JP2021087002A - Substrate processing method, substrate processing apparatus, and recipe selection method - Google Patents

Abstract

To provide a substrate processing method and a substrate processing apparatus capable of efficiently removing an object to be removed from the surface of a substrate having a surface in which regions in which different substances are exposed are present.SOLUTION: A pretreatment film is formed on the surface of a substrate (pretreatment film forming step). By supplying peeling liquid, the pretreatment film holding a removal target is peeled from the surface of the substrate (pretreatment film peeling step). After the pretreatment film peeling step, a treatment film is formed on the surface of the substrate (treatment film forming step). By supplying peeling liquid, the treatment film holding the removal target is peeled from the surface of the substrate (treatment film peeling step). The removal power of the treatment film to remove the removal target existing in a non-exposed region is higher than the removal power of the pretreatment film to remove the removal target existing in the non-exposed region, and the removal power of the pretreatment film to remove the removal target existing in an exposed region is higher than the removal power of the treatment film to remove the removal target existing in the exposed region.SELECTED DRAWING: Figure 5

Description

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate, and a recipe selection method for selecting a recipe for performing the substrate processing method. The substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for FPDs (Flat Panel Display) such as organic EL (Electroluminescence) display devices, substrates for optical disks, substrates for magnetic disks, and substrates for opto-magnetic disks. Includes substrates such as substrates, photomask substrates, ceramic substrates, and solar cell substrates.

In the manufacturing process of a semiconductor device, various contaminants adhering to a substrate, residues such as a treatment liquid and a resist used in the previous process, various particles, etc. (hereinafter, may be collectively referred to as “objects to be removed”) are removed. The process is carried out.
Specifically, by supplying deionized water (DIW) or the like to the substrate, the object to be removed is removed by the physical action of DIW, or a chemical solution that chemically reacts with the object to be removed is applied to the substrate. It is common to chemically remove the object to be removed by supplying it.

However, the uneven pattern formed on the substrate is becoming finer and more complicated. Therefore, it is becoming difficult to remove the object to be removed by DIW or a chemical solution while suppressing damage to the uneven pattern.
Therefore, by supplying the treatment liquid to the surface of the substrate and solidifying the treatment liquid on the substrate to form a holding layer for holding the object to be removed existing on the substrate, the release liquid is supplied to the upper surface of the substrate. , A method has been proposed in which the holding layer is peeled off from the surface of the substrate together with the object to be removed and removed (see Patent Document 1).

JP-A-2019-62171

The removing force with which the retaining layer removes the object to be removed from the surface of the substrate varies depending on the type of substance exposed from the surface of the substrate. Therefore, when there are regions on the surface of the substrate where the exposed substances are different from each other, simply forming a specific holding layer on the surface of the substrate and peeling the holding layer from the surface of the substrate is sufficient to remove the object to be removed. It may not be removed. Depending on the substance exposed from the surface of the substrate, it is necessary to perform appropriate treatment to remove the object to be removed.

Therefore, one object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of efficiently removing an object to be removed from the surface of the substrate in a substrate having a surface in which regions where different substances are exposed exist. It is to be.
Another object of the present invention is to provide a recipe selection method capable of selecting a recipe for executing an appropriate substrate processing method according to the surface condition of the substrate.

One embodiment of the present invention is a substrate processing method for processing a substrate having a surface on which a first region and a second region where different substances are exposed are present.
The substrate treatment method exists on the surface of the substrate by solidifying or curing the pretreatment liquid supply step of supplying the pretreatment liquid to the surface of the substrate and the pretreatment liquid supplied to the surface of the substrate. A pretreatment film forming step of forming a pretreatment film for holding the first removal target on the surface of the substrate, and a state in which a release liquid is supplied to the surface of the substrate to hold the first removal target. The pretreatment film peeling step of peeling the pretreatment film from the surface of the substrate, the treatment liquid supply step of supplying the treatment liquid to the surface of the substrate after the pretreatment film peeling step, and the surface of the substrate. A treatment film forming step of solidifying or curing the supplied treatment liquid to form a treatment film on the surface of the substrate for holding the first removal object existing on the surface of the substrate, and peeling on the surface of the substrate. It includes a treatment film peeling step of supplying a liquid and peeling the treated film in a state of holding the first removal object from the surface of the substrate.

Then, the removing force for removing the first removal object existing in the second region is higher than the removing force for removing the first removal object existing in the second region by the pretreatment membrane. Is higher, and the pretreatment membrane removes the first removal target object existing in the first region than the removing force for removing the first removal target object existing in the first region. Power is high.
According to this method, the first removal target is removed from the surface of the substrate by peeling the pretreatment film having a high removing power for removing the first removal target existing in the first region. After that, the first removal target is removed from the surface of the substrate by peeling the treatment film having a high removing power for removing the first removal target existing in the second region. That is, the removal of the first removal target is performed in two steps using the pretreatment membrane and the treatment membrane in which the regions having high removing power for removing the first removal target are different from each other.

Therefore, even when the substrate has a surface on which a region in which different substances are exposed exists, the first removal target can be efficiently removed.
In one embodiment of the present invention, the removing force for removing the first removal target object holds the first removal target object existing in the first region or the second region on the treatment membrane or the pretreatment membrane. The pretreated film is composed of a holding force to be removed and a peeling property indicating the ease of peeling of the treated film or the pretreated film in a state of holding the first removal object, and the pretreated film is formed in the first region. The peelability is higher than that of the treated film, and the treated film has a higher holding power than the pretreated film in the second region.

Therefore, in the first region, most of the first removal target can be removed by peeling the pretreatment liquid film, and in the second region, most of the first removal countermeasures can be removed by peeling the treatment membrane. be able to. Therefore, even when the substrate has a surface on which a region in which different substances are exposed exists, the first removal target can be efficiently removed.
In one embodiment of the present invention, the first region is an exposed region where the metal is exposed, and the second region is a non-exposed region other than the exposed region. The removing force for removing the first removing object existing in the non-exposed region is higher than the removing force for removing the first removing object existing in the unexposed region by the pretreated membrane. The pretreatment film has a higher removing force for removing the first removing object existing in the exposed region than the removing force for removing the first removing object existing in the exposed region.

According to this method, the peeling of the pretreatment film having a relatively high removing power for removing the first removal target existing in the exposed region is compared with the removing power for removing the first removal target existing in the non-exposed region. The first object to be removed is removed from the surface of the substrate by performing both high-level peeling of the treated film. Therefore, the first removal target can be efficiently removed from the substrate having a surface having an exposed region and a non-exposed region.

In one embodiment of the present invention, the substrate processing method supplies a removing liquid to the surface of the substrate after the processing film peeling step to remove the residue of the treated film remaining on the surface of the substrate. It further includes a residue removing step. According to this method, even when the residue of the treatment film adheres to the surface of the substrate after the treatment film is peeled by the release liquid, the residue can be removed by the removal liquid.

In one embodiment of the present invention, the treated film peeling step includes a step of peeling a portion of the treated film that covers the unexposed region without peeling the portion of the treated film that covers the exposed region. Then, the treatment film residue removing step includes a step of dissolving and removing the portion of the treated film covering the exposed region in the removing liquid.
Even if the portion of the treated membrane that covers the exposed region remains on the exposed region without being stripped by the supply of the stripping liquid to the surface of the substrate, the portion can be dissolved in the removing liquid and removed from the exposed region. it can.

When the portion of the treated membrane that covers the exposed region is dissolved in the removal liquid, the first object to be removed released from the holding by the portion of the treated membrane that covers the exposed region may reattach to the exposed region. Therefore, if the pretreated film having a relatively high removing power for removing the first removal object existing in the exposed region is removed from the exposed region by peeling, and then the treated film is formed, the treated film is formed. Most of the first removal objects have been removed from the exposed area before being removed.

Therefore, even if the portion of the treated membrane that covers the exposed region is dissolved in the removing liquid and removed from the exposed region, it is possible to sufficiently suppress the remaining of the first removal target in the exposed region.
In one embodiment of the present invention, the treatment film forming step holds the first removal target object existing in the non-exposed region on the surface of the substrate and covers the non-exposed region, and the peeling target film. The step of forming the treated film having a protective film for covering and protecting the exposed region on the surface of the substrate is included. Then, the substrate treatment method further includes a cleaning step of supplying a cleaning liquid to the surface of the substrate after the treatment film peeling step and removing the second removal object existing on the surface of the substrate by the cleaning liquid. ..

According to this method, the treatment liquid supplied to the surface of the substrate is solidified or hardened to cover the non-exposed region of the surface of the substrate, and the protective film covering the exposed region of the surface of the substrate. Is formed.
By supplying the release liquid to the surface of the substrate on which the release target film and the protective film are formed, the release target film is peeled from the surface of the substrate while holding the first removal target object. Therefore, the first object to be removed is removed from the surface of the substrate. On the other hand, the second removal target remains on the surface of the substrate.

Then, the cleaning liquid removes the second object to be removed from the surface of the substrate, and then the removing liquid removes the protective film from the surface of the substrate.
When the cleaning liquid is supplied to the surface of the substrate, the exposed area where the metal is exposed on the surface of the substrate is covered with a protective film. Therefore, even if the cleaning liquid has the property of deteriorating (for example, oxidizing) the metal exposed on the surface of the substrate, it is possible to remove the second object to be removed without deteriorating the metal. it can.

Therefore, it is possible to efficiently remove a plurality of types of objects to be removed (first object to be removed and second object to be removed) from the surface of the substrate while suppressing deterioration of the metal exposed on the surface of the substrate.
In one embodiment of the present invention, the substrate processing method supplies a removing liquid to the surface of the substrate after the processing film peeling step to remove the residue of the treated film remaining on the surface of the substrate. It further includes a residue removing step. Then, the treatment film residue removing step includes a step of removing the protective film as the residue.

According to this method, even when the residue of the treatment film adheres to the surface of the substrate after the treatment film is peeled by the release liquid, the residue can be removed by the removal liquid. The protective film that remains on the substrate without being peeled by the stripping liquid is also dissolved by the removing liquid and removed from the exposed region.
Further, since the treated film is formed after the pretreated film having a relatively high removing power for removing the first removal object existing in the exposed region is removed from the exposed region by peeling, before the treated film is formed. Most of the first removal object has been removed from the exposed area. Therefore, even if the protective film is dissolved in the removing liquid and removed from the exposed region, it is possible to sufficiently prevent the first removal target from remaining in the exposed region.

In one embodiment of the present invention, the first removal target and the second removal target are residues produced by dry etching.
In the back end process (BOOL: Back End of the Line) in which a multi-layered metal layer is formed on the surface of a substrate, a dry etching process is performed to expose the metal on the surface of the substrate. That is, an exposed region where the metal is exposed and an unexposed region other than the exposed region are formed on the surface of the substrate.

_{The reaction product of the etching gas such as CF x} (for example, carbon tetrafluoride (CF ₄ )) used in the dry etching process and the portion constituting the non-exposed region in the substrate is used as the residue after the dry etching process. , Adhering to the surface of the substrate. The portion of the surface of the substrate that constitutes the non-exposed region includes surfaces such as a Low-k film (low dielectric constant interlayer insulating film), an oxide film, and a metal hard mask.

Specifically, in the non-exposed region of the surface of the substrate, a film-like reactant (film-like residue) of the etching gas and the low dielectric constant interlayer insulating film, and an etching gas and the low dielectric constant interlayer insulating film, an oxide film, or Granular reactants (granular residue) with the metal hard mask are attached. Granular means spherical, ellipsoidal, polyhedral, and the like. The granular residue also adheres to the exposed area on the surface of the substrate.
The granular residue can be peeled off by physical force, but the film-like residue covers at least a part of the unexposed area and is peeled off from the surface of the substrate by physical force as compared with the granular residue. Is difficult.

Therefore, if the configuration is such that the granular residue as the first object to be removed is removed by peeling the film to be peeled off, and the film-like residue as the second object to be removed is dissolved with a cleaning liquid to be removed, the residue is exposed on the surface of the substrate. It is possible to efficiently remove the object to be removed from the substrate while suppressing the deterioration of the metal.
Specifically, the peeling target film is formed by forming the peeling target film and the protective film on the surface of the substrate after the dry etching treatment, and supplying the peeling liquid to the surface of the substrate in which the peeling target film and the protective film are formed. It is peeled off from the surface of the substrate while holding the granular residue. Therefore, the granular residue is removed from the surface of the substrate. On the other hand, a film-like residue remains in the unexposed region on the surface of the substrate. Then, the cleaning liquid dissolves the film-like residue and removes it from the surface of the substrate, and then the removing liquid removes the protective film from the surface of the substrate.

When the cleaning liquid is supplied to the surface of the substrate, the exposed area where the metal is exposed on the surface of the substrate is covered with a protective film. Therefore, even if the cleaning liquid has the property of deteriorating (for example, oxidizing) the metal exposed on the surface of the substrate, the film-like residue can be removed without deteriorating the metal.
In one embodiment of the present invention, the treatment liquid has a first solute and a first solvent that dissolves the first solute. The first solute has a first highly soluble component and a first low soluble component that is less soluble in the stripping solution than the first highly soluble component. Then, the treatment film peeling step includes a step of selectively dissolving the first highly soluble component in a solid state in the stripping liquid.

According to this method, the first highly soluble component in the solid state in the treated membrane is selectively dissolved in the stripping solution. "The first highly soluble component in the solid state is selectively dissolved" does not mean that only the first highly soluble component in the solid state is dissolved. "The first highly soluble component in the solid state is selectively dissolved" means that the first highly soluble component in the solid state is also slightly dissolved, but most of the first highly soluble component in the solid state is dissolved. Means that is dissolved.

By dissolving the first highly soluble component in the solid state in the stripping solution, the stripping solution passes through the treatment membrane through the trace of the presence of the first highly soluble component in the solid state. As a result, the stripping liquid can act on the contact interface between the treated film and the substrate. On the other hand, the first low-solubility component in the treated membrane is maintained in a solid state without being dissolved. Therefore, the stripping liquid can act on the contact interface between the first low-solubility component in the solid state and the substrate while holding the first object to be removed by the first low-solubility component in the solid state. As a result, the treated film can be quickly removed from the surface of the substrate, and the first object to be removed together with the treated film can be efficiently removed from the surface of the substrate.

In one embodiment of the present invention, the treated film peeling step includes a first through hole forming step in which the treated film is partially dissolved in the peeling liquid to form a first through hole in the treated film.
Therefore, the stripping liquid can pass through the treated film through the first through hole and quickly reach the vicinity of the interface between the treated film and the surface of the substrate. Therefore, the treatment film can be efficiently peeled from the substrate by allowing the release liquid to act on the interface between the treatment film and the substrate. As a result, the first object to be removed can be efficiently removed from the surface of the substrate.

In one embodiment of the present invention, the pretreatment liquid has a second solute and a second solvent that dissolves the second solute. The second solute has a second highly soluble component and a second less soluble component that is less soluble in the stripping solution than the second highly soluble component. The pretreatment membrane peeling step includes a step of selectively dissolving the second highly soluble component in a solid state in the stripping liquid.
According to this method, the second highly soluble component in the solid state in the pretreatment membrane is selectively dissolved in the stripping solution. "The second highly soluble component in the solid state is selectively dissolved" does not mean that only the second highly soluble component in the solid state is dissolved. "The second highly soluble component in the solid state is selectively dissolved" means that the second highly soluble component in the solid state is also slightly dissolved, but most of the second highly soluble component in the solid state is dissolved. Means that is dissolved.

By dissolving the second highly soluble component in the solid state in the stripping solution, the stripping solution passes through the pretreatment membrane through the trace of the presence of the second highly soluble component in the solid state. As a result, the release 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 membrane is maintained in a solid state without being dissolved. Therefore, the release liquid can act on the contact interface between the second low-solubility component in the solid state and the substrate while holding the first object to be removed by the second low-solubility component in the solid state. As a result, the pretreatment film can be quickly removed from the surface of the substrate, and the first removal target can be efficiently removed from the surface of the substrate together with the pretreatment film.

In one embodiment of the present invention, the pretreatment film peeling step comprises a second through hole forming step in which the pretreatment film is partially dissolved in the peeling liquid to form a second through hole in the pretreatment film. Including.
Therefore, the release liquid can pass through the pretreatment film through the second through hole and quickly reach the vicinity of the interface between the pretreatment film and the surface of the substrate. Therefore, the pretreatment film can be efficiently peeled from the substrate by allowing the release liquid to act on the interface between the pretreatment film and the substrate. As a result, the first object to be removed can be efficiently removed from the surface of the substrate.

Another embodiment of the present invention provides a substrate processing apparatus that processes a substrate having a surface in which a first region and a second region are exposed to different substances.
The substrate processing apparatus includes a treatment liquid supply unit that supplies a treatment liquid to the surface of the substrate, a treatment film forming unit that solidifies or cures the treatment liquid to form a treatment film on the surface of the substrate, and a treatment film forming unit on the surface of the substrate. A pretreatment liquid supply unit that supplies the pretreatment liquid, a pretreatment film forming unit that solidifies or cures the pretreatment liquid to form a pretreatment film on the surface of the substrate, and a release liquid that supplies the release liquid to the surface of the substrate. The stripping liquid supply unit includes the pretreatment liquid supply unit, the pretreatment membrane forming unit, the treatment liquid supply unit, the treatment membrane forming unit, and a controller that controls the stripping liquid supply unit.

The controller supplies the pretreatment liquid from the pretreatment liquid supply unit toward the surface of the substrate, and the pretreatment film forming unit solidifies or cures the pretreatment liquid on the surface of the substrate, and the pretreatment liquid is solidified or cured. A pretreatment film for holding the object to be removed existing on the surface of the substrate is formed on the surface of the substrate, and the release liquid is supplied from the release liquid supply unit to the surface of the substrate to hold the object to be removed. The pretreatment film in the present state is peeled off from the surface of the substrate, the pretreatment film is peeled off, the treatment liquid is supplied from the treatment liquid supply unit to the surface of the substrate, and the treatment film forming unit provides the substrate. The treatment liquid on the surface of the substrate is solidified or hardened to form a treatment film on the surface of the substrate that holds the object to be removed existing on the surface of the substrate, and the treatment liquid is peeled from the release liquid supply unit to the surface of the substrate. It is programmed to supply a liquid to peel off the treated film in a state of holding the object to be removed from the surface of the substrate.

Then, the removing force for removing the removal target object existing in the second region is higher than the removing force for removing the removal target object existing in the second region by the pretreatment membrane. Further, the removing power for removing the removal target object existing in the first region by the pretreatment membrane is higher than the removing power for removing the removal target object existing in the first region.
According to this configuration, the same effect as that of the substrate processing method described above can be obtained.

In another embodiment of the present invention, the removing force for removing the object to be removed is a holding force for holding the object to be removed existing in the first region or the second region on the treated membrane or the pretreated membrane. And the peelability indicating the ease of peeling of the treated film or the pretreated film in a state of holding the object to be removed. Then, in the first region, the pretreated membrane has higher peelability than the treated membrane, and in the second region, the treated membrane has higher holding power than the pretreated membrane.

Therefore, in the first region, most of the substances to be removed can be removed by peeling the pretreatment liquid film, and in the second region, most of the substances to be removed can be removed by peeling the treatment film. Therefore, even when the substrate has a surface on which a region in which different substances are exposed exists, the object to be removed can be efficiently removed.
Yet another embodiment of the present invention provides a recipe selection method for selecting a recipe for performing a substrate processing method for processing a substrate to be processed. The recipe selection method includes an information acquisition step of acquiring information about the surface of the processing target substrate, and an exposed region where the processing target substrate is exposed to a specific substance based on the information acquired by the information acquisition step. A surface determination step of determining which of a substrate has a surface having both an unexposed region where a specific substance is not exposed and a substrate having a surface having only the unexposed region. When the surface determination step determines that only the non-exposed region exists on the surface of the processing target substrate, the first substrate processing method of removing the removal target object from the processing target substrate using the treatment liquid is executed. When the first recipe is selected and the surface determination step determines that both the exposed region and the non-exposed region are present on the surface of the processing target substrate, the removal target is removed from the exposed region. A second substrate treatment method in which the removal target is removed from the treatment target substrate using a pretreatment liquid having a force higher than that of the treatment liquid, and then the removal target is removed from the treatment target substrate using the treatment liquid. Includes a recipe selection step of selecting a second recipe to execute.

It is preferable to treat the substrate by a different substrate processing method between the substrate in which the exposed region on which the specific substance is exposed does not exist on the surface and the substrate in which both the exposed region and the non-exposed region are present on the surface. Specifically, when only an unexposed region exists on the surface of the substrate to be processed, the first substrate processing method of removing the object to be removed from the substrate to be processed using a treatment liquid can be executed from the surface of the substrate. The object to be removed can be sufficiently removed.

On the other hand, when both the exposed region and the non-exposed region are present on the surface of the substrate to be treated, simply removing the object to be removed from the substrate to be treated with the treatment liquid is sufficient to remove the object to be removed from the non-exposed region. Even if it can be removed, it may not be possible to sufficiently remove the object to be removed from the exposed area.
Therefore, when both the exposed region and the unexposed region are present on the surface of the substrate to be treated, the target to be removed from the substrate is a pretreatment liquid having a higher removing power than the treatment liquid to remove the object to be removed from the specific substance. After removing the substance, it is necessary to execute the second substrate processing method of removing the object to be removed from the substrate using the treatment liquid.

Therefore, when only the unexposed region exists on the surface of the substrate to be processed, the first recipe for executing the first substrate processing method is selected, and both the exposed region and the unexposed region exist on the surface of the substrate to be processed. In this case, by selecting the second recipe for executing the second substrate processing method, an appropriate substrate processing method can be executed according to the state of the surface of the substrate.
In yet another embodiment of the invention, the pretreatment liquid has a first component and a second component. The second component has a higher removing power for removing an object to be removed from the specific substance than the first component. The recipe selection method is based on the information acquired by the information acquisition step when the surface determination step determines that both the exposed region and the non-exposed region are present on the surface of the processing target substrate. A type determination step of determining the type of the specific substance exposed from the surface of the substrate to be processed is further included. Then, in the recipe selection step, the concentration of the second component in the pretreatment liquid used in the second substrate treatment method is set according to the specific substance of the type determined by the type determination step. The step of selecting the second recipe is included.

According to this method, when both the exposed region and the unexposed region are present on the surface of the substrate to be processed, a second recipe suitable for removing the object to be removed from the exposed region is provided according to the type of the specific substance. You can choose.

FIG. 1 is a schematic plan view showing the layout of the substrate processing apparatus according to the first embodiment of the present invention. FIG. 2 is an example of a cross-sectional view of the surface layer of the substrate processed by the substrate processing apparatus. FIG. 3 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit provided in the substrate processing apparatus. FIG. 4 is a block diagram showing the hardware of the controller provided in the substrate processing apparatus. FIG. 5 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus. FIG. 6A is a schematic view for explaining the state of the pretreatment liquid supply step (step S2) of the substrate treatment. FIG. 6B is a schematic view for explaining the state of the pretreatment film forming step (step S3) of the substrate treatment. FIG. 6C is a schematic view for explaining the state of the pretreatment film forming step (step S3). FIG. 6D is a schematic view for explaining the state of the pretreatment film peeling step (step S4) of the substrate treatment. FIG. 6E is a schematic view for explaining the state of the stripping liquid removing step (step S5) of the substrate treatment. FIG. 6F is a schematic view for explaining the state of the pretreatment film residue removing step (step S6) of the substrate treatment. FIG. 6G is a schematic diagram for explaining the state of the processing liquid supply step (step S7) of the substrate processing. FIG. 6H is a schematic view for explaining the state of the processing film forming step (step S8) of the substrate processing. FIG. 6I is a schematic view for explaining the state of the treated film forming step (step S8). FIG. 6J is a schematic view for explaining the state of the processing film peeling step (step S9) of the substrate processing. FIG. 6K is a schematic view for explaining the state of the stripping liquid removing step (step S10) of the substrate treatment. FIG. 6L is a schematic view for explaining the state of the treatment film residue removing step (step S11) of the substrate treatment. FIG. 6M is a schematic view for explaining the state of the spin-drying step (step S12) of the substrate processing. FIG. 7A is a schematic view for explaining a state near the surface of the substrate in a state where the pretreatment film is formed by executing the pretreatment film forming step (step S3). FIG. 7B is a schematic view for explaining a state near the surface of the substrate during the execution of the pretreatment film peeling step (step S4). FIG. 7C is a schematic view for explaining a state near the surface of the substrate in a state where the treated film is formed by executing the treated film forming step (step S8). FIG. 7D is a schematic view for explaining a state near the surface of the substrate during the execution of the treated film peeling step (step S9). FIG. 7E is a schematic view for explaining a state near the surface of the substrate in a state where the residue of the treated film is removed by executing the process of removing the residue of the treated film (step S11). FIG. 8A is a schematic view for explaining how the pretreatment film is peeled off from the substrate. FIG. 8B is a schematic view for explaining how the pretreatment film is peeled off from the substrate. FIG. 8C is a schematic view for explaining how the pretreatment film is peeled off from the substrate. FIG. 9A is a schematic view for explaining how the treated film is peeled off from the substrate. FIG. 9B is a schematic view for explaining how the treated film is peeled off from the substrate. FIG. 9C is a schematic view for explaining how the treated film is peeled off from the substrate. FIG. 10A is a schematic view for explaining how the exposed region covering portion covering the exposed region where the metal film is exposed on the surface of the substrate is removed from the substrate. FIG. 10B is a schematic view for explaining how the exposed region covering portion is removed from the substrate. FIG. 10C is a schematic view for explaining how the exposed region covering portion is removed from the substrate. FIG. 11 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit provided in the substrate processing apparatus according to the second embodiment of the present invention. FIG. 12 is an example of a cross-sectional view of the surface layer of the substrate processed by the substrate processing apparatus according to the second embodiment. FIG. 13 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus according to the second embodiment. FIG. 14A is a schematic view for explaining the state of the cleaning step (step S20) of the substrate processing according to the second embodiment. FIG. 14B is a schematic view for explaining the state of the cleaning liquid removing step (step S21) of the substrate treatment according to the second embodiment. FIG. 15A is a schematic view for explaining a state near the surface of the substrate in a state where the pretreatment film is formed by executing the pretreatment film forming step (step S3) in the substrate treatment according to the second embodiment. FIG. 15B is a schematic view for explaining a state near the surface of the substrate during execution of the pretreatment film peeling step (step S4) in the substrate treatment according to the second embodiment. FIG. 15C is a schematic view for explaining a state near the surface of the substrate in a state where the treated film is formed by executing the treated film forming step (step S12) in the substrate processing according to the second embodiment. FIG. 15D is a schematic view for explaining a state near the surface of the substrate during execution of the processing film peeling step (step S13) in the substrate treatment according to the second embodiment. FIG. 15E is a schematic view for explaining a state near the surface of the substrate during execution of the cleaning step (step S20) of the substrate treatment according to the second embodiment. FIG. 16 shows a change in the particle removing power from the copper film due to changing the ratio of the first component and the second component of the highly soluble component in the polymer-containing liquid used as the treatment liquid and the pretreatment liquid. It is a table for explaining the result of the experiment for verifying. FIG. 17 is a schematic view of the first moving nozzle and the third moving nozzle of the processing unit provided in the substrate processing apparatus according to the third embodiment of the present invention, and the members around them. FIG. 18 is a flow chart for explaining an example of a recipe selection process executed for selecting a recipe in the substrate processing apparatus according to the third embodiment. FIG. 19 is a flow chart for explaining another example of the recipe selection process in the substrate processing apparatus according to the third embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
<First Embodiment>
FIG. 1 is a schematic plan view showing the layout of the substrate processing apparatus 1 according to the embodiment of the present invention.
The substrate processing device 1 is a single-wafer type device that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a disk-shaped substrate.

The substrate processing apparatus 1 includes a load port LP on which a plurality of processing units 2 for processing the substrate W with a fluid, a carrier C accommodating a plurality of substrates W processed by the processing unit 2, and a load port LP are mounted. It includes transfer robots IR and CR that transfer the substrate W between the substrate processing unit 2 and the processing unit 2, and a controller 3 that controls the substrate processing apparatus 1.
The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing unit 2. The plurality of processing units 2 have, for example, a similar configuration. As will be described in detail later, the treatment fluid supplied to the substrate W in the treatment unit 2 includes a rinse liquid, a treatment liquid, a pretreatment liquid, a stripping liquid, a cleaning liquid, a removal liquid, a heat medium, an inert gas (gas), and the like. Is included.

Each processing unit 2 includes a chamber 4 and a processing cup 7 arranged in the chamber 4, and processes the substrate W in the processing cup 7. The chamber 4 is formed with an entrance / exit (not shown) for loading / unloading the substrate W and unloading the substrate W by the transfer robot CR. The chamber 4 is provided with a shutter unit (not shown) that opens and closes the doorway.

FIG. 2 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 near the surface of the substrate W.
A fine uneven pattern 160 is formed on the surface of the untreated substrate W before being processed by the processing unit 2. The uneven pattern 160 includes a fine convex structure 161 formed on the surface of the substrate W and a concave portion (groove) 162 formed between adjacent structures 161. The structure 161 is composed of 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.

The surface of the uneven pattern 160, that is, the surface of the structure 161 (convex portion) and the surface of the concave portion 162 form the uneven pattern surface 165. The pattern surface 165 is included in the surface of the substrate W. On the pattern surface 165 of the substrate W, there is a region where various substances are exposed. In the example shown in FIG. 2, 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 in which the surface of the metal film 163 is exposed and an unexposed region 171 in which the metal film 163 is not exposed. The non-exposed area 171 is an area other than the exposed area 170 on the pattern surface 165 of the substrate W.

In this embodiment, a metal such as copper is an example of a specific substance. The exposed region 170 corresponds to the first region, and the non-exposed region 171 corresponds to the second region.
The object to be removed 103 is attached to both the unexposed area 171 and the exposed area 170. The object to be removed 103 is, for example, granular. Granular means spherical, ellipsoidal, polyhedral, and the like. The object to be removed 103 is an example of the first object to be removed.

FIG. 3 is a schematic diagram for explaining a configuration example of the processing unit 2. The processing unit 2 includes a spin chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11, a central nozzle 12, and a lower surface nozzle 13. including.
The spin chuck 5 rotates the substrate W around the vertical rotation axis A1 (vertical axis) passing through the central portion of the substrate W while holding the substrate W horizontally. The spin chuck 5 includes a plurality of chuck pins 20, a spin base 21, a rotating shaft 22, and a spin motor 23.

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

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 spin base 21. The spin motor 23 applies a rotational force to the rotating shaft 22. The spin base 21 is rotated by rotating the rotating shaft 22 by the spin motor 23. As a result, the substrate W is rotated around the rotation axis A1. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

The facing member 6 faces the substrate W held by the spin chuck 5 from above. The facing member 6 is formed in 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 (upper surface) of the substrate W. The facing surface 6a is arranged above the spin chuck 5 and substantially along the horizontal plane.
A hollow shaft 60 is fixed to the facing member 6 on the side opposite to the facing surface 6a. A communication hole 6b that vertically penetrates the facing member 6 is formed in a portion of the facing member 6 that overlaps the rotation axis A1 in a plan view. The communication hole 6b communicates with the internal space 60a of the hollow shaft 60.

The facing member 6 shields the atmosphere in the space between the facing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the opposing member 6 is also referred to as a blocking plate.
The processing unit 2 further includes an opposing member elevating unit 61 that drives the elevating and lowering of the opposing member 6. The facing member elevating unit 61 can position the facing member 6 in the vertical direction at an arbitrary position (height) from the lower position to the upper position. The lower position is a position where the facing surface 6a is closest to the substrate W in the movable range of the facing member 6. The upper position is a position where the facing surface 6a is most distant from the substrate W in the movable range of the facing member 6. When the opposing member 6 is located at the upper position, the transfer robot CR can access the spin chuck 5 for loading and unloading the substrate W.

The facing member elevating unit 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) that supports the hollow shaft 60, and an electric motor (not shown) that applies a driving force to the ball screw mechanism. Includes) and. The facing member elevating unit 61 is also referred to as a facing member lifter (blocking plate lifter).
The processing cup 7 includes a plurality of guards 71 that receive the liquid scattered outward from the substrate W held by the spin chuck 5, a plurality of cups 72 that receive the liquid guided downward by the plurality of guards 71, and a plurality of cups 72. Includes a cylindrical outer wall member 73 that surrounds the guard 71 and the plurality of cups 72.

In this embodiment, an example is shown in which two guards 71 (first guard 71A and second guard 71B) and two cups 72 (first cup 72A and second cup 72B) are provided.
Each of the first cup 72A and the second cup 72B has the form of an annular groove that is open upward.

The first guard 71A is arranged so as to surround the spin base 21. The second guard 71B is arranged so as to surround the spin base 21 on the outer side in the rotational radial direction of the substrate W than the first guard 71A.
The first guard 71A and the second guard 71B each have a substantially cylindrical shape. The upper end of each guard 71 is inclined inward toward the spin base 21.

The first cup 72A receives the liquid guided downward by the first guard 71A. The second cup 72B is integrally formed with the first guard 71A, and receives the liquid guided downward by the second guard 71B.
The processing unit 2 includes a guard elevating unit 74 that separately elevates the first guard 71A and the second guard 71B in the vertical direction. The guard elevating unit 74 raises and lowers the first guard 71A between the lower position and the upper position. The guard elevating unit 74 raises and lowers the second guard 71B between the lower position and the upper position.

When both the first guard 71A and the second guard 71B are located at the upper positions, the liquid scattered from the substrate W is received by the first guard 71A. When the first guard 71A is located in the lower position and the second guard 71B is located in the upper position, the liquid scattered from the substrate W is received by the second guard 71B. When both the first guard 71A and the second guard 71B are located at the lower positions, the transfer robot CR can access the spin chuck 5 for loading and unloading the substrate W.

The guard elevating unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first guard 71A, a first motor (not shown) that applies a driving force to the first ball screw mechanism, and a second. It includes a second ball screw mechanism (not shown) coupled to the guard 71B and a second motor (not shown) that applies a driving force to the second ball screw mechanism. The guard elevating unit 74 is also referred to as a guard lifter.

The first moving nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (discharges) the processing liquid toward the upper surface of the substrate W held by the spin chuck 5.
The first moving nozzle 9 is moved in the horizontal direction and the vertical direction by the first nozzle moving unit 35. The first moving nozzle 9 can move between the center position and the home position (retracted position) in the horizontal direction. When the first moving nozzle 9 is located at the center position, the first moving nozzle 9 faces the center of rotation on the upper surface of the substrate W. The rotation center of the upper surface of the substrate W is a position intersecting with the rotation axis A1 on the upper surface of the substrate W.

When the first moving nozzle 9 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The first moving nozzle 9 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.
The first nozzle moving unit 35 includes, for example, an arm (not shown) coupled to the first moving nozzle 9 and extending horizontally, a rotating shaft (not shown) coupled to the arm and extending in the vertical direction, and rotation. Includes a rotating shaft drive unit (not shown) that raises and lowers and rotates the moving shaft.

The rotation shaft drive unit swings the arm by rotating the rotation shaft around a vertical rotation axis. Further, the rotating shaft drive unit moves the arm up and down by moving the rotating shaft up and down along the vertical direction. The first moving nozzle 9 moves in the horizontal direction and the vertical direction according to the swinging and raising / lowering of the arm.
The first moving nozzle 9 is connected to a processing liquid pipe 40 that guides the processing liquid. When the treatment liquid valve 50 interposed in the treatment liquid pipe 40 is opened, the treatment liquid is discharged downward from the first moving nozzle 9 in a continuous flow.

The treatment liquid discharged from the first moving nozzle 9 contains a solute and a solvent. The treatment liquid solidifies or hardens by volatilizing (evaporating) at least a part of the solvent. The treatment liquid solidifies or hardens on the substrate W to form a solid treatment film that holds the object to be removed 103 present on the substrate W.
Here, "solidification" means, for example, that the solute is solidified by the force acting between molecules or atoms as the solvent volatilizes. "Curing" refers to the hardening of a solute by, for example, a chemical change such as polymerization or cross-linking. Therefore, "solidification or hardening" means that the solute "solidifies" due to various factors.

The solute contained in the treatment liquid discharged from the first moving nozzle 9 includes a low-solubility component and a high-solubility component.
When the metal is exposed on the surface of the substrate W, it is preferable that the solute contained in the treatment liquid discharged from the first moving nozzle 9 contains a corrosion preventing component. As will be described in detail later, the corrosion-preventing component is, for example, BTA (benzotriazole).

As the low-solubility component and the high-solubility component contained in the treatment solution discharged from the first moving nozzle 9, substances having different solubilities in the stripping solution can be used. The low-solubility component contained in the treatment liquid discharged from the first moving nozzle 9 is, for example, novolak. The highly soluble component contained in the treatment solution discharged 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 liquid, and the treatment membrane is also referred to as a polymer membrane.

The solvent contained in the treatment liquid discharged from the first moving nozzle 9 may be any liquid that dissolves the low-solubility component and the high-solubility component. The solvent contained in the treatment liquid is preferably a liquid having compatibility (miscibility) with the stripping liquid.
The solvent contained in the treatment liquid is referred to as a first solvent, and the solute contained in the treatment liquid is referred to as a first solute. The low-solubility component contained in the treatment solution is referred to as a first low-solubility component, and the highly soluble component contained in the treatment solution is referred to as a first high-solubility component.

Details of the solvent, the low-solubility component, the highly-soluble component, and the corrosion-preventing component contained in the treatment liquid discharged from the first moving nozzle 9 will be described later.
The second moving nozzle 10 is an example of a stripping liquid nozzle (peeling liquid supply unit) that supplies (discharges) a stripping liquid such as ammonia water in a continuous flow toward the upper surface of the substrate W held by the spin chuck 5. The stripping liquid is a liquid for stripping the treated film holding the object to be removed 103 from the upper surface of the substrate W. Specifically, in the treated film, only the portion covering the non-exposed region 171 is peeled from the substrate W by the peeling liquid.

The second moving nozzle 10 is moved in the horizontal direction and the vertical direction by the second nozzle moving unit 36. The second moving nozzle 10 can move between the center position and the home position (retracted position) in the horizontal direction.
When the second moving nozzle 10 is located at the center position, the second moving nozzle 10 faces the center of rotation on the upper surface of the substrate W. When the second moving nozzle 10 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The second moving nozzle 10 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

The second nozzle moving unit 36 has the same configuration as the first nozzle moving unit 35. That is, the second nozzle moving unit 36 has, for example, an arm (not shown) coupled to the second moving nozzle 10 and extending horizontally, and a rotating shaft (not shown) coupled to the arm and extending in the vertical direction. And a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

As the stripping liquid discharged from the second moving nozzle 10, a liquid that easily dissolves the highly soluble component contained in the solute of the treatment liquid is used rather than the low solubility component contained in the solute of the treatment liquid. The stripping liquid discharged from the second moving nozzle 10 is not limited to ammonia water.
The stripping liquid discharged from the second moving nozzle 10 may be, for example, an alkaline aqueous solution (alkaline liquid) other than ammonia water. Specific examples of the alkaline aqueous solution other than the aqueous ammonia include a TMAH (tetramethylammonium hydroxide) aqueous solution, a choline aqueous solution, and a combination thereof.

The stripping liquid discharged from the second moving nozzle 10 may be pure water (preferably DIW) or a neutral or acidic aqueous solution (non-alkaline aqueous solution).
The second moving nozzle 10 is connected to the upper stripping liquid pipe 41 that guides the stripping liquid to the second moving nozzle 10. When the upper release liquid valve 51 interposed in the upper release liquid pipe 41 is opened, the release liquid is discharged downward from the discharge port of the second moving nozzle 10 in a continuous flow.

The third moving nozzle 11 is an example of a pretreatment liquid nozzle (pretreatment liquid supply unit) that supplies (discharges) the pretreatment liquid toward the upper surface of the substrate W held by the spin chuck 5.
The third moving nozzle 11 is moved in the horizontal direction and the vertical direction by the third nozzle moving unit 37. The third moving nozzle 11 can move between the center position and the home position (retracted position) in the horizontal direction.

When the third moving nozzle 11 is located at the center position, it faces the rotation center of the upper surface of the substrate W. When the third moving nozzle 11 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The third moving nozzle 11 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.
The third nozzle moving unit 37 has the same configuration as the first nozzle moving unit 35. That is, the third nozzle moving unit 37 is, for example, an arm (not shown) coupled to the third moving nozzle 11 and extending horizontally, and a rotating shaft (not shown) coupled to the arm and extending in the vertical direction. And a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

The pretreatment liquid discharged from the third moving nozzle 11 contains a solute and a solvent. The pretreatment liquid solidifies or hardens by volatilizing (evaporating) at least a part of the solvent. The pretreatment liquid solidifies or hardens on the substrate W to form a pretreatment film that holds the object to be removed 103 present on the substrate W.
The solute contained in the pretreatment liquid discharged from the third moving nozzle 11 includes a low-solubility component and a high-solubility component.

When the metal is exposed on the surface of the substrate W, it is preferable that the solute contained in the pretreatment liquid discharged from the third moving nozzle 11 contains a corrosion preventing component. As will be described in detail later, the corrosion-preventing component is, for example, BTA.
As the low-solubility component and the high-solubility component contained in the pretreatment solution, substances having different solubilities in the stripping solution can be used. The low-solubility component contained in the pretreatment liquid discharged from the third moving nozzle 11 is, for example, novolak. The highly soluble components contained in the pretreatment solution discharged from the third moving nozzle 11 are 2,2-bis (4-hydroxyphenyl) propane (first component) and 3,6-dimethyl-4-octyne-3. , 6-diol (second component) is included. The pretreatment liquid is also referred to as a polymer-containing liquid, and the pretreatment membrane is also referred to as a polymer membrane.

The solvent contained in the pretreatment liquid discharged from the third moving nozzle 11 may be a liquid that dissolves the low-solubility component and the high-solubility component. The solvent contained in the pretreatment liquid is preferably a liquid having compatibility (miscibility) with the stripping liquid.
The solvent contained in the pretreatment liquid is referred to as a second solvent, and the solute contained in the pretreatment liquid is referred to as a second solute. The low-solubility component contained in the treatment solution is referred to as a second low-solubility component, and the highly soluble component contained in the treatment solution is referred to as a second high-solubility component.

Details of the solvent, the low-solubility component, the highly-soluble component, and the corrosion-preventing component contained in the pretreatment liquid discharged from the third moving nozzle 11 will be described later.
In the pretreatment film, both the portion covering the exposed region 170 and the portion covering the unexposed region 171 are peeled from the substrate W by the stripping liquid.
The removing power of the polymer film such as the treated film or the pretreatment film to remove the object to be removed 103 is the case where the object 103 to be removed is removed from the exposed region 170 and the case where the object 103 to be removed is removed from the unexposed area 171. And it is significantly different.

The removing force with which the polymer film removes the object to be removed 103 is composed of the holding force of the object to be removed and the peelability. The removal target holding force is the ability to hold the removal target 103 existing in the target region (exposed region 170 or non-exposed region 171) in at least one of the film and the surface of the polymer film. The peelability is a property that indicates the ease of peeling when the polymer film holding the object to be removed 103 is peeled by the peeling liquid. High peelability means that it is easily peeled off by the peeling liquid. The removing force of the polymer film is the ability to remove the object to be removed 103 from the target area when the polymer film is peeled off by the stripping liquid while holding the object to be removed 103 existing in the target area.

The pretreated film exhibits high removal object retention in both the unexposed area 171 and the exposed area 170, whereas the treated film removes even higher than the pretreated film in both the unexposed area 171 and the exposed area 170. Demonstrate object holding power. On the other hand, the pretreated film has higher peelability than the treated film in the exposed region 170. Therefore, the pretreated film exerts a higher removing power than the treated film in the exposed region 170, and the treated film exerts a higher removing power than the pretreated film in the non-exposed region 171.

Specifically, the removing force for removing the removal target object 103 existing in the non-exposed region 171 by the treatment film is higher than the removing force for removing the removal target object 103 existing in the non-exposed area 171 by the pretreatment film. The removing force for removing the removal target 103 existing in the exposed region 170 by the pretreatment film is higher than the removing force for removing the removal target 103 existing in the exposed region 170 by the treatment film.
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 interposed in the pretreatment liquid pipe 42 is opened, the pretreatment liquid is discharged downward from the discharge port of the third moving nozzle 11 in a continuous flow.

The central nozzle 12 is housed in the internal space 60a of the hollow shaft 60 of the facing member 6. The discharge port 12a provided at the tip of the central nozzle 12 faces the central region on the upper surface of the substrate W from above. The central region of the upper surface of the substrate W is a region on the upper surface of the substrate W that includes the center of rotation of the substrate W and its periphery.
The central nozzle 12 includes a plurality of tubes (first tube 31, second tube 32, and third tube 33) for discharging the fluid downward, and a tubular 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 discharge port 12a of the central nozzle 12 is also a discharge port of the first tube 31, a discharge port of the second tube 32, and a discharge port of the third tube 33.

The first tube 31 (center 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 (center nozzle 12) is an example of a removal liquid supply unit that supplies a removal liquid such as IPA to the upper surface of the substrate W. The third tube 33 (center nozzle 12) is _{an example of a gas supply unit that supplies a gas such as nitrogen gas (N 2} ) 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.

The first tube 31 is connected to the upper rinse liquid pipe 43 that guides the rinse liquid to the first tube 31. When the upper rinse liquid valve 53 interposed in the upper rinse liquid pipe 43 is opened, the rinse liquid is continuously discharged from the first tube 31 (center nozzle 12) toward the central region on the upper surface of the substrate W. ..
Examples of the rinsing solution include DIW, carbonated water, electrolytic ionized water, hydrochloric acid water having a dilution concentration (for example, about 1 ppm to 100 ppm), ammonia water having a dilution concentration (for example, about 1 ppm to 100 ppm), reduced water (hydrogen water), and the like. Can be mentioned.

The second tube 32 is connected to a removal liquid pipe 44 that guides the removal liquid to the second tube 32. When the removal liquid valve 54 interposed in the removal liquid pipe 44 is opened, the removal liquid is discharged from the second tube 32 (center nozzle 12) toward the central region on the upper surface of the substrate W in a continuous flow.
The removal liquid discharged from the second tube 32 removes a portion of the treated membrane that was not peeled from the upper surface of the substrate W by the stripping liquid and a portion of the pretreatment membrane that was not stripped from the upper surface of the substrate W by the stripping liquid. It is a liquid to do. The removing liquid is preferably a liquid having higher volatility than the rinsing liquid. The removing liquid discharged from the second tube 32 is preferably compatible with the rinsing liquid.

The removing liquid discharged from the second tube 32 is, for example, an organic solvent. The organic solvent discharged from the second tube 32 is at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether) and Trans-1,2-dichloroethylene. Examples include liquids containing.

Further, the organic solvent discharged from the second tube 32 does not have to consist of only a single component, and may be a liquid mixed with other components. For example, it may be a mixed solution of IPA and DIW, or it may be a mixed solution of IPA and HFE.
The third tube 33 is connected to a gas pipe 45 that guides the gas to the third tube 33. When the gas valve 55 interposed in the gas pipe 45 is opened, gas is discharged downward from the third tube 33 (center nozzle 12) in a continuous flow.

The gas discharged from the third tube 33 is, for example, an inert gas such as nitrogen gas. The gas discharged from the third tube 33 may be air. The inert gas is not limited to the nitrogen gas, but is a gas that is inert to the upper surface of the substrate W and the uneven pattern 160 (see FIG. 2) formed on the upper surface of the substrate W. Examples of the inert gas include rare gases such as argon in addition to nitrogen gas.

The lower surface nozzle 13 is inserted into a through hole 21a that opens at the center of the upper surface of the spin base 21. The discharge port 13a of the lower surface nozzle 13 is exposed from the upper surface of the spin base 21. The discharge port 13a of the lower surface nozzle 13 faces the central region of the lower surface (lower surface) of the substrate W from below. The central region of the lower surface of the substrate W is a region on the lower surface of the substrate W including the rotation center of the substrate W.

One end of a common pipe 80 that commonly guides the rinse liquid, the stripping liquid, and the heat medium to the bottom nozzle 13 is connected to the bottom nozzle 13. At the other end of the common pipe 80, a lower rinse liquid pipe 81 that guides the rinse liquid to the common pipe 80, a lower peeling liquid pipe 82 that guides the stripping liquid to the common pipe 80, and a heat medium are applied to the common pipe 80. The heat medium pipe 83 for guiding is connected.
When the lower rinse liquid valve 86 interposed in the lower rinse liquid pipe 81 is opened, the rinse liquid is discharged from the lower surface nozzle 13 toward the central region of the lower surface of the substrate W in a continuous flow. When the lower release liquid valve 87 interposed in the lower release liquid pipe 82 is opened, the release liquid is discharged from the lower surface nozzle 13 toward the central region of the lower surface of the substrate W in a continuous flow. When the heat medium valve 88 interposed in the heat medium pipe 83 is opened, the heat medium is discharged from the lower surface nozzle 13 toward the central region of the lower surface of the substrate W in a continuous flow.

The lower surface nozzle 13 is an example of a lower rinse liquid supply unit that supplies the rinse liquid to the lower surface of the substrate W. Further, the lower surface nozzle 13 is an example of a lower release liquid supply unit that supplies a release liquid to the lower surface of the substrate W. Further, 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 bottom surface nozzle 13 is also a substrate heating unit that heats the substrate W.

The heat medium discharged from the bottom nozzle 13 is, for example, a 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, for example, DIW at 60 ° C. to 80 ° C. is used as the heat medium. The heat medium discharged from the bottom nozzle 13 is not limited to the high temperature DIW, but is 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. You may.

FIG. 4 is a block diagram showing the hardware of the controller 3. The controller 3 is a computer including a computer main body 3a and a peripheral device 3d connected to the computer main body 3a. The computer main body 3a includes a CPU 3b (central processing unit) that executes various instructions and a main storage device 3c that stores information. The peripheral device 3d includes an auxiliary storage device 3e that stores information such as the program P, a reading device 3f that reads information from the removable media RM, and a communication device 3g that communicates with other devices such as a host computer.

The controller 3 is connected to the input device 3A, the display device 3B, and the alarm device 3C. The input device 3A is operated when an operator such as a user or a maintenance person inputs information to the board processing device 1. The information is displayed on the screen of the display device 3B. The input device 3A may be any of a keyboard, a pointing device, and a touch panel, or may be a device other than these. The substrate processing device 1 may be provided with a touch panel display that also serves as an input device 3A and a display device 3B. The alarm device 3C issues an alarm using one or more of light, sound, letters, and graphics. When the input device 3A is a touch panel display, the input device 3A may also serve as the alarm device 3C.

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, may be sent from the removable media RM to the auxiliary storage device 3e through the reader 3f, or may be a host. It may be sent from an external device such as a computer to the auxiliary storage device 3e through the communication device 3g.

The auxiliary storage device 3e and the removable media 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 media RM is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable media RM is an example of a computer-readable recording medium on which the program P is recorded. Removable media RM is a non-temporary tangible recording medium.

The auxiliary storage device 3e stores a plurality of recipes R. Recipe R is information that defines the processing content, processing conditions, and processing procedure of the substrate W. The plurality of recipes R are different from each other in at least one of the processing contents, processing conditions, and processing procedures of the substrate W.
The controller 3 controls the substrate processing device 1 so that the substrate W is processed according to the recipe R set in the main storage device 3c. Each of the following steps is executed by the controller 3 controlling the substrate processing device 1. In other words, the controller 3 is programmed to perform each of the following steps.

FIG. 5 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus 1. FIG. 5 mainly shows the processing realized by the controller 3 executing the program. 6A to 6M are schematic views for explaining the state of each step of the substrate processing.
In the substrate processing by the substrate processing apparatus 1, for example, as shown in FIG. 5, the substrate carrying step (step S1), the pretreatment liquid supply step (step S2), the pretreatment film forming step (step S3), and the pretreatment film peeling are performed. Step (step S4), release liquid removing step (step S5), pretreatment film residue removing step (step S6), treatment liquid supply step (step S7), treatment film forming step (step S8), treatment film peeling step (step) S9), the stripping liquid removing step (step S10), the treated film residue removing step (step S11), the spin drying step (step S12), and the substrate unloading step (step S13) are executed in this order.

First, the unprocessed substrate W is carried into the processing unit 2 from the carrier C by the transfer robots IR and CR (see FIG. 1) and passed to the spin chuck 5 (step S1). As a result, the substrate W is held horizontally by the spin chuck 5 (board holding step). The substrate W is held by the spin chuck 5 so that the pattern surface 165 is on the upper surface. When the substrate W is carried in, the opposing member 6 is retracted to the upper position.

The holding of the substrate W by the spin chuck 5 is continued until the spin drying step (step S12) is completed. The guard elevating unit 74 has the first guard 71A and the second guard so that at least one guard 71 is located at the upper position from the start of the substrate holding step to the end of the spin drying step (step S12). Adjust the height position of 71B.
Next, after the transfer robot CR is retracted to the outside of the processing unit 2, the pretreatment liquid supply step (step S2) is started. In the pretreatment liquid supply step, first, the spin motor 23 rotates the spin base 21. As a result, the horizontally held substrate W is rotated (board rotation step).

The third nozzle moving unit 37 moves the third moving nozzle 11 to the processing position while the facing member 6 is located at the upper position. The processing position of the third moving nozzle 11 is, for example, the central position. Then, the pretreatment liquid valve 52 is opened. As a result, as shown in FIG. 6A, the pretreatment liquid is supplied (discharged) from the third moving nozzle 11 toward the central region of the upper surface of the rotating substrate W (pretreatment liquid supply step, pretreatment liquid). Discharge process). As a result, a liquid film 201 (pretreatment liquid film) of the pretreatment liquid is formed on the substrate W (pretreatment liquid film forming step).

The supply of the pretreatment liquid from the third moving nozzle 11 is continued for a predetermined time, for example, 2 to 4 seconds. In the pretreatment liquid supply step, the substrate W is rotated at a predetermined pretreatment liquid rotation speed, for example, 10 rpm to 1500 rpm.
Next, the pretreatment film forming step (step S3) is executed. In the pretreatment film forming step, the pretreatment liquid on the substrate W is solidified or hardened, and the pretreatment film 200 (see FIG. 7A described later) that holds the object to be removed 103 existing on the substrate W is formed on the substrate W. It is formed on the upper surface.

In the pretreatment film forming step, first, a pretreatment liquid thinning step (pretreatment liquid spin-off step) of reducing the thickness of the liquid film 201 of the pretreatment liquid on the substrate W is executed. Specifically, the pretreatment liquid valve 52 is closed. As a result, the supply of the pretreatment liquid to the substrate W is stopped. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to the home position.
As shown in FIG. 6B, in the pretreatment liquid thinning step, the supply of the pretreatment liquid to the upper surface of the substrate W was stopped so that the thickness of the liquid film 201 on the substrate W became an appropriate thickness. In this state, a part of the pretreatment liquid is removed from the upper surface of the substrate W by centrifugal force.

Even after the third moving nozzle 11 moves to the home position, the opposing member 6 is maintained in the upper position.
In the pretreatment liquid thinning step, the spin motor 23 changes the rotation speed of the substrate W to a predetermined pretreatment liquid thinning speed. The pretreatment liquid thinning rate is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W may be kept constant within the range of 300 rpm to 1500 rpm, or may be appropriately changed within the range of 300 rpm to 1500 rpm during the process of thinning the pretreatment liquid. The pretreatment liquid thinning step is carried out for a predetermined time, for example, 30 seconds.

In the pretreatment film forming step, after the pretreatment liquid thinning step, a pretreatment liquid solvent evaporation step of evaporating (volatilizing) a part of the solvent from the liquid film 201 of the pretreatment liquid is executed. In the pretreatment liquid solvent evaporation step, the liquid film 201 on the substrate W is heated in order to evaporate a part of the solvent of the pretreatment liquid on the substrate W.
Specifically, as shown in FIG. 6C, the facing member elevating unit 61 moves the facing member 6 to a close position between the upper position and the lower position. The proximity position may be the lower position. The proximity 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.

Then, the gas valve 55 is opened. As a result, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 201) and the facing surface 6a of the facing member 6 (gas supply step).
By spraying the gas onto the liquid film 201 on the substrate W, the evaporation (volatilization) 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 for forming the pretreatment film 200 (see FIG. 7A) can be shortened. The central nozzle 12 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the pretreatment liquid.

Also, the heat medium valve 88 is opened. As a result, the heat medium is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (heat medium supply step, heat medium discharge step). The heat medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W is continued for a predetermined time, for example, 60 seconds. In the pretreatment liquid solvent evaporation step, the substrate W is rotated at a predetermined evaporation rotation speed, for example, 1000 rpm.

By supplying the heat medium to the lower surface of the substrate W, the liquid film 201 on the substrate W is heated via the substrate W. As a result, evaporation (volatilization) 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 for forming the pretreatment film 200 (see FIG. 7A) can be shortened. The bottom surface nozzle 13 functions as an evaporation unit (evaporation promotion unit) that evaporates (volatilizes) the solvent in the pretreatment liquid.

By executing the pretreatment liquid film thinning step and the pretreatment liquid film solvent evaporation step, the pretreatment liquid is solidified or hardened, and the pretreatment film 200 (see FIG. 7A) is formed on the substrate W. .. In this way, the substrate rotation unit (spin motor 23), the central nozzle 12, and the lower surface nozzle 13 solidify or harden the pretreatment liquid to form the pretreatment film 200 (solid film). Forming unit).

In the pretreatment liquid solvent evaporation step, it is preferable that the substrate W is heated so that the temperature of the pretreatment liquid on the substrate W is lower than the boiling point of the solvent. By heating the pretreatment liquid to a temperature lower than the boiling point of the solvent, the solvent can be appropriately left in the pretreatment membrane 200. Therefore, as compared with the case where the solvent does not remain in the pretreatment film 200, the release liquid is more easily blended with the pretreatment film 200 in the subsequent pretreatment film peeling step (step S4).

Next, the pretreatment film peeling step (step S4) for peeling the pretreatment film 200 is executed. Specifically, the heat medium valve 88 is closed. As a result, the supply of the heat medium to the lower surface of the substrate W is stopped. Also, the gas valve 55 is closed. As a result, 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.
Then, the facing member elevating unit 61 moves the facing member 6 to the upper position. The second nozzle moving unit 36 moves the second moving nozzle 10 to the processing position while the facing member 6 is located at the upper position. The processing position of the second moving nozzle 10 is, for example, the central position.

Then, the upper release liquid valve 51 is opened with the second moving nozzle 10 located at the processing position. As a result, as shown in FIG. 6D, the release liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the rotating substrate W (upper release liquid supply step, upper release liquid discharge). Process). The stripping liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W due to centrifugal force. As a result, the pretreatment film (see FIG. 7A) on the upper surface of the substrate W is peeled off, and is discharged to the outside of the substrate W together with the peeling liquid. In the pretreatment film peeling step, the substrate W is rotated at a predetermined pretreatment film peeling rotation speed, for example, 800 rpm.

At the same time that the upper release liquid valve 51 is opened, the lower release liquid valve 87 is opened. As a result, the release liquid is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower release liquid supply step, lower release liquid discharge step). The stripping liquid supplied to the lower surface of the substrate W spreads over the entire lower surface of the substrate W due to centrifugal force.
Here, the pretreatment liquid supplied to the upper surface of the substrate W in the pretreatment liquid supply step (step S2) shown in FIG. 6A may wrap around the lower surface of the substrate W along the peripheral edge of the substrate W. Further, the pretreatment liquid scattered from the substrate W may bounce off the guard 71 and adhere to the lower surface of the substrate W. Even in such a case, as shown in FIG. 6C, since the heat medium is supplied to the lower surface of the substrate W in the pretreatment film forming step, the pretreatment liquid is supplied from the lower surface of the substrate W due to the flow of the heat medium. Can be excluded.

Further, the pretreatment liquid adhering to the lower surface of the substrate W due to the pretreatment liquid supply step (step S2) may solidify or harden to form a solid. As shown in FIG. 6D, while the release liquid is supplied to the upper surface of the substrate W in the pretreatment film peeling step (step S4), the release liquid is supplied (discharged) from the lower surface nozzle 13 to the lower surface of the substrate W. Therefore, even when a solid of the pretreatment liquid is formed on the lower surface of the substrate W, the solid can be peeled off from the lower surface of the substrate W and removed.

After the pretreatment film peeling step (step S4), the stripping liquid removing step (step S5) for removing (rinsing) the stripping liquid from the substrate W is executed by supplying the rinsing liquid. Specifically, the upper release liquid valve 51 and the lower release liquid valve 87 are closed. As a result, the supply of the stripping liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the second nozzle moving unit 36 moves the second moving nozzle 10 to the home position. Then, as shown in FIG. 6E, the facing member elevating unit 61 moves the facing member 6 to the processing position.

Then, the upper rinse liquid valve 53 is opened with the facing member 6 located at the processing position. As a result, the rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region on the upper surface of the rotating substrate W (upper rinse liquid supply step, upper rinse liquid discharge step).
In the stripping liquid removing step, the substrate W is rotated at a predetermined stripping liquid removing rotation speed, for example, 800 rpm. The processing position is a position separated above the upper surface of the substrate W from the proximity 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.

The rinse liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force. As a result, the stripping liquid adhering to the upper surface of the substrate W is washed away with the rinsing liquid (rinsing step).
Further, at the same time that the upper rinse liquid valve 53 is opened, the lower rinse liquid valve 86 is opened. As a result, the rinse liquid is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower rinse liquid supply step, lower rinse liquid discharge step). As a result, the stripping liquid adhering to the lower surface of the substrate W is washed away with the rinsing liquid. The supply of the rinse liquid to the upper surface and the lower surface of the substrate W is continued for a predetermined time, for example, 35 seconds.

After the stripping liquid removing step (step S5), the pretreatment membrane residue removing step (step S6) of removing the residue of the pretreatment film 200 existing on the upper surface of the substrate W with the removing liquid is executed.
Specifically, the upper rinse liquid valve 53 and the lower rinse liquid valve 86 are closed. As a result, the supply of the rinse liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the removal liquid valve 54 is opened while the facing member 6 is maintained at the processing position. As a result, as shown in FIG. 6F, the removal liquid is supplied (discharged) from the central nozzle 12 toward the central region on the upper surface of the rotating substrate W (removal liquid supply step, removal liquid discharge step). The supply of the removing liquid to the upper surface of the substrate W is continued for a predetermined time, for example, 30 seconds. In the pretreatment membrane residue removal step, the substrate W is rotated at a predetermined pretreatment membrane residue removal rotation speed, for example, 300 rpm.

The removing liquid supplied to the upper surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire upper surface of the substrate W. As a result, the rinsing liquid on the upper surface of the substrate W is replaced with the removing liquid. The removing liquid supplied to the upper surface of the substrate W dissolves the residue of the pretreatment film (see FIG. 7A) remaining on the upper surface of the substrate W, and then is discharged from the peripheral edge of the upper surface of the substrate W.
Next, the processing liquid supply step (step S7) of supplying the processing liquid to the upper surface of the substrate W is executed. Specifically, the first nozzle moving unit 35 moves the first moving nozzle 9 to the processing position while the facing member 6 is located at the upper position. The processing position of the first moving nozzle 9 is, for example, the central position. Then, the processing liquid valve 50 is opened. As a result, as shown in FIG. 6G, the processing liquid is supplied (discharged) from the first moving nozzle 9 toward the central region of the upper surface of the rotating substrate W (treatment liquid supply step, treatment liquid discharge step). .. As a result, a liquid film 101 (treatment liquid film) of the treatment liquid is formed on the substrate W (treatment liquid film forming step).

The supply of the treatment liquid from the first moving nozzle 9 is continued for a predetermined time, for example, 2 seconds to 4 seconds. In the treatment liquid supply step, the substrate W is rotated at a predetermined treatment liquid rotation speed, for example, 10 rpm to 1500 rpm.
Next, the treatment film forming step (step S8) is executed. In the treatment film forming step, the treatment liquid on the substrate W is solidified or hardened, and the treatment film 100 (see FIG. 7C described later) holding the removal target 103 existing on the substrate W is formed on the upper surface of the substrate W. Will be done.

In the treatment film forming step, first, a treatment liquid thinning step (treatment liquid spin-off step) of reducing the thickness of the liquid film 101 of the treatment liquid on the substrate W is executed. Specifically, the treatment liquid valve 50 is closed. As a result, the supply of the processing liquid to the substrate W is stopped. Then, the first moving nozzle 9 is moved to the home position by the first nozzle moving unit 35.
As shown in FIG. 6H, in the treatment liquid thinning step, the supply of the treatment 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. A part of the treatment liquid is removed from the upper surface of the substrate W by centrifugal force. Even after the first moving nozzle 9 moves to the home position, the opposing member 6 is maintained in the upper position.

In the treatment liquid thinning step, the spin motor 23 changes the rotation speed of the substrate W to a predetermined treatment liquid thinning speed. The treatment liquid thinning rate is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W may be kept constant within the range of 300 rpm to 1500 rpm, or may be appropriately changed within the range of 300 rpm to 1500 rpm during the process liquid thinning step. The treatment liquid thinning step is executed for a predetermined time, for example, 30 seconds.

In the treatment film forming step, after the treatment liquid thinning step, a treatment liquid solvent evaporation step of evaporating (volatilizing) a part of the solvent from the liquid film 101 of the treatment liquid is executed. In the treatment liquid solvent evaporation step, the liquid film 101 on the substrate W is heated in order to evaporate a part of the solvent of the treatment liquid on the substrate W.
Specifically, as shown in FIG. 6I, the opposing member elevating unit 61 moves the opposing member 6 to a close position.

Then, the gas valve 55 is opened. As a result, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 101) and the facing surface 6a of the facing member 6 (gas supply step).
By spraying the gas onto the liquid film 101 on the substrate W, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (treatment liquid solvent evaporation step, treatment liquid solvent evaporation promotion step). Therefore, the time required for forming the treated membrane 100 (see FIG. 7C) can be shortened. Also in the treatment film forming step, the central nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the treatment liquid.

Also, the heat medium valve 88 is opened. As a result, the heat medium is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (heat medium supply step, heat medium discharge step). The heat medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W is continued for a predetermined time, for example, 60 seconds. In the treatment liquid solvent evaporation step, the substrate W is rotated at a predetermined evaporation rotation speed, for example, 1000 rpm.

By supplying the heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated via the substrate W. As a result, evaporation (volatilization) of the solvent in the liquid film 101 is promoted (treatment liquid solvent evaporation step, treatment liquid solvent evaporation promotion step). Therefore, the time required for forming the treated membrane 100 (see FIG. 7C) can be shortened. Also in the treatment film forming step, the lower surface nozzle 13 functions as an evaporation unit (evaporation promotion unit) for evaporating (volatilizing) the solvent in the treatment liquid.

The treatment liquid is solidified or hardened by executing the treatment liquid thinning step and the treatment liquid solvent evaporation step. As a result, the processing film 100 that holds the object to be removed 103 is formed on the entire upper surface of the substrate W. In this way, the substrate rotation unit (spin motor 23), the central nozzle 12, and the lower surface nozzle 13 solidify or harden the treatment liquid to form the treatment film 100 (solid film). Consists of.

In the treatment liquid solvent evaporation step, it is preferable that the substrate W is heated so that the temperature of the treatment liquid on the substrate W is lower than the boiling point of the solvent. By heating the treatment liquid to a temperature lower than the boiling point of the solvent, the solvent can be appropriately left in the treatment membrane 100. As a result, in the subsequent treatment film peeling step (step S9), the peeling liquid can be easily applied to the treatment film 100 as compared with the case where the solvent does not remain in the treatment film 100.

Next, the treatment film peeling step (step S9) of peeling the treatment film 100 with the peeling liquid is executed. Specifically, the heat medium valve 88 is closed. As a result, the supply of the heat medium to the lower surface of the substrate W is stopped. Also, the gas valve 55 is closed. As a result, 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.
Then, the facing member elevating unit 61 moves the facing member 6 to the upper position. The second nozzle moving unit 36 moves the second moving nozzle 10 to the processing position while the facing member 6 is located at the upper position.

Then, the upper release liquid valve 51 is opened with the second moving nozzle 10 located at the processing position. As a result, as shown in FIG. 6J, the release liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the rotating substrate W (upper release liquid supply step, upper release liquid discharge). Process). The stripping liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W due to centrifugal force. As a result, the pretreatment film on the upper surface of the substrate W is peeled off, and the pretreatment film is discharged to the outside of the substrate W together with the peeling liquid. In the treatment film peeling step, the substrate W is rotated at a predetermined treatment film peeling rotation speed, for example, 800 rpm.

At the same time that the upper release liquid valve 51 is opened, the lower release liquid valve 87 is opened. As a result, the release liquid is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower release liquid supply step, lower release liquid discharge step). The stripping liquid supplied to the lower surface of the substrate W spreads over the entire lower surface of the substrate W due to centrifugal force.
Here, for the same reason as the pretreatment liquid supply step shown in FIG. 6A, the treatment liquid may adhere to the lower surface of the substrate W in the treatment liquid supply step (step S7) shown in FIG. 6G. Even in such a case, as shown in FIG. 6I, 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.

Further, similarly to the pretreatment liquid, the treatment liquid adhering to the lower surface of the substrate W due to the treatment liquid supply step (step S7) may form a solid. Even in such a case, as shown in FIG. 6J, since the stripping liquid is supplied (discharged) to the lower surface of the substrate W, the solid can be peeled off from the lower surface of the substrate W and removed.
Then, after the treatment film peeling step (step S9), the peeling liquid removing step (step S10) for removing (rinsing) the stripping liquid from the substrate W is executed by supplying the rinsing liquid. Specifically, the upper release liquid valve 51 and the lower release liquid valve 87 are closed. As a result, the supply of the stripping liquid to the upper surface and the lower surface of the substrate W is stopped. Then, the second nozzle moving unit 36 moves the second moving nozzle 10 to the home position. Then, as shown in FIG. 6K, the facing member elevating unit 61 moves the facing member 6 to the processing position.

Then, the upper rinse liquid valve 53 is opened with the facing member 6 located at the processing position. As a result, the rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region on the upper surface of the rotating substrate W (upper rinse liquid supply step, upper rinse liquid discharge step).
In the stripping liquid removing step, the substrate W is rotated at a predetermined stripping liquid removing rotation speed, for example, 800 rpm. The processing position is a position separated above the upper surface of the substrate W from the proximity position. The rinse liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force. As a result, the stripping liquid adhering to the upper surface of the substrate W is washed away with the rinsing liquid (rinsing step).

Further, at the same time that the upper rinse liquid valve 53 is opened, the lower rinse liquid valve 86 is opened. As a result, the rinse liquid is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower rinse liquid supply step, lower rinse liquid discharge step). As a result, the stripping liquid adhering to the lower surface of the substrate W is washed away with the rinsing liquid. The supply of the rinse liquid to the upper surface and the lower surface of the substrate W is continued for a predetermined time, for example, 35 seconds.

Next, after the stripping liquid removing step (step S10), the treated membrane residue removing step (step S11) of removing the residue of the treated membrane 100 existing on the upper surface of the substrate W with the removing liquid is executed. Specifically, the upper rinse liquid valve 53 and the lower rinse liquid valve 86 are closed. As a result, the supply of the rinse liquid to the upper surface and the lower surface of the substrate W is stopped.
Then, the removal liquid valve 54 is opened with the facing member 6 located at the processing position. As a result, as shown in FIG. 6L, the removal liquid is supplied (discharged) from the central nozzle 12 toward the central region on the upper surface of the rotating substrate W (removal liquid supply step, removal liquid discharge step). The supply of the removing liquid to the upper surface of the substrate W is continued for a predetermined time, for example, 30 seconds. In the treated membrane residue removing step, the substrate W is rotated at a predetermined treated membrane residue removing rotation speed, for example, 300 rpm.

The removing liquid supplied to the upper surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire upper surface of the substrate W. As a result, the rinsing liquid on the upper surface of the substrate W is replaced with the removing liquid. The removing liquid supplied to the upper surface of the substrate W dissolves the residue of the treatment film 100 remaining on the upper surface of the substrate W, and then is discharged from the peripheral edge of the upper surface of the substrate W.
Next, a spin-drying step (step S12) of rotating the substrate W at high speed to dry the upper surface of the substrate W is executed. Specifically, the removal liquid valve 54 is closed. As a result, the supply of the removing liquid to the upper surface of the substrate W is stopped. Then, as shown in FIG. 6M, the facing member elevating unit 61 moves the facing member 6 to a drying position below the processing position. When the facing member 6 is located in the dry position, the distance between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 55 is opened. As a result, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

Then, the spin motor 23 accelerates the rotation of the substrate W to rotate the substrate W at high speed. The substrate W in the spin drying step is rotated at a drying rate, for example, 1500 rpm. The spin-drying step is performed for a predetermined time, for example 30 seconds. As a result, a large centrifugal force acts on the removing liquid on the substrate W, and the removing liquid on the substrate W is shaken off around the substrate W. In the spin-drying step, the evaporation of the removing liquid is promoted by supplying gas to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

Then, the spin motor 23 stops the rotation of the substrate W. The guard elevating unit 74 moves the first guard 71A and the second guard 71B to the lower position. The gas valve 55 is closed. Then, the facing member elevating unit 61 moves the facing member 6 to the upper position.
The transfer robot CR enters the processing unit 2, scoops the processed substrate W from the chuck pin 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S13). The substrate W is passed from the transfer robot CR to the transfer robot IR, and is housed in the carrier C by the transfer robot IR.

In this spin-drying step of substrate processing, the rinse liquid such as DIW on the substrate W is shaken off, so that the upper surface of the substrate W is not dried, but the rinse liquid on the substrate W is replaced by a removal liquid such as IPA. After that, the upper surface of the substrate W is dried by shaking off the removing liquid on the substrate W. That is, since the spin-drying step is executed after being replaced by IPA having a lower surface tension than DIW, it acts on the uneven pattern 160 (see FIG. 2) on the upper surface of the substrate W when the upper surface of the substrate W is dried. The surface tension to be applied can be reduced.

Next, the state near the upper surface of the substrate W during the substrate processing will be described. 7A to 7E are schematic views for explaining a state near the upper surface of the substrate W during substrate processing.
FIG. 7A is a schematic view for explaining a state near the upper surface of the substrate W in a state where the pretreatment film 200 is formed by executing the pretreatment film forming step (step S3). As shown in FIG. 7A, the pretreatment film 200 holds the object to be removed 103.

When the release liquid is supplied to the upper surface of the substrate W on which the pretreatment film 200 is formed, as shown in FIG. 7B, the pretreatment film 200 is removed from the upper surface of the substrate W together with the object 103 to be removed by the release action of the release liquid. It will be peeled off. When the pretreated film 200 is peeled off from the upper surface of the substrate W, it splits into a film piece 205.
Then, after the peeling of the pretreatment film 200, the supply of the peeling liquid to the upper surface of the substrate W is continued, so that the divided film piece 205 of the pretreatment film 200 is excluded from the substrate W together with the peeling liquid. As a result, the film piece 205 of the pretreatment film 200 in the state of holding the object to be removed 103 is removed from the upper surface of the substrate W.

As described above, the pretreated film 200 has a relatively high removing power (compared to the treated film 100) for removing the removal target 103 existing in the exposed region 170.
Therefore, as shown in FIG. 7B, the majority of the objects to be removed 103 can be removed from the exposed region 170 by the pretreatment film peeling step (step S4). On the other hand, the pretreated film 200 has a relatively low removing force (compared to the treated film 100) for removing the removal target 103 existing in the unexposed region 171. Therefore, the object to be removed 103 that could not be removed by the pretreatment film 200 may remain in the non-exposed area 171.

After that, as shown in FIG. 7C, the treatment film 100 holding the object to be removed 103 is formed. Since the treatment film 100 has a higher removal target object holding force for holding the removal target object 103 existing in the non-exposed region 171 than the pretreatment film 200, the treatment film 100 can hold the removal target object 103. When the release liquid is supplied to the upper surface of the substrate W on which the treatment film 100 is formed, as shown in FIG. 7D, the treatment film 100 is separated from the upper surface of the substrate W together with the object to be removed 103 by the release action of the release liquid. To. When the treated film 100 is peeled off from the upper surface of the substrate W, it splits into a film piece 105.

The treated film 100 has a high removing power for removing the removal target 103 existing in the unexposed region 171. Therefore, in the pretreatment film peeling step (step S4), even when the removal target 103 that could not be removed by the pretreatment film 200 is present on the unexposed region 171 (see FIG. 7B), the treatment film peeling is performed. By executing the step (step S9), the object to be removed 103 can be removed from the substrate W.

Even after the treatment film 100 is peeled off with the peeling liquid in the treatment film peeling step (step S9), as shown in FIG. 7D, the portion of the treatment film 100 that covers the exposed region 170 (exposed region covering portion 130) remains as a residue. It remains on the exposed area 170. The exposed region covering portion 130 is dissolved by the removing liquid supplied to the upper surface of the substrate W in the subsequent treatment film residue removing step (step S11), and is removed from the upper surface of the substrate W as shown in FIG. 7E.

Next, the state of peeling of the pretreatment film 200 will be described with reference to FIGS. 8A to 8C.
As shown in FIG. 8A, the pretreatment film 200 holds the object to be removed 103. Specifically, the pretreatment membrane 200 has a highly soluble solid 210 (a second highly soluble component in a solid state) and a poorly soluble solid 211 (a second poorly soluble component in a solid state). The highly soluble solid 210 and the low soluble solid 211 are formed by evaporation of at least a portion of the solvent contained in the pretreatment solution.

In the pretreatment membrane 200, the highly soluble solid 210 and the poorly soluble solid 211 are mixed in a single layer. Strictly speaking, in the pretreatment film 200, the highly soluble solid 110 and the low solubility solid 111 are not uniformly distributed throughout the pretreatment film 200, and the highly soluble solid 210 is unevenly distributed. There is a portion and a portion where the low-solubility solid 211 is unevenly distributed.
The pretreatment film 200 has a structure in which the pretreatment film 200 is mixed in a single layer regardless of the region (location) where the pretreatment film 200 is formed on the upper surface of the substrate W. In other words, the pretreatment film 200 has a structure mixed in a single layer in any region of the exposed region 170 and the unexposed region 171.

With reference to FIG. 8B, the highly soluble solid 210 is dissolved due to the supply of stripping liquid. That is, the pretreatment membrane 200 is partially dissolved. By dissolving the highly soluble solid 210, through holes 202 are formed in the portion of the pretreatment membrane 200 where the highly soluble solid 210 is unevenly distributed.
The through hole 202 is particularly likely to be formed in a portion of the pattern surface 165 in which the highly soluble solid 210 extends in the normal direction T (which is also the thickness direction of the treated film 100). The through hole 202 has a size of, for example, several nm in diameter in a plan view.

The solubility of the low-solubility component in the stripping solution is low, and the low-solubility solid 211 is hardly dissolved by the stripping solution. Therefore, the low-solubility solid 211 is only slightly dissolved in the vicinity of its surface by the stripping solution. Therefore, the stripping liquid that reaches the vicinity of the upper surface (pattern surface 165) of the substrate W through the through hole 202 slightly dissolves the portion of the low-solubility solid 211 near the upper surface of the substrate W. As a result, as shown in the enlarged view of FIG. 8B, the release liquid gradually dissolves the low-solubility solid 211 near the upper surface of the substrate W, and the gap G2 between the pretreatment film 200 and the upper surface of the substrate W (Peeling liquid entry process).

Then, for example, the pretreatment film 200 splits into a film piece 205 starting from the peripheral edge of the through hole 202, and as shown in FIG. 8C, the film piece 205 of the pretreatment film 200 holds the object to be removed 103. It is peeled from the substrate W in this state (pretreatment membrane splitting step, peeling step). Then, by continuing to supply the stripping liquid, the pretreated film 200 that has become the film piece 205 is washed away (pushed out of the substrate W) while holding the object 103 to be removed, and the substrate W It is removed from the upper surface of the (removal object removal step).

The state of peeling of the treated film 100 will be described in detail with reference to FIGS. 9A to 9C. 9A to 9C are schematic views for explaining how the portion of the treated film 100 that covers the non-exposed region 171 (non-exposed region covering portion 131) is peeled off from the non-exposed region 171.
As shown in FIG. 9A, the treated film 100 holds the object to be removed 103. Specifically, the portion of the treated membrane 100 that covers the non-exposed region 171 is a highly soluble solid 110 (first highly soluble component in a solid state) and a poorly soluble solid 111 (first poorly soluble component in a solid state). ) And. The highly soluble solid 110 and the low soluble solid 111 are formed by evaporating at least a part of the solvent contained in the treatment solution.

In the non-exposed region covering portion 131, the highly soluble solid 110 and the low soluble solid 111 are mixed in a single layer. Strictly speaking, in the non-exposed region covering portion 131, the highly soluble solid 110 and the low solubility solid 111 are not uniformly distributed over the entire treated film 100, and the highly soluble solid 110 is unevenly distributed. There is a portion where the low-solubility solid 111 is unevenly distributed and a portion where the low-solubility solid 111 is unevenly distributed.

With reference to FIG. 9B, the highly soluble solid 110 is dissolved due to the supply of stripping liquid. That is, the unexposed region covering portion 131 is partially dissolved. By dissolving the highly soluble solid 110, a through hole 102 is formed in a portion of the non-exposed region covering portion 131 in which the highly soluble solid 110 is unevenly distributed (through hole forming step).
The through hole 102 is particularly likely to be formed in a portion of the pattern surface 165 in which the highly soluble solid 110 extends in the normal direction T (which is also the thickness direction of the treated film 100). The through hole 102 has a size of, for example, several nm in diameter in a plan view.

The solubility of the low-solubility component in the stripping solution is low, and the low-solubility solid 111 is hardly dissolved by the stripping solution. Therefore, the low-solubility solid 111 is only slightly dissolved in the vicinity of its surface by the stripping solution. Therefore, the stripping liquid that has reached the vicinity of the upper surface of the substrate W through the through hole 102 slightly dissolves the portion of the low-solubility solid 111 near the upper surface of the substrate W. As a result, as shown in the enlarged view of FIG. 9B, the release liquid gradually dissolves the low-solubility solid 111 near the upper surface of the substrate W, and between the unexposed region covering portion 131 and the upper surface of the substrate W. It enters the gap G1 (release liquid entry step).

Then, for example, the non-exposed region covering portion 131 splits into a film piece 105 starting from the peripheral edge of the through hole 102, and as shown in FIG. 9C, the film piece 105 of the non-exposed region covering portion 131 removes the object 103 to be removed. It is peeled from the substrate W while being held (processed membrane splitting step, peeling step). Then, by continuing to supply the stripping liquid, the unexposed region covering portion 131 that has become the film piece 105 is washed away (pushed out of the substrate W) while holding the object to be removed 103. It is removed from the upper surface of the substrate W (removal object removal step).

With reference to FIGS. 9A to 9C, the step of partially melting the unexposed region covering portion 131 of the treated film 100 to form the through hole 102 is an example of the first through hole forming step, and is formed by this step. The through hole 102 is an example of the first through hole. Further, referring to FIGS. 8A to 8C, the step of partially melting the pretreatment film 200 to form the through hole 202 is an example of the second through hole forming step, and the through hole formed by this is an example. 202 is an example of the second through hole.

Next, the state of removal of the exposed region covering portion 130 that covers the exposed region 170 will be described in detail with reference to FIGS. 10A to 10C. 10A to 10C are schematic views for explaining how the exposed region covering portion 130 is removed from the upper surface of the substrate W.
As described above, the majority of the objects to be removed 103 are removed from the exposed region 170 by the pretreatment film peeling step (step S4), but the objects 103 to be removed are also exposed when the treatment film 100 is formed. It may be slightly present in region 170.

The exposed region covering portion 130 has a highly soluble solid 110 (the first highly soluble component in the solid state) and a low soluble solid 111 (the first poorly soluble component in the solid state). The highly soluble solid 110 and the low soluble solid 111 are formed by evaporating at least a part of the solvent contained in the treatment solution.
The exposed region covering portion 130 is arranged at a position in contact with the metal film 163 and is arranged on the opposite side of the metal film 163 with respect to the low solubility layer 180 made of the low solubility solid 111 and the low solubility layer 180 and is highly soluble. It has a highly soluble layer 181 made of the sex solid 110. That is, the low-solubility layer 180 is located between the metal film 163 and the high-solubility layer 181.

The highly soluble solid 110 is dissolved in the stripping solution, but the low soluble solid 111 is hardly dissolved in the stripping solution. Therefore, when the stripping solution is supplied to the upper surface of the substrate W in the treatment film stripping step (step S9), the highly soluble layer 181 is dissolved by the stripping solution as shown in FIG. 10B. On the other hand, the low-solubility layer 180 is maintained in a state of covering the exposed region 170 without exposing the metal film 163, although the surface thereof is slightly dissolved. Therefore, it is difficult for the release liquid 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 remains on the exposed region 170 without being peeled off by the stripping solution. Therefore, the treated film 100 has lower peelability than the pretreated film 200 in the exposed region 170.

The object to be removed 103 adhering to the exposed region 170 is separated from the exposed region 170 when the treatment film 100 is formed. In the treatment film residue removing step (step S8), the exposed region covering portion 130 is dissolved in the removing liquid. When the exposed region covering portion 130 is dissolved by the removing liquid, as shown in FIG. 10C, the removal target object 103 floats in the removing liquid in a state of being separated from the exposed region 170. Therefore, by continuing to supply the removal liquid, the removal target 103 floating in the removal liquid is removed from the upper surface of the substrate W together with the removal liquid.

According to the first embodiment, the removal target 103 is removed from the upper surface of the substrate W by peeling the pretreatment film 200 having a high removing power for removing the removal target 103 existing in the exposed region 170 (first region). To. After that, the removal target 103 is removed from the upper surface of the substrate W by peeling the treatment film 100 having a high removing power for removing the removal target 103 existing in the non-exposed region 171 (second region). That is, the peeling of the pretreatment film 200 having a relatively high removing power for removing the removal target object 103 existing in the exposed region 170 and the treatment having a relatively high removing power for removing the removal target object 103 existing in the non-exposed area 171. Both peeling of the film 100 is performed. More simply, the removal of the object to be removed 103 is performed in two steps by using the pretreatment film 200 and the treatment film 100 in which the regions having high removing power for removing the object to be removed 103 are different from each other.

Therefore, the object to be removed 103 can be efficiently removed from the substrate W having a surface on which the exposed region 170 where the metal film 163 is exposed and the other non-exposed region 171 are present.
Further, according to the first embodiment, after the treatment film peeling step (step S9), the removal liquid is supplied to the upper surface of the substrate W to remove the residue of the treatment film 100 remaining on the upper surface of the substrate W. The removal step (step S11) is executed. Therefore, even if the residue of the treatment film 100 adheres to the exposed region 170 and the non-exposed region 171 after the treatment film 100 is peeled off by the release liquid, the residue can be removed by the removal liquid. ..

Further, according to the first embodiment, in the treatment film peeling step, the non-exposed region covering portion 131 is peeled off without peeling the exposed region covering portion 130. Then, in the treatment film residue removing step, the exposed region covering portion 130 is removed as a residue of the treatment film 100.
Therefore, even if the exposed region covering portion 130 remains on the exposed region 170 without being peeled off by the supply of the peeling liquid to the upper surface of the substrate W, the exposed region covering portion 130 is dissolved in the removing liquid to dissolve the exposed region covering portion 130 in the removing liquid to expose the exposed region 170. Can be removed from.

When the exposed region covering portion 130 of the treatment film 100 is dissolved in the removing liquid, the removal target 103 released from the holding by the exposed region covering portion 130 may reattach to the exposed region 170. According to the first embodiment, the treatment film 100 is formed after the pretreatment film 200 having a relatively high removing power for removing the removal target 103 existing in the exposed region 170 is removed from the exposed region 170 by peeling. .. Therefore, most of the objects to be removed 103 are removed from the exposed region 170 before the treated film 100 is formed.

Therefore, even if the exposed region covering portion 130 is dissolved in the removing liquid to remove the exposed region covering portion 130 from the exposed region 170, it is possible to sufficiently suppress the remaining object 103 to be removed in the exposed region 170. Can be done.
Further, according to the first embodiment, the highly soluble solid 110 and the low soluble solid 111 are mixed in a single layer in the non-exposed region covering portion 131 of the treated film 100. Then, in the treatment film peeling step (step S9), the highly soluble solid 110 is selectively dissolved in the stripping liquid.

By dissolving the highly soluble solid 110 in the stripping solution, the stripping solution passes through the non-exposed region covering portion 131 of the treatment film 100 through the trace (through hole 102) where the highly soluble solid 110 was present. .. As a result, it is possible to quickly reach the vicinity of the interface between the treated film 100 and the non-exposed region 171 on the surface of the substrate W.
On the other hand, the low-solubility solid 111 in the non-exposed region covering portion 131 is maintained in a solid state without being dissolved. Therefore, the stripping solution can act on the contact interface between the low-solubility solid 111 and the substrate W while holding the object to be removed 103 with the low-solubility solid 111. As a result, the non-exposed region covering portion 131 can be quickly removed from the upper surface of the substrate W, and the object to be removed 103 together with the non-exposed region covering portion 131 of the treated film 100 can be efficiently removed from the upper surface of the substrate W.

Further, according to the first embodiment, the highly soluble solid 110 and the low soluble solid 111 are mixed in the pretreated membrane 200. The highly soluble solid 210 in the pretreatment membrane 200 is selectively dissolved in the stripping solution. By dissolving the highly soluble solid 210 in the stripping solution, the stripping solution passes through the pretreatment membrane 200 through the trace (through hole 202) where the highly soluble solid 210 was present. As a result, it is possible to quickly reach the vicinity of the interface between the pretreatment film 200 and the upper surface of the substrate W.

On the other hand, the low-solubility solid 211 in the pretreatment membrane 200 is maintained in a solid state without being dissolved. Therefore, the stripping solution can be allowed to act on the contact interface between the low-solubility solid 211 and the substrate W while holding the object 103 to be removed by the low-solubility solid 211. As a result, the pretreatment film 200 can be quickly removed from the upper surface of the substrate W, and the object to be removed 103 together with the pretreatment film 200 can be efficiently removed from the upper surface of the substrate W.

"The highly soluble solids 110 and 210 are selectively dissolved" does not mean that only the highly soluble solids 110 and 210 are dissolved. "The highly soluble solids 110 and 210 are selectively dissolved" means that the low solubility solids 111 and 211 are also slightly dissolved, but most of the highly soluble solids 110 and 210 are dissolved. Is.
Further, the metal film 163 whose surface is exposed in the exposed region 170 is not limited to the 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. Further, the film whose surface is exposed in the exposed region 170 does not have to be the metal film 163, and may be, for example, a nitride film such as a silicon nitride film or a titanium nitride film. Even when the substrate treatment according to the above-described 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 effect as that of the above-described embodiment is obtained.

<Second Embodiment>
FIG. 11 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit 2 provided in the substrate processing apparatus 1P according to the second embodiment. In FIG. 11, a configuration equivalent to the configuration shown in FIGS. 1 to 10C described above is designated by the same reference reference numerals as those in FIG. 1 and the like, and the description thereof will be omitted. Similarly, in FIGS. 12 to 15E described later, the same reference numerals as those in FIGS. 1 and the like are added and the description thereof will be omitted.

With reference to FIG. 11, the substrate processing apparatus 1P according to the second embodiment is mainly different from the substrate processing apparatus 1 according to the first embodiment (see FIG. 3) in that the substrate processing apparatus according to the second embodiment is mainly different. In 1P, the substrate W that has been subjected to the dry etching treatment is subjected to the substrate treatment.
FIG. 12 is an example of a cross-sectional view of the surface layer of the substrate W processed by the substrate processing apparatus 1P. On the substrate W, the first removal target object 203 is attached to both the unexposed area 171 and the exposed area 170. The first object to be removed 203 is a residue generated by the dry etching process in the previous step. The first object to be removed 203 is a granular residue (granular residue). It is a reaction product of an etching gas such _{as CF x} (for example, carbon tetrafluoride (CF ₄ )) used in the dry etching process and the structure 161.

The second removal object 104 is attached to the non-exposed area 171. The second object to be removed 104 is also a residue of the dry etching process. The second object to be removed 104 is a film-like residue (film-like residue) that covers at least a part of the unexposed area 171. In the example of FIG. 12, the second removal object 204 covers the surface of the low dielectric constant interlayer insulating film 161B. The second object to be removed 104 is a reaction product of the etching gas and the low dielectric constant interlayer insulating film 161B.

With reference to FIG. 11, the processing unit 2 according to the second embodiment includes a fourth moving nozzle 14. The fourth moving nozzle 14 is an example of a cleaning liquid nozzle (cleaning liquid supply unit) that supplies (discharges) a cleaning liquid such as SC1 in a continuous flow toward the upper surface of the substrate W held by the spin chuck 5. The cleaning liquid is a liquid for dissolving the second object to be removed 204, which cannot be peeled from the upper surface of the substrate W with the peeling liquid, and removing it from the upper surface of the substrate W.

The fourth moving nozzle 14 is moved in the horizontal direction and the vertical direction by the fourth nozzle moving unit 38. The fourth moving nozzle 14 can move between the center position and the home position (retracted position) in the horizontal direction.
When the fourth moving nozzle 14 is located at the center position, it faces the rotation center of the upper surface of the substrate W. When the fourth moving nozzle 14 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The fourth moving nozzle 14 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

The fourth nozzle moving unit 38 has the same configuration as the first nozzle moving unit 35. That is, the fourth nozzle moving unit 38 has, for example, an arm (not shown) coupled to the fourth moving nozzle 14 and extending horizontally, and a rotating shaft (not shown) coupled to the arm and extending in the vertical direction. And a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

The fourth moving nozzle 14 is connected to a cleaning liquid pipe 46 that guides the cleaning liquid to the fourth moving nozzle 14. When the cleaning liquid valve 56 interposed in the cleaning liquid pipe 46 is opened, the cleaning liquid is discharged downward from the discharge port of the fourth moving nozzle 14 in a continuous flow.
The cleaning liquid discharged from the fourth moving nozzle 14 is preferably a liquid having a higher oxidizing power than the stripping liquid. The cleaning liquid discharged from the fourth moving nozzle 14 is not limited to SC1, and _{may be hydrofluoric acid or diluted ammonia water (dNH 4} OH).

FIG. 13 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus 1P according to the second embodiment. 14A and 14B are schematic views for explaining the state of each process of substrate processing by the substrate processing apparatus 1P.
In the substrate processing by the substrate processing apparatus 1P, the substrate W after the dry etching process is used. As shown in FIG. 13, in the substrate processing by the substrate processing apparatus 1P, unlike the substrate processing by the substrate processing apparatus 1 (see FIG. 5), the stripping liquid removing step (step S10) and the treated film residue removing step (step S11). ), A cleaning step (step S20) and a cleaning liquid removing step (step S21) are executed.

The cleaning step (step S20) is a step of removing the second removal object 204 adhering to the upper surface of the substrate W and cleaning the upper surface of the substrate W. The cleaning liquid removing step (step S21) is a step of removing (rinsing) the cleaning liquid from the upper surface of the substrate W by supplying the rinsing liquid.
Hereinafter, the cleaning step (step S20) and the cleaning liquid removing step (step S21) will be described in detail.

After the upper rinse liquid valve 53 and the lower rinse liquid valve 86 are closed in order to stop the supply of the rinse liquid in the stripping liquid removing step (step S10), the facing member elevating unit 61 moves the facing member 6 to the upper position. Move. The fourth nozzle moving unit 38 moves the fourth moving nozzle 14 to the processing position while the facing member 6 is located at the upper position. The processing position of the fourth moving nozzle 14 is, for example, the central position.

Then, the cleaning liquid valve 56 is opened with the fourth moving nozzle 14 located at the processing position. As a result, as shown in FIG. 14A, the cleaning liquid is supplied (discharged) from the fourth moving nozzle 14 toward the central region of the upper surface of the rotating substrate W (cleaning liquid supply step, cleaning liquid discharge step). The cleaning liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force. In the cleaning step, 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 washing rotation speed is preferably 800 rpm.

The cleaning liquid supplied to the upper surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire upper surface of the substrate W. As a result, the rinsing liquid on the upper surface of the substrate W is replaced with the cleaning liquid.
After the cleaning step (step S20), the cleaning liquid removing step (step S21) is executed. Specifically, the cleaning liquid valve 56 is closed. As a result, the supply of the cleaning liquid to the upper surface of the substrate W is stopped. Then, the 4th nozzle moving unit 38 moves the 4th moving nozzle 14 to the home position. Then, as shown in FIG. 14B, the facing member elevating unit 61 moves the facing member 6 to the processing position.

Then, the upper rinse liquid valve 53 is opened with the facing member 6 located at the processing position. As a result, the rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region on the upper surface of the rotating substrate W (upper rinse liquid supply step, upper rinse liquid discharge step). In the cleaning liquid removing step, the substrate W is rotated at a predetermined cleaning liquid removing rotational rotation speed, for example, 800 rpm.

The rinse liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force. As a result, the cleaning liquid adhering to the upper surface of the substrate W is washed away with the rinsing liquid.
Further, at the same time that the upper rinse liquid valve 53 is opened, the lower rinse liquid valve 86 is opened. As a result, the rinse liquid is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower rinse liquid supply step, lower rinse liquid discharge step). As a result, even when the cleaning liquid wraps around from the upper surface of the substrate W to the lower surface of the substrate W and the cleaning liquid adheres to the lower surface of the substrate W, the cleaning liquid adhering to the lower surface of the substrate W is washed away with the rinsing liquid. The supply of the rinse liquid to the upper surface and the lower surface of the substrate W is continued for a predetermined time, for example, 35 seconds.

15A to 15E are schematic views for explaining a state near the upper surface of the substrate W during substrate processing by the substrate processing apparatus 1P.
FIG. 15A is a schematic view for explaining a state near the upper surface of the substrate W in a state where the pretreatment film 200 is formed by executing the pretreatment film forming step (step S3). As shown in 15A, the pretreatment film 200 holds the first removal target object 203.

When the stripping liquid is supplied to the upper surface of the substrate W on which the pretreatment film 200 is formed, as shown in FIG. 15B, the pretreatment film 200 is separated from the substrate W together with the first removal target 203 by the peeling action of the stripping liquid. It is peeled off from the top surface. When the pretreated film 200 is peeled off from the upper surface of the substrate W, it splits into a film piece 205.
Then, after the peeling of the pretreatment film 200, the supply of the peeling liquid to the upper surface of the substrate W is continued, so that the divided film piece 205 of the pretreatment film 200 is excluded from the substrate W together with the peeling liquid. As a result, the film piece 205 of the pretreatment film 200 in the state of holding the first removal object 203 is removed from the upper surface of the substrate W.

The removal power, the removal target holding power, and the peelability of the polymer film with respect to the first removal target 203 existing in the target region (exposed area 170 or non-exposed region 171) are the removal targets described in the first embodiment, respectively. It is the same as the removing power of the polymer film, the holding power of the object to be removed, and the peelability of the object 103.
Therefore, the pretreated film 200 exhibits high retention of objects to be removed in both the unexposed area 171 and the exposed area 170, whereas the treated film 100 exhibits the pretreated film 200 in both the unexposed area 171 and the exposed area 170. Demonstrates even higher holding power for objects to be removed. On the other hand, the pretreated film 200 has higher peelability than the treated film 100 in the exposed region 170.

Therefore, the removing force for the treatment film 100 to remove the first removal object 203 existing in the non-exposed area 171 is larger than the removing force for the pretreatment film 200 to remove the first removal object 203 existing in the non-exposed area 171. Is also expensive. The removing force for the pretreatment film 200 to remove the first removal object 203 existing in the exposed region 170 is higher than the removing power for the treatment film 100 to remove the first removal object 203 existing in the exposed region 170.

Therefore, as shown in FIG. 15B, the majority of the first removal target 203 can be removed from the exposed region 170 by the pretreatment film peeling step (step S4). On the other hand, the pretreated film 200 has a relatively low removing force (compared to the treated film 100) for removing the first removal object 203 existing in the unexposed region 171. Therefore, the first removal target object 203 that could not be held by the pretreatment film 200 with sufficient holding force for the removal target object may remain in the non-exposed region 171. The second object to be removed 204 is not peeled together with the pretreatment film 200 and is not dissolved by the peeling liquid, so that it remains in the unexposed region 171 on the upper surface of the substrate W.

After that, as shown in FIG. 15C, the treatment film 100 holding the first removal object 203 is formed. Since the treatment film 100 has a higher removal target object holding force for holding the first removal target object 203 existing in the non-exposed region 171 than the pretreatment film 200, the treatment film 100 can hold the first removal target object 203. When the release liquid is supplied to the upper surface of the substrate W on which the treatment film 100 is formed, as shown in FIG. 15D, the treatment film 100 is removed from the upper surface of the substrate W together with the first removal object 203 due to the release action of the release liquid. It will be peeled off. When the treated film 100 is peeled off from the upper surface of the substrate W, it splits into a film piece 105.

In the treated film 100, the non-exposed region covering portion 131 that covers the non-exposed region 171 is peeled off by the release liquid. On the other hand, as shown in FIG. 15D, the exposed region covering portion 130 remains on the exposed region 170 as a residue. That is, the non-exposed region covering portion 131 functions as a peeling target film to be peeled by the peeling liquid.
The treated film 100 has a high removing power for removing the first removal target object 203 existing in the non-exposed region 171. Therefore, in the pretreatment film peeling step (step S4), even if the first removal target object 203 that could not be removed by the pretreatment film 200 is present on the unexposed region 171 (see FIG. 15B), the treatment is performed. By executing the film peeling step (step S9), the first removal object 203 can be removed from the substrate W. The second object to be removed 204 is not peeled together with the pretreatment film 200 and is not dissolved by the peeling liquid, so that it remains in the unexposed region 171 on the upper surface of the substrate W.

By supplying the cleaning liquid to the upper surface of the substrate W in the subsequent cleaning step (step S20), the second object to be removed 204 is dissolved as shown in FIG. 15E. Since the metal film 163 is covered by the exposed region covering portion 130, the metal film 163 is protected without being exposed to the cleaning liquid, as shown in FIG. 15E, while the cleaning liquid is supplied to the upper surface of the substrate W. .. That is, the exposed region covering portion 130 functions as a protective film that protects the metal film 163. In this way, the cleaning liquid can be supplied to the upper surface of the substrate W in a state where 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.

In the subsequent protective film removing step (step S8), the exposed region covering portion 130 of the treated film 100 can be dissolved in the removing liquid to smoothly remove the exposed region covering portion 130 from the upper surface of the substrate W.
According to the second embodiment, the same effect as that of the first embodiment is obtained.
Further, according to the second embodiment, the following effects are also obtained.

By supplying the release liquid to the upper surface of the substrate W in which the treated film 100 is formed, the non-exposed region covering portion 131 (the film to be peeled off) holds the first removal target object 203 on the substrate W. It is peeled off from the top surface. Therefore, the first object to be removed 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 object 204 is removed from the upper surface of the substrate W by the cleaning liquid, and then the exposed region covering portion 130 (protective film) is removed from the upper surface of the substrate W by the removal liquid.

When the cleaning liquid is supplied to the upper surface of the substrate W, the exposed region 170 on the upper surface of the substrate W where the metal film 163 is exposed is covered with the exposed region covering portion 130. Therefore, although the cleaning liquid used for removing the second object to be removed 204 has a property of oxidizing the metal film 163, the second object to be removed 204 is removed without oxidizing the metal film 163. can do.

Therefore, it is possible to efficiently remove a plurality of types of objects to be removed (first object to be removed 203 and second object to be removed 204) from the upper surface of the substrate W while suppressing oxidation of the metal film 163.
When the exposed region covering portion 130 of the treatment film 100 is dissolved in the removing liquid, the first removal target object 203 released from the holding by the exposed region covering portion 130 may reattach to the exposed region 170. According to the second embodiment, the treated film 100 is formed after the pretreated film 200 having a relatively high removing force for removing the first removal object 203 existing in the exposed region 170 is removed from the exposed region 170 by peeling. Will be done. Therefore, most of the first removal target 203 is removed from the exposed region 170 before the treatment film 100 is formed.

Therefore, even if the exposed region covering portion 130 is dissolved in the removing liquid and removed from the exposed region 170, it is possible to sufficiently prevent the first removal target object 203 from remaining in the exposed region 170.
Also in the second embodiment, even when the substrate treatment according to the above-described 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 above-described embodiment is also performed. Has the same effect as.

<Details of treatment liquid>
Hereinafter, each component in the treatment liquid used in the above-described embodiment will be described.
In the following, _{"C x to y",} wherein such _"C X to _{C y"} and _{"C x"} means the number of carbons in the molecule or substituent. For example, C _1-6 alkyl means an alkyl chain having 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

If the polymer has multiple repeating units, these repeating units will copolymerize. Unless otherwise specified, these copolymers may be any of alternating copolymers, random copolymers, block copolymers, graft copolymers, or a mixture thereof. When a polymer or resin is represented by a structural formula, n, m, etc., which are also written in parentheses, indicate the number of repetitions.
<Low solubility component>
(A) The low-solubility component is at least one of novolak, polyhydroxystyrene, polystyrene, polyacrylic acid derivative, polymaleic acid derivative, polycarbonate, polyvinyl alcohol derivative, polymethacrylic acid derivative, and a copolymer of a combination thereof. including. Preferably, the low solubility component (A) may contain at least one of novolak, polyhydroxystyrene, polyacrylic acid derivative, polycarbonate, polymethacrylic acid derivative, and a copolymer of a combination thereof. More preferably, the low solubility component (A) may contain at least one of novolak, polyhydroxystyrene, polycarbonate, and a copolymer of a combination thereof. The novolak may be a phenol novolak.

The treatment liquid may contain one or a combination of two or more of the above-mentioned preferred examples as the (A) low-solubility component. For example, (A) the poorly soluble component may contain both novolak and polyhydroxystyrene.
It is a preferred embodiment that the low-solubility component (A) is formed into a film by drying, and the film is peeled off while holding the object to be removed without being largely dissolved by the stripping solution. It is permissible that the stripping solution dissolves only a small part of the (A) low-solubility component.

Preferably, the low solubility component (A) does not contain fluorine and / or silicon, more preferably both.
The copolymerization is preferably random copolymerization or block copolymerization.
Although there is no intention of limiting the scope of rights, specific examples of (A) the low-solubility component include the compounds represented by the following chemical formulas 1 to 7.

(Asterisk * indicates a combination to adjacent building blocks.)

(R _{means a substituent such as C 1-4} alkyl. An asterisk * indicates a bond to an adjacent structural unit.)

(Me means a methyl group.)
The weight average molecular weight (Mw) of the low-solubility component (A) is preferably 150 to 500,000, more preferably 300 to 300,000, still more preferably 500 to 100,000, and even more preferably. Is 1,000 to 50,000.
(A) The low-solubility component can be obtained by synthesizing. You can also buy it. When purchasing, the following are examples of supply destinations. It is also possible for the supplier to synthesize the polymer (A).
Novolac: Showa Kasei Co., Ltd., Asahi Organic Materials Co., Ltd., Gun Ei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.
Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.
Polyacrylic acid derivative: Japan Catalytic Polycarbonate Co., Ltd .: Sigma-Aldrich Polymethacrylic acid derivative: Sigma-Aldrich The low-solubility component is 0.1 to 50% by mass, preferably 0.1 to 50% by mass, as compared with the total mass of the treatment liquid. Is 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass. That is, the total mass of the treatment liquid is 100% by mass, and based on this, the (A) low-solubility component is 0.1 to 50% by mass. That is, "compared with" can be rephrased as "based on". Unless otherwise specified, the same applies to the following.

Solubility can be evaluated by known methods. For example, under the conditions of 20 ° C. to 35 ° C. (more preferably 25 ± 2 ° C.), 100 ppm of the above (A) or (B) described below is added to 5.0 mass% aqueous ammonia, covered and shaken. By shaking with a flask for 3 hours, it can be determined whether (A) or (B) is dissolved. The shaking may be stirring. Dissolution can also be visually determined. If it is not dissolved, the solubility is less than 100 ppm, and if it is dissolved, the solubility is 100 ppm or more. If the solubility is less than 100 ppm, it is insoluble or sparingly soluble, and if the solubility is 100 ppm or more, it is soluble. In a broad sense, soluble includes slightly soluble. Solubility is low in the order of insoluble, sparingly