA, uric acid, caffeine, pterin, adenine, glyoxylic acid, glucose, fructose, mannose, and the like.

[0571] <Details of pretreatment solution>

[0572] Hereinafter, each component in the pretreatment liquid used in the above embodiment will be described. The (A) low-soluble component, (C) solvent, (D) other additives, and (E) anticorrosive component contained in the pretreatment liquid can be selected from components that can be used to treat a film.

[0573] The (B) highly soluble component contained in the pretreatment liquid is different from the (B) highly soluble component contained in the treatment liquid. The (B) highly soluble component contained in the pretreatment liquid includes a first component selected from the components exemplified as the highly soluble components contained in the treatment liquid, and a second component selected from the following (B-1) and (B-2). If supplemented, the treatment liquid described above includes only the first component as the (B) highly soluble component.

[0574] (B-1) is represented by the following chemical formula 11.

[0575] [Chemistry 11]

[0576]

[0577] R 21 , R 22 , R 23 and R 24 are independently hydrogen or C 1～5 The alkyl group is preferably hydrogen, methyl, ethyl, tert-butyl or isopropyl, more preferably hydrogen, methyl or ethyl, further preferably methyl or ethyl.

[0578] Linker L 21 and connector L 22 C 1～20 Alkylene, C 1～20 Cycloalkylene, C 2～4 Alkenylene, C 2～4 Alkynylidene or C 6～20 These groups can be C 1～5 Here, the so-called alkenylene group refers to a divalent hydrocarbon group having one or more double bonds, and the so-called alkynylene group refers to a divalent hydrocarbon group having one or more triple bonds. Linker L 21 and connector L 22 Preferred C 2～4 alkylene, ethynylene (C2 alkynylene) or phenylene, more preferably C 2～4 An alkylene group or an ethynylene group, and an ethynylene group is further preferred.

[0579] n b2 It is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

[0580] Although not intended to limit the scope of the invention, suitable examples of (B-1) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another aspect, 3-hexyne-2,5-diol, 1,4-butyne diol, 2,4-hexanediyl-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol can also be mentioned as suitable examples of (B-1).

[0581] (B-2) is a polymer including a structural unit represented by the following Chemical Formula 12 and having a weight average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

[0582] [Chemistry 12]

[0583]

[0584] Here, R 25 It is -H, -CH3 or -COOH, preferably -H or -COOH. It is also acceptable for one (B-2) polymer to contain two or more structural units represented by Chemical Formula 12, respectively.

[0585] Although not intended to limit the scope of the invention, suitable examples of the polymer (B-2) include polymers of acrylic acid, maleic acid, or combinations thereof. Polyacrylic acid and maleic acid-acrylic acid copolymers are further suitable examples.

[0586] In the case of copolymerization, random copolymerization or block copolymerization is suitable, and random copolymerization is more suitable.

[0587] As an example, a maleic acid acrylic acid copolymer represented by the following chemical formula 13 is used for illustration. This copolymer is contained in (B-2) and has two structural units represented by chemical formula 12, one of which has R 25 -H, another structural unit in which R 25 It is -COOH.

[0588] [Chemistry 13]

[0589]

[0590] <Peeling test>

[0591] In order to verify the change in the peeling state of the polymer film from the copper film and the particle removal force, a peeling experiment of peeling the polymer film from the copper film was performed, which was caused by changing the ratio of the first component and the second component of the highly soluble component in the polymer-containing solution used as the treatment liquid and the pretreatment liquid. The so-called polymer film is a solid film formed by evaporating at least a part of the solvent in the polymer-containing solution.

[0592] First, a small-piece substrate (small-piece substrate) with particles of SiO2 or the like attached to the surface is prepared. The small-piece substrate is a square substrate with a side of 3 cm when viewed from the normal direction of the main surface and a copper film is formed on the entire surface.

[0593] A small piece of substrate is placed on a rotatable stage, and a polymer solution is supplied to the surface of the small piece of substrate to form a polymer film. Then, while rotating the stage, dilute ammonia water (dNH4OH, 1:68) is supplied to the surface (main surface) of the small piece of substrate to peel off the polymer film. Then, carbonated water is used to rinse the surface of the small piece of substrate, and then IPA is supplied to the surface of the small piece of substrate to remove the residue of the polymer film. After removing the residue of the polymer film, the small piece of substrate is rotated at high speed for spin drying. Then, a scanning electron microscope (SEM) is used to confirm the degree of particle removal (removal force).

[0594] Fig.16 This is a table for explaining the results of the peeling experiment. Fig.16 In the formula (A), the ratio of the first component to the second component, which is a highly soluble component in the polymer solution, is expressed in terms of the amount added. Fig.16 , the degree of particle removal when the ratio and the addition amount of the first component and the second component are changed is shown.

[0595] For the combination of the amount of the first component added and the amount of the second component added that cannot remove particles, "D" is given as the evaluation of the removal power. Fig.16 There is no combination with a removal force evaluation of "D". Similarly, for a combination of the amount of the first component added and the amount of the second component added that partially removes particles, "C" is assigned as the removal force evaluation. For a combination of the amount of the first component added and the amount of the second component added that can roughly remove particles, "B" is assigned as the removal force evaluation. In the case where particles can be removed, "A" is assigned as the removal force evaluation. In addition, in the case where particles can be fully removed, "AA" is assigned as the removal force evaluation.

[0596] For example, when the amount of the first component added is 0.1 and the amount of the second component added is 0.5, it means that the ratio of the second component to the first component in the polymer-containing solution is 5:1. Furthermore, when the amount of the first component and the second component added is both 0.5, the ratio of the second component to the first component in the polymer-containing solution is 1:1. When the amount of the first component and the second component added is both 3.0, the ratio of the second component to the first component in the polymer-containing solution is also 1:1. It means that when the amount of the first component and the second component added is both 3.0, the ratio of the highly soluble component (the total amount of the first component and the second component) in the polymer-containing solution is 6 times the ratio of the highly soluble component (the total amount of the first component and the second component) in the polymer-containing solution when the amount of the first component and the second component added is both 0.5.

[0597] like Fig.16As shown, when the amount of the second component added is 0, the evaluation of the removal force is "C", and when the amount of the first component added is 0, the evaluation of the removal force is "B".

[0598] When the amount of the second component added was smaller than the amount of the first component added, or when the amount of the second component added was the same as the amount of the first component added, the evaluation of the removal force was "B" in many cases.

[0599] For example, when the amount of the second component added is 0.5 and the amount of the first component added is 1.0, the evaluation of the removal force is "B". When the amount of the second component and the first component added is both 0.5, the evaluation of the removal force is also "B". When the amount of the second component and the first component added is both 1.0, the evaluation of the removal force is also "B". Moreover, when the amount of the first component added and the amount of the second component added are both 3.0, the evaluation of the removal force is "A".

[0600] When the amount of the second component added was larger than the amount of the first component added, the evaluation of the removal force was "A" or "AA" in any of the test results.

[0601] Based on the above results, it is inferred that the polymer film containing the first component and the second component as highly soluble components has a higher removal force for removing particles from the copper film (metal film) than the polymer film containing only the first component as a highly soluble component. This suggests that when a polymer film is used to remove particles from a copper film, it is preferred to prepare a polymer-containing solution in a manner such that the content of the second component is greater than that of the first component.

[0602] <Third Embodiment>

[0603] Fig.17 Schematic diagram of the first movable nozzle 9 and the third movable nozzle 11 of the processing unit 2 included in the substrate processing apparatus 1Q according to the third embodiment of the present invention and their peripheral components. Fig.17 For the Figures 1 to 16 The same structure as shown is marked with Figure 1 The same reference numerals as above are used and their description is omitted. Fig.18 In the same way, Figure 1 The same reference numerals are used and their descriptions are omitted.

[0604] Reference Fig.17 The substrate processing apparatus 1Q of the third embodiment is different from the substrate processing apparatus 1 of the first embodiment (see Figure 3 ) and the substrate processing apparatus 1P of the second embodiment (refer to Fig.11 ) is that, in the substrate processing apparatus 1Q of the third embodiment, the concentration of the highly soluble component contained in the processing liquid or the pre-processing liquid can be adjusted.

[0605] The first moving nozzle 9 is supplied with a treatment liquid prepared by mixing a first component liquid of a highly soluble first component and a solvent and a low-soluble component liquid of a low-soluble component and a solvent.

[0606] Specifically, the other end of the treatment liquid pipe 40 connected to the first movable nozzle 9 is commonly connected to a low-solubility component liquid pipe 140 and a first component liquid pipe 141. The low-solubility component liquid pipe 140 is connected to a low-solubility component liquid supply source, and the first component liquid pipe 141 is connected to the first component liquid supply source.

[0607] The low-solubility component liquid piping 140 is provided with a low-solubility component liquid valve 150 for adjusting the flow rate of the low-solubility component liquid supplied from the low-solubility component liquid piping 140 to the processing liquid piping 40. The first component liquid piping 141 is provided with a first component liquid valve 151 for adjusting the flow rate of the first component liquid supplied from the first component liquid piping 141 to the processing liquid piping 40.

[0608] By changing the opening degrees of the low-solubility component liquid valve 150 and the first component liquid valve 151 , the concentration of the first component in the processing liquid flowing through the processing liquid pipe 40 can be changed.

[0609] The third movable nozzle 11 is supplied with a pretreatment liquid prepared by mixing a first component liquid, a second component liquid and a low-solubility component liquid, wherein the first component liquid is a mixture of a first component of a high-solubility component and a solvent, the second component liquid is a mixture of a second component of a high-solubility component and a solvent, and the low-solubility component liquid is a mixture of a low-solubility component and a solvent.

[0610] Specifically, the other end of the pretreatment liquid pipe 42 connected to the third movable nozzle 11 at one end is commonly connected to a low-solubility component liquid pipe 142, a first component liquid pipe 143, and a second component liquid pipe 144. The low-solubility component liquid pipe 142 is connected to a low-solubility component liquid supply source. The first component liquid pipe 143 is connected to the first component liquid supply source. The second component liquid pipe 144 is connected to the second component liquid supply source.

[0611] The low-solubility component liquid piping 142 is provided with a low-solubility component liquid valve 152 for adjusting the flow rate of the low-solubility component liquid supplied from the low-solubility component liquid piping 142 to the pretreatment liquid piping 42. The first component liquid piping 143 is provided with a first component liquid valve 153 for adjusting the flow rate of the first component liquid supplied from the first component liquid piping 143 to the pretreatment liquid piping 42. The second component liquid piping 144 is provided with a second component liquid valve 154 for adjusting the flow rate of the second component liquid supplied from the second component liquid piping 144 to the pretreatment liquid piping 42.

[0612] By changing the openings of the low-solubility component liquid valve 152 , the first component liquid valve 153 , and the second component liquid valve 154 , the concentration of the first component and the concentration of the second component in the pretreatment liquid flowing through the pretreatment liquid pipe 42 can be changed.

[0613] In the substrate processing apparatus 1Q, before substrate processing is performed on the substrate W, a recipe selection process is performed, that is, a recipe R is selected based on information related to the upper surface of the substrate W.

[0614] Figure 4 The plurality of recipes R stored in the auxiliary storage device 3 e shown include a first recipe R1 and a second recipe R2 having different processing contents.

[0615] The first formula R1 is a formula R for executing the first substrate processing method, which uses a processing liquid to remove the removal object from the substrate W. The first substrate processing method is a substrate processing method (for example, the substrate processing method of the fourth embodiment described later) in which the pre-processing liquid supply process (step S2) to the pre-processing film residue removal process (step S6) are omitted in the substrate processing of the first embodiment or the second embodiment. That is, in the first substrate processing method, the removal object 103 (the first removal object 203) is not removed using the pre-processing liquid, but only the removal object 103 (the first removal object 203) is removed using the processing liquid.

[0616] The second recipe R2 is a recipe for executing a second substrate processing method, which is to remove the removal object 103 (first removal object 203) from the substrate W using a processing liquid after removing the removal object 103 (first removal object 203) from the substrate W using a pre-processing liquid. The second substrate processing method is the substrate processing of the first embodiment or the substrate processing of the second embodiment.

[0617] The second formula R2 is prepared for each type of specific substance exposed from the substrate W. The concentration of the second component contained in the pretreatment liquid is changed according to the type of the specific substance. That is, the concentration of the second component in the pretreatment liquid used in the second substrate processing method is set according to the type of the specific substance. In detail, in each second formula R2, the opening of the low-solubility component liquid valve 152, the first component liquid valve 153, and the second component liquid valve 154 when the pretreatment liquid is supplied to the upper surface of the substrate W is set according to the type of the specific substance.

[0618] Fig.18 1 is a flowchart for explaining an example of recipe selection processing. First, the controller 3 acquires information related to the surface of the substrate W to be processed (processing target substrate) (information acquisition process: step S30). The information related to the surface of the substrate W can be acquired based on information input by the user using the input device 3A, or it can be configured to read information from a mark such as a barcode set on the substrate W.

[0619] After step S30, the controller 3 determines whether the substrate W is a substrate having both an exposed area 170 and a non-exposed area 171, or a substrate having a surface with only the non-exposed area 171, based on the information related to the surface of the substrate W acquired in the information acquisition process (surface determination process: step S31).

[0620] In step S31, when the controller 3 determines that the substrate W is a substrate having a surface with only the non-exposed area 171 (step S31: NO), the controller 3 selects the first recipe R1 (recipe selection process: step S32). The controller 3 sets the selected first recipe R1 in the main storage device 3c and then executes the first substrate processing method.

[0621] On the other hand, in step S31, when the controller 3 determines that the substrate W is the following substrate, that is, a substrate having a surface with both an exposed area 170 and a non-exposed area 171 (step S31: YES), the controller 3 determines the type of the specific substance exposed from the surface of the substrate W based on the information related to the surface of the substrate W acquired in the information acquisition process (type determination process: step S33). After step S33, the controller 3 selects the second recipe R2 based on the type of the specific substance exposed from the surface of the substrate W (recipe selection process: step S34). The controller 3 sets the selected second recipe R2 in the main storage device 3c, and then executes the second substrate processing method.

[0622] According to the third embodiment, when only the non-exposed area 171 exists on the upper surface of the substrate W, the first recipe R1 of the first substrate processing method is selected to be executed, and when both the exposed area 170 and the non-exposed area 171 exist on the upper surface of the substrate W, the second recipe R2 of the second substrate processing method is selected to be executed. Therefore, an appropriate substrate processing method can be executed according to the state of the upper surface of the substrate W.

[0623] When both the exposed region 170 and the non-exposed region 171 exist on the upper surface of the substrate W, the second recipe R2 suitable for removing the removal object 103 (first removal object 203) from the exposed region 170 may be selected according to the type of the specific substance.

[0624] In the third embodiment, the second formula R2 is prepared for each type of the specific substance exposed from the substrate W. However, instead of setting the second formula R2 for each type of the specific substance, a common second formula R2 may be used regardless of the specific substance. Fig.19 As shown, in the recipe selection process, when it is determined that the substrate W is the following substrate, that is, a substrate having a surface with both an exposed area 170 and a non-exposed area 171 (step S31: YES), the second recipe R2 is selected without determining the type of specific substance (recipe selection process: step S35).

[0625] <Fourth embodiment>

[0626] Fig. 20 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit 2 included in a substrate processing apparatus 1R according to the fourth embodiment. Fig. 20 For the Figures 1 to 19 The same structure as shown is marked with Figure 1 The same reference numerals as above are used and their description is omitted. Figure 21 to Figure 24D In the same way, Figure 1 The same reference numerals are used and their descriptions are omitted.

[0627] In the fourth embodiment, the non-exposed region covering portion 131 of the processing film 100 is sometimes referred to as a peeling target film 100A, and the exposed region covering portion 130 of the processing film 100 is sometimes referred to as a protective film 100B. Fig.12 The substrate W is shown.

[0628] Therefore, although detailed description is omitted, first removal objects 203 are attached to both non-exposed region 171 and exposed region 170 , and second removal objects 204 are attached to non-exposed region 171 .

[0629] Reference Fig. 20 The substrate processing apparatus 1R of the fourth embodiment is different from the substrate processing apparatus 1 of the first embodiment (see Figure 3 ) is that, in the substrate processing apparatus 1Q of the fourth embodiment, a nozzle (third movable nozzle 11) for ejecting a pre-processing liquid is not provided, but a nozzle (fourth movable nozzle 14) for ejecting a cleaning liquid is provided.

[0630] Fig.21 It is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1R according to the fourth embodiment. Figures 22A to 22D 1 is a schematic diagram for explaining a state near the surface of a substrate W during substrate processing by the substrate processing apparatus 1R.

[0631] like Fig. 20 As shown, the substrate processing apparatus 1R performs the following substrate processing, that is, the substrate processing performed by the substrate processing apparatus 1P of the second embodiment (see Fig.13 ), the pretreatment liquid supplying step (step S2) to the pretreatment film residue removing step (step S6) are omitted.

[0632] Below, refer to Figure 6G to Figure 6M , Fig.14A , Fig. 14B and Figures 22A to 22D , the substrate processing of the fourth embodiment is described in detail.

[0633] First, the substrate W after the dry etching process is carried out by the transfer robot IR and the transfer robot CR (see Figure 1 ) is carried from the carrier C to the processing unit 2 and handed over to the spin chuck 5 (step S1). Thus, the substrate W is held horizontally by the spin chuck 5 (substrate holding process). The substrate W is held in a manner such that the pattern surface 165 becomes the upper surface. When the substrate W is carried in, the facing member 6 retreats to the upper position.

[0634] The spin chuck 5 continues to hold the substrate W until the spin drying process (step S12) is completed. The guard plate lifting unit 74 adjusts the height positions of the first guard plate 71A and the second guard plate 71B so that at least one guard plate 71 is located in the upper position during the period from the start of the substrate holding process to the end of the spin drying process (step S12).

[0635] Next, after the transfer robot CR retreats outside the processing unit 2, the processing liquid supply process starts (step S2). In the processing liquid supply process, the rotation motor 23 first rotates the rotating base 21. Thus, the substrate W held horizontally rotates (substrate rotating process).

[0636] When the facing member 6 is in the upper position, the first nozzle moving unit 35 moves the first movable nozzle 9 to the processing position. The processing position of the first movable nozzle 9 is, for example, the central position. Next, the processing liquid valve 50 is opened. Thus, the processing liquid is supplied (discharged) from the first movable nozzle 9 to the central area of ​​the upper surface of the substrate W in the rotating state (processing liquid supplying process, processing liquid discharging process) (refer to Figure 6G ). Thus, a liquid film 101 of the processing liquid (processing liquid film) is formed on the substrate W (processing liquid film forming step).

[0637] The supply of the processing liquid from the first movable nozzle 9 is continued for a predetermined time, for example, 2 to 4 seconds. In the processing liquid supplying step, the substrate W is rotated at a predetermined processing liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0638] Next, a process film forming step is performed (step S8). In the process film forming step, the process liquid on the substrate W is solidified or hardened to form a process film 100 on the upper surface of the substrate W (see Fig.22A ), the processing film 100 maintains the first removal object 203 present on the substrate W.

[0639] In the process film forming step, firstly, a process liquid thinning step (process liquid spin removal step) is performed, that is, the thickness of the process liquid film 101 on the substrate W is reduced. Specifically, the process liquid valve 50 is closed. Thus, the supply of the process liquid to the substrate W is stopped. Next, the first movable nozzle 9 is moved to the original position by the first nozzle moving unit 35.

[0640] In the thin film forming step of the processing liquid, a portion of the processing liquid is removed from the upper surface of the substrate W by centrifugal force while the supply of the processing liquid to the upper surface of the substrate W is stopped so that the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness (see Figure 6H ).

[0641] After the first movable nozzle 9 moves to the original position, the facing member 6 is also maintained at the upper position.

[0642] In the process of thinning the processing liquid into a thin film, the rotary motor 23 changes the rotation speed of the substrate W to a predetermined speed of thinning the processing liquid into a thin film. The speed of thinning the processing liquid into a thin film is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept constant 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 process of thinning the processing liquid into a thin film. The process of thinning the processing liquid into a thin film is performed for a predetermined time, for example, 30 seconds.

[0643] In the process film forming step, after the process liquid thin film forming step, the process liquid solvent evaporation step is performed, that is, a part of the solvent is evaporated (volatized) from the process liquid film 101. In the process liquid solvent evaporation step, the liquid film 101 on the substrate W is heated to evaporate a part of the solvent of the process liquid on the substrate W.

[0644] Specifically, the opposing member lifting unit 61 moves the opposing member 6 to a close position between the upper position and the lower position (see Fig.6I ).

[0645] Next, the gas valve 55 is opened to thereby supply gas to the upper surface of the substrate W (upper surface of the liquid film 101 ) and the space between the opposing surface 6 a of the opposing member 6 (gas supplying step).

[0646] By spraying gas onto the liquid film 101 on the substrate W, the evaporation (volatization) of the solvent in the liquid film 101 is promoted (process liquid solvent evaporation step, process liquid solvent evaporation promotion step). Therefore, the time for forming the process film 100 (see Fig.22A The central nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0647] Then, the heat medium valve 88 is opened. Thus, the heat medium is supplied (ejected) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (heat medium supply process, heat medium ejection process). The heat medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W is radially expanded by the centrifugal force and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W continues for a predetermined time, for example, for 60 seconds. In the process of evaporating the processing liquid solvent, the substrate W is rotated at a predetermined evaporation rotation speed, for example, at 1000 rpm.

[0648] By supplying a heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated through the substrate W. As a result, the evaporation (volatization) of the solvent in the liquid film 101 is promoted (process liquid solvent evaporation step, process liquid solvent evaporation promotion step). Therefore, the time required to form the process film 100 (see Fig.22A The lower surface nozzle 13 functions as an evaporation unit (evaporation promotion unit) for evaporating (volatizing) the solvent in the processing liquid.

[0649] By performing the process of thinning the treatment liquid and evaporating the treatment liquid solvent, the treatment liquid is solidified or hardened. Fig.22AAs shown, a processing film 100 holding the first removal object 203 is formed on the entire upper surface of the substrate W. In this way, the substrate rotating unit (rotation motor 23), the central nozzle 12 and the lower surface nozzle 13 constitute a processing film forming unit (film forming unit) that solidifies or hardens the processing liquid to form a solid film (processing film 100).

[0650] In the process liquid solvent evaporation step, the substrate W is preferably heated so that the temperature of the process liquid on the substrate W is lower than the boiling point of the solvent. By heating the process liquid to a temperature lower than the boiling point of the solvent, the solvent can be left appropriately in the process film 100. Thus, in the subsequent process film stripping step (step S9), the stripping liquid is easily fused to the process film 100, compared with a case where no solvent remains in the process film 100.

[0651] Next, the process film stripping step is performed (step S9). The process film stripping step is a stripping target film stripping step, that is, the protective film 100B (exposed region covering portion 130) is not stripped, but the stripping target film 100A (non-exposed region covering portion 131) is stripped. Specifically, the heat medium valve 88 is closed. Thus, the supply of heat medium to the lower surface of the substrate W is stopped. In addition, the gas valve 55 is closed. Thus, the supply of gas to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is stopped.

[0652] Next, the facing member lifting unit 61 moves the facing member 6 to the upper position. In a state where the facing member 6 is located at the upper position, the second nozzle moving unit 36 ​​moves the second moving nozzle 10 to the processing position.

[0653] Next, when the second movable nozzle 10 is located at the processing position, the upper stripping liquid valve 51 is opened. Thus, the stripping liquid is supplied (discharged) from the second movable nozzle 10 to the central area of ​​the upper surface of the rotating substrate W (upper stripping liquid supplying step, upper stripping liquid discharging step) (see Figure 6J ). The stripping liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. In the stripping target film stripping step, the substrate W is rotated at a predetermined stripping target film stripping rotation speed, for example, 800 rpm.

[0654] When the upper stripping liquid valve 51 is opened, the lower stripping liquid valve 87 is opened. Thus, the stripping liquid is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower stripping liquid supplying step, lower stripping liquid discharging step). The stripping liquid supplied to the lower surface of the substrate W spreads to the entire lower surface of the substrate W due to the centrifugal force.

[0655] By supplying the stripping liquid to the upper surface of the substrate W, Fig. 22BAs shown, due to the peeling action of the peeling liquid, the peeling target film 100A is peeled off from the non-exposed region 171 of the upper surface of the substrate W together with the first removal object 203. When peeling off from the upper surface of the substrate W, the peeling target film 100A is split into film pieces 105.

[0656] After the peeling target film 100A is peeled off, the peeling liquid is continuously supplied to the upper surface of the substrate W, so that the film piece 105 of the peeling target film 100A is discharged to the outside of the substrate W together with the peeling liquid. Thus, the film piece 105 of the peeling target film 100A, which remains in the state of the first removal object 203, is removed from the upper surface of the substrate W.

[0657] The peeling target film 100A is peeled off from the non-exposed region 171 , while the protection film 100B covering (protecting) the exposed region 170 of the processing film 100 is not peeled off and remains covering the exposed region 170 .

[0658] Next, after the film stripping process (step S9), a stripping liquid removal process (step S10) is performed, that is, the stripping liquid is removed from the substrate W by supplying a rinse liquid. Specifically, the upper stripping liquid valve 51 and the lower stripping liquid valve 87 are closed. Thus, the supply of the stripping liquid to the upper and lower surfaces of the substrate W is stopped. Next, the second nozzle moving unit 36 ​​moves the second movable nozzle 10 to the original position. Next, the opposing member lifting unit 61 moves the opposing member 6 to the processing position (refer to Figure 6K ).

[0659] Next, with the facing member 6 at the processing position, the upper eluent valve 53 is opened to supply (discharge) eluent from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (upper eluent supplying step, upper eluent discharging step).

[0660] In the stripping liquid removing step, the substrate W is rotated at a predetermined stripping liquid removing rotation speed, for example, 800 rpm.

[0661] The rinsing liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. Thus, the stripping liquid attached to the upper surface of the substrate W is washed away by the rinsing liquid (rinsing step).

[0662] Furthermore, while the upper eluent valve 53 is opened, the lower eluent valve 86 is opened. Thus, the eluent is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower eluent supplying process, lower eluent discharging process). Thus, the stripping liquid attached to the lower surface of the substrate W is washed away by the eluent. The supply of the eluent to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, for 35 seconds.

[0663] Next, a cleaning process (step S20) is performed, that is, the second removal object 204 attached to the upper surface of the substrate W is removed, and the upper surface of the substrate W is cleaned. Specifically, the upper eluent valve 53 and the lower eluent valve 86 are closed. Thus, the supply of eluent to the upper and lower surfaces of the substrate W is stopped.

[0664] Next, the facing member lifting unit 61 moves the facing member 6 to the upper position. With the facing member 6 in the upper position, the fourth nozzle moving unit 38 moves the fourth moving nozzle 14 to the processing position (eg, the center position).

[0665] Next, when the fourth movable nozzle 14 is located at the processing position, the cleaning liquid valve 56 is opened. Thus, the cleaning liquid is supplied (discharged) from the fourth movable nozzle 14 to the central area of ​​the upper surface of the rotating substrate W (cleaning liquid supplying step, cleaning liquid discharging step) (see Fig.14A ). The cleaning liquid supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to centrifugal force. In the cleaning process, the substrate W is rotated at a predetermined cleaning rotation speed. The cleaning rotation speed is, for example, a speed in the range of 10 rpm to 1000 rpm. The cleaning rotation speed is preferably 800 rpm.

[0666] The cleaning liquid supplied to the upper surface of the substrate W is radially spread by the centrifugal force and spreads to the entire upper surface of the substrate W. As a result, the rinse liquid on the upper surface of the substrate W is replaced by the cleaning liquid. Fig. 22C As shown, the cleaning liquid supplied to the upper surface of the substrate W removes the second removal object 204 (see Fig. 22B The cleaning liquid in which the second removal object 204 is dissolved is discharged from the periphery of the upper surface of the substrate W.

[0667] After the cleaning process (step S20), a cleaning liquid removal process (step S21) is performed, that is, the cleaning liquid is removed from the substrate W by supplying a rinse liquid. Specifically, the cleaning liquid valve 56 is closed. Thus, the supply of the cleaning liquid to the upper surface of the substrate W is stopped. Next, the fourth nozzle moving unit 38 moves the fourth movable nozzle 14 to the home position. Next, the opposing member lifting unit 61 moves the opposing member 6 to the processing position (refer to Fig. 14B ).

[0668] Next, when the facing member 6 is located at the processing position, the upper eluent valve 53 is opened. Thus, the eluent is supplied (discharged) from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (upper eluent supplying step, upper eluent discharging step). In the cleaning liquid removing step, the substrate W is rotated at a predetermined cleaning liquid removing rotation speed, for example, 800 rpm.

[0669] The eluent supplied to the upper surface of the substrate W spreads to the entire upper surface of the substrate W due to the centrifugal force. Thus, the cleaning liquid attached to the upper surface of the substrate W is washed away by the eluent.

[0670] Furthermore, while the upper eluent valve 53 is opened, the lower eluent valve 86 is opened. Thus, the eluent is supplied (discharged) from the lower surface nozzle 13 to the central area of ​​the lower surface of the rotating substrate W (lower eluent supplying process, lower eluent discharging process). Thus, even if the cleaning liquid flows from the upper surface of the substrate W to the lower surface of the substrate W and adheres to the lower surface of the substrate W, the cleaning liquid adhered to the lower surface of the substrate W is rinsed by the eluent. The supply of the eluent to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, for 35 seconds.

[0671] Next, a process film residue removal step is performed (step S11). The process film residue removal step is also a protective film removal step for removing the protective film 100B. Specifically, the upper eluent valve 53 and the lower eluent valve 86 are closed. Thus, the supply of eluent to the upper and lower surfaces of the substrate W is stopped.

[0672] Next, with the facing member 6 located at the processing position, the removal liquid valve 54 is opened. As a result, the removal liquid is supplied (discharged) from the central nozzle 12 to the central area of ​​the upper surface of the rotating substrate W (removal liquid supplying step, removal liquid discharging step) (see Figure 6L ). The supply of the removal liquid to the upper surface of the substrate W is continued for a predetermined time, for example, for 30 seconds. In the protective film removal step, the substrate W is rotated at a predetermined removal rotation speed, for example, at 300 rpm.

[0673] The removal liquid supplied to the upper surface of the substrate W is radially spread by the centrifugal force and spreads to the entire upper surface of the substrate W. Thus, the rinse liquid on the upper surface of the substrate W is replaced by the removal liquid. Fig.22D As shown, the removal liquid supplied to the upper surface of the substrate W removes the protective film 100B (see Fig. 22C ) is dissolved and then discharged from the periphery of the upper surface of the substrate W.

[0674] Next, a spin drying process (step S12) is performed, that is, the substrate W is rotated at a high speed to dry the upper surface of the substrate W. Specifically, the removal liquid valve 54 is closed. Thus, the supply of the removal liquid to the upper surface of the substrate W is stopped. Next, the opposing member lifting unit 61 moves the opposing member 6 to a drying position below the processing position (see FIG. Figure 6M ). Next, the gas valve 55 is opened. Thus, the gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

[0675] Next, the rotary motor 23 accelerates the rotation of the substrate W, so that the substrate W rotates at a high speed. The substrate W in the spin drying process rotates at a drying speed, for example, at 1500 rpm. The spin drying process is performed for a predetermined time, for example, for a period of 30 seconds. As a result, a large centrifugal force acts on the removal liquid on the substrate W, and the removal liquid on the substrate W is spun off to the periphery of the substrate W. In the spin drying process, 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 removal liquid.

[0676] Next, the rotary motor 23 stops the rotation of the substrate W. The shield lifting unit 74 moves the first shield 71A and the second shield 71B to the lower position. The gas valve 55 is closed. Next, the opposing member lifting unit 61 moves the opposing member 6 to the upper position.

[0677] The transfer robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S10). The substrate W is handed over by the transfer robot CR to the transfer robot IR, which stores it on the carrier C.

[0678] In the spin drying process of the substrate treatment of the fourth embodiment, after the rinsing liquid on the substrate W is replaced by the removal liquid such as IPA, the removal liquid on the substrate W is spun off, thereby drying the upper surface of the substrate W. That is, the spin drying process is performed after the rinsing liquid is replaced by IPA having a lower surface tension than DIW, so that the concave-convex pattern 160 (see Fig.12 )'s surface tension.

[0679] use Figures 23A to 23C , the peeling condition of the peeling target film 100A is described in detail.

[0680] Figures 23A to 23C This is a schematic diagram for explaining a state in which the peeling target film 100A covering the non-exposed region 171 is peeled off from the upper surface of the substrate W. FIG.

[0681] like Fig.23A As shown, the peeling target film 100A holds the first removal target 203. Specifically, the peeling target film 100A contains a high-solubility solid 110 (a high-solubility component in a solid state) and a low-solubility solid 111 (a low-solubility component in a solid state). The high-solubility solid 110 and the low-solubility solid 111 are formed by evaporating at least a portion of the solvent contained in the processing liquid.

[0682] In the stripping target film 100A, the high-soluble solid 110 and the low-soluble solid 111 are mixed. Strictly speaking, in the stripping target film 100A, the high-soluble solid 110 and the low-soluble solid 111 are not evenly distributed in the entire processing film 100, but there are parts where the high-soluble solid 110 is unevenly distributed and parts where the low-soluble solid 111 is unevenly distributed.

[0683] Reference Fig. 23B , the highly soluble solid 110 is dissolved by supplying the stripping liquid. That is, the stripping target film 100A is partially dissolved. As the highly soluble solid 110 is dissolved, the through hole 102 (first through hole) is formed in the portion where the highly soluble solid 110 is unevenly distributed in the stripping target film 100A (first through hole forming step).

[0684] The through hole 102 is particularly likely to be formed in a portion where the high-soluble solid 110 extends in the normal direction T (also the thickness direction of the processing film 100) of the pattern surface 165. The through hole 102 has a diameter of, for example, several nanometers in plan view.

[0685] The low-soluble component has low solubility in the stripping liquid, and the low-soluble solid 111 is hardly dissolved by the stripping liquid. Therefore, only the vicinity of the surface of the low-soluble solid 111 is slightly dissolved by the stripping liquid. Therefore, the stripping liquid that reaches the vicinity of the upper surface of the substrate W through the through hole 102 slightly dissolves the portion of the low-soluble solid 111 near the upper surface of the substrate W. As a result, Fig. 23B As shown in the enlarged view of , the stripping liquid gradually enters the gap G1 between the stripping target film 100A and the upper surface of the substrate W while slowly dissolving the low-soluble solid 111 near the upper surface of the substrate W (stripping liquid entering step).

[0686] Next, the peeling target film 100A is split into film pieces 105, for example, starting from the periphery of the through hole 102. Fig.23C As shown, the film sheet 105 of the peeling target film 100A is peeled off from the substrate W while retaining the first removal target object 203 (peeling target film splitting step, peeling target film peeling step). Next, by continuously supplying the peeling liquid, the peeling target film 100A, which has become the film sheet 105, is rinsed (pushed out of the substrate W) while retaining the first removal target object 203, and is removed from the upper surface of the substrate W (first removal target object removing step).

[0687] Next, use Figures 24A to 24D The removal of the protective film 100B will be described in detail.

[0688] Figures 24A to 24D This is a schematic diagram for explaining a state in which the protective film 100B covering the exposed region 170 is removed from the upper surface of the substrate W. FIG.

[0689] like Fig.24A As shown, the protective film 100B holds the first removal object 203. Specifically, the protective film 100B contains a high-soluble solid 110 (a high-soluble component in a solid state) and a low-soluble solid 111 (a low-soluble component in a solid state). The high-soluble solid 110 and the low-soluble solid 111 are formed by evaporating at least a portion of the solvent contained in the treatment liquid.

[0690] The protective film 100B includes: a low solubility layer 180, which is arranged at a position in contact with the metal film 163 and includes a low solubility solid 111; and a high solubility layer 181, which is arranged on the opposite side of the metal film 163 relative to the low solubility layer 180 and includes a high solubility solid 110. That is, the low solubility layer 180 is located between the metal film 163 and the high solubility layer 181.

[0691] The high-soluble solid 110 dissolves in the stripping liquid, but the low-soluble solid 111 hardly dissolves in the stripping liquid. Therefore, if the stripping liquid is supplied to the upper surface of the substrate W in the stripping target film stripping step (step S4), Fig. 24B As shown in FIG. 1 , the high solubility layer 181 is dissolved by the stripping liquid. On the other hand, the low solubility layer 180 is slightly dissolved on its surface, but the metal film 163 is not exposed, and the exposed region 170 is covered. Therefore, the stripping liquid is unlikely to enter between the low solubility layer 180 and the upper surface of the substrate W. Therefore, the low solubility layer 180 of the protective film 100B is not stripped by the stripping liquid, and remains on the exposed region 170.

[0692] The metal film 163 is covered by the protective film 100B, so during the period of supplying the cleaning liquid to the upper surface of the substrate W in the subsequent cleaning process (step S6), the metal film 163 is covered by the protective film 100B. Fig.24C As shown, the metal film 163 is not exposed to the cleaning solution and is protected.

[0693] Therefore, if Fig. 22C As shown in FIG. 1 , the cleaning liquid can be supplied to the surface of the substrate W while appropriately protecting the metal film 163 exposed from the upper surface of the substrate W, thereby removing the second removal object 204 from the substrate W. By the subsequent protective film removal step (step S8), the second removal object 204 can be removed from the substrate W. Fig.24D As shown, the protective film 100B is dissolved in the removing liquid, and the protective film 100B is removed smoothly from the upper surface of the substrate W.

[0694] The first removal object 203 attached to the exposed region 170 is peeled off from the exposed region 170 when the protective film 100B is formed. In the protective film removal process (process film residue removal process: step S11) after the cleaning process (step S20), the protective film 100B is dissolved in the removal liquid. When the protective film 100B is dissolved by the removal liquid, the first removal object 203 floats in the removal liquid in a state of being peeled off from the exposed region 170. Therefore, by continuously supplying the removal liquid, the first removal object 203 floating in the removal liquid is removed from the upper surface of the substrate W together with the removal liquid.

[0695] Furthermore, the removal liquid can also dissolve the peeling target film 100A. Therefore, even if residues of the peeling target film 100A adhere to the upper surface of the substrate W after peeling with the peeling liquid, the residues can be removed with the removal liquid.

[0696] The types of removal objects attached to the upper surface of the substrate W vary depending on the content of the previous process. Depending on the content of the previous process, multiple types of removal objects may be attached to the upper surface of the substrate W. For example, after dry etching, the first removal object 203 as granular residue and the second removal object 204 as film residue may be attached to the upper surface of the substrate W. There are also removal objects that cannot be removed unless a liquid having a strong removal force to the extent of deteriorating the metal (specific substance) exposed from the surface of the substrate is used.

[0697] According to the fourth embodiment, by solidifying or curing the processing liquid supplied to the upper surface of the substrate W, the peeling target film 100A covering the non-exposed area 171 of the upper surface of the substrate W and the protective film 100B covering the exposed area 170 of the upper surface of the substrate W are formed.

[0698] By supplying the stripping liquid to the upper surface of the substrate W on which the stripping target film 100A and the protective film 100B are formed, the stripping target film 100A is stripped from the upper surface of the substrate W while the first removal target object 203 is retained. Therefore, the first removal target object 203 is removed from the upper surface of the substrate W. On the other hand, the second removal target object 204 remains on the upper surface of the substrate W. Then, the second removal target object 204 is removed from the upper surface of the substrate W using the cleaning liquid, and then the protective film 100B is removed from the upper surface of the substrate W using the removing liquid.

[0699] When the cleaning liquid is supplied to the upper surface of the substrate W, the exposed area 170 of the upper surface of the substrate W is covered with the protective film 100B. Therefore, although the cleaning liquid for removing the second removal object 204 has an oxidizing force that oxidizes the metal film 163, the second removal object 204 can be removed without oxidizing the metal film 163.

[0700] Therefore, the oxidation of the metal film 163 is suppressed, and the plurality of removal objects (the first removal objects 203 and the second removal objects 204 ) can be removed from the upper surface of the substrate W efficiently.

[0701] According to the first embodiment, in the peeling target film 100A, the high-soluble solid 110 and the low-soluble solid 111 are mixed. In the peeling target film peeling step (process film peeling step: step S9), the high-soluble solid 110 is selectively dissolved in the peeling liquid.

[0702] Since the highly soluble solid 110 is dissolved in the stripping liquid, the stripping liquid passes through the stripping target film 100A along the traces (through holes 102) of the highly soluble solid 110. Thus, the stripping liquid can quickly reach the interface between the stripping target film 100A and the non-exposed region 171 on the surface of the substrate W.

[0703] On the other hand, the low-soluble solid 111 in the stripping target film 100A does not dissolve but remains in a solid state. Therefore, while the first removal object 203 is held by the low-soluble solid 111, the stripping liquid can act on the contact interface between the low-soluble solid 111 and the substrate W. As a result, the stripping target film 100A can be quickly removed from the upper surface of the substrate W, and the first removal object 203 can be efficiently removed from the upper surface of the substrate W together with the stripping target film 100A.

[0704] As in the first embodiment, when the substrate processing of the fourth embodiment is performed on a substrate in which the specific substance exposed in the exposed region 170 is a metal other than copper or a nitride, the same effects as those of the first embodiment can be achieved.

[0705] <Other embodiments>

[0706] The present invention is not limited to the above-described embodiments, and can be implemented in other forms.

[0707] For example, in the process film forming step (step S8), when the liquid film 101 of the process liquid is thinned, the liquid film 101 is solidified or hardened by evaporation of the solvent. In this case, it is not necessary to heat the substrate W or spray gas onto the upper surface of the substrate W in order to solidify or harden the liquid film 101 of the process liquid after thinning the liquid film 101 of the process liquid.

[0708] The same is true when the pretreatment film 200 is formed by evaporating the solvent when the pretreatment liquid film 201 is thinned in the pretreatment film forming step (step S3). That is, in this case, heating of the substrate W or gas spraying onto the upper surface of the substrate W can be omitted.

[0709] Furthermore, in the substrate processing of the second embodiment, a cleaning liquid removing step (step S21) is performed after the cleaning step (step S20). However, the cleaning liquid removing step may be omitted. Specifically, when the cleaning liquid supplied to the substrate W in the cleaning step is compatible with the processing film residue removing liquid supplied to the substrate W in the processing film residue removing step (step S11) performed after the cleaning liquid removing step, the cleaning liquid removing step does not need to be performed.

[0710] Furthermore, in the above embodiment, in the process film peeling step (step S9), the exposed region covering portion 130 is not peeled off by the peeling liquid and remains in the exposed region 170. However, the exposed region covering portion 130 may be peeled off by the peeling liquid in the process film peeling step.

[0711] In the first to fourth embodiments, a polymer-containing solution containing only the first component as a highly soluble component is used as a treatment solution, and a polymer-containing solution containing both the first component and the second component as highly soluble components is used as a pretreatment solution. However, a polymer-containing solution containing both the first component and the second component as highly soluble components may be used as a treatment solution, and a polymer-containing solution containing only the first component as a highly soluble component may be used as a pretreatment solution. In this case, the non-exposed area 171 where a specific substance such as copper is not exposed is equivalent to the first area of ​​the present invention, and the exposed area 170 where a specific substance such as copper is exposed is equivalent to the second area of ​​the present invention.

[0712] Furthermore, in the first embodiment, the exposed region covering portion 130 is not peeled off by the peeling liquid but is dissolved by the removing liquid. However, in the first embodiment, the exposed region covering portion 130 may be peeled off together with the non-exposed region covering portion 131 by the peeling liquid.

[0713] The substrate processing of the second embodiment and the fourth embodiment is not limited to the substrate after the dry etching process, and can be applied to various substrates. In particular, the substrate processing of the second embodiment and the fourth embodiment is useful when multiple removal objects are attached to the substrate and one of the removal objects cannot be removed by peeling off the treatment film or the pre-treatment film.

[0714] In the present specification, when “to” or “-” is used to express a numerical range, unless otherwise specified, these numerical ranges include both end points and have the same unit.

[0715] Although the embodiments of the present invention have been described in detail, these descriptions are only specific examples for illustrating the technical contents of the present invention, and the present invention should not be construed as being limited to these specific examples. The scope of the present invention is limited only by the appended claims.

Claims

1. A substrate processing method, comprising processing a substrate having a surface having an exposed area where a specific substance is exposed and a non-exposed area other than the exposed area, the substrate processing method comprising: a processing liquid supplying step of supplying the processing liquid to the surface of the substrate; A film forming step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a stripping target film and a protective film on the surface of the substrate, wherein the stripping target film holds the first removal target present in the non-exposed area of ​​the surface of the substrate and covers the non-exposed area, and the protective film covers the exposed area to protect the first removal target; a peeling target film peeling step of supplying a peeling liquid to the surface of the substrate to peel the peeling target film, which is in a state of maintaining the first removal target object, from the surface of the substrate; a cleaning step of supplying a cleaning liquid to the surface of the substrate after the stripping target film stripping step, and removing a second removal target present on the surface of the substrate by using the cleaning liquid; as well as The protective film removing step is to supply a removing liquid to the surface of the substrate after the cleaning step to remove the protective film from the surface of the substrate.

2. The substrate processing method according to claim 1, characterized in that: The treatment liquid contains a first solute and a first solvent that dissolves the first solute. The first solute includes a first high-solubility component and a first low-solubility component that is less soluble in the stripping solution than the first high-solubility component. The protective film includes: a low solubility layer, which is arranged at a position in contact with the specific substance and contains the first low solubility component in a solid state; and a high solubility layer, which is arranged on the opposite side of the specific substance relative to the low solubility layer and contains the first high solubility component in a solid state.

3. The substrate processing method according to claim 1, characterized in that: The treatment liquid contains a first solute and a first solvent that dissolves the first solute. The first solute includes a first high-solubility component and a first low-solubility component that is less soluble in the stripping solution than the first high-solubility component. The film forming step includes the steps of forming the peeling target film containing the first high-solubility component in a solid state and the first low-solubility component in a solid state, The stripping target film stripping step includes the step of selectively dissolving the first highly soluble component in a solid state in the stripping solution.

4. The substrate processing method according to claim 1 or 2, characterized in that: The peeling-off film peeling step includes a first through-hole forming step of partially dissolving the peeling-off film in the peeling liquid to form a through-hole in the peeling-off film.

5. The substrate processing method according to claim 1 or 2, characterized in that: Also includes: a pre-treatment liquid supplying step of supplying the pre-treatment liquid to the surface of the substrate before the treatment liquid supplying step; a pretreatment film forming step of solidifying or hardening the pretreatment liquid supplied to the surface of the substrate before the treatment liquid supplying step to form a pretreatment film on the surface of the substrate, wherein the pretreatment film maintains the first removal object existing in the exposed area on the surface of the substrate; as well as The pretreatment film peeling step is to supply a peeling liquid to the surface of the substrate before the treatment liquid supplying step, and peel the pretreatment film together with the first removal object from the exposed area on the surface of the substrate.

6. The substrate processing method according to claim 5, characterized in that: The pretreatment solution contains a second solute and a second solvent that dissolves the second solute. The second solute includes a second high-solubility component and a second low-solubility component that is less soluble in the stripping solution than the second high-solubility component. The pretreatment film forming step includes: forming the pretreatment film containing the second high-solubility component in a solid state and the second low-solubility component in a solid state, The pretreatment film stripping step includes a step of selectively dissolving the second highly soluble component in a solid state in the pretreatment film in the stripping solution.

7. The substrate processing method according to claim 5, characterized in that: The pretreatment film stripping step includes a second through-hole forming step of partially dissolving the pretreatment film in the stripping solution to form a second through-hole in the pretreatment film.

8. The substrate processing method according to claim 1 or 2, characterized in that: The specific substance is a metal, The cleaning liquid has an oxidizing force to oxidize the metal exposed on the surface of the substrate.

9. The substrate processing method according to claim 8, characterized in that: The first removal object and the second removal object are residues generated by dry etching.

10. The substrate processing method according to claim 9, characterized in that: The first object to be removed is granular residue, The second object to be removed is a film-like residue covering at least a portion of the non-exposed region on the surface of the substrate.

11. The substrate processing method according to claim 1 or 2, characterized in that: The removing liquid has a property of dissolving the protective film and the film to be peeled off.

12. A substrate processing device for processing a substrate having a surface, wherein the surface has an exposed area where a specific substance is exposed and a non-exposed area other than the exposed area, the substrate processing device comprising: a processing liquid supply unit for supplying processing liquid to the surface of the substrate; A film forming unit that solidifies or hardens the treatment liquid to form a solid film; a stripping liquid supplying unit for supplying a stripping liquid to the surface of the substrate; a cleaning liquid supply unit for supplying cleaning liquid to the surface of the substrate; a removing liquid supplying unit for supplying the removing liquid to the surface of the substrate; as well as a controller for controlling the processing liquid supply unit, the film forming unit, the stripping liquid supply unit, the cleaning liquid supply unit, and the removing liquid supply unit, The controller is programmed to: supplying the processing liquid from the processing liquid supply unit to the surface of the substrate, The processing liquid on the surface of the substrate is solidified or hardened by the film forming unit to form a stripping target film and a protective film on the surface of the substrate, wherein the stripping target film covers the non-exposed area while maintaining the first removal target present on the surface of the substrate, and the protective film covers the exposed area to protect it. The stripping liquid is supplied from the stripping liquid supply unit to the surface of the substrate, so that the stripping target film and the first removal target object are stripped from the surface of the substrate. After the stripping target film is stripped, a cleaning liquid is supplied from the cleaning liquid supply unit to the surface of the substrate to remove the second removal target object present on the surface of the substrate. After the cleaning liquid is supplied, the removing liquid is supplied from the removing liquid supply unit to the surface of the substrate to remove the protective film from the surface of the substrate.

Images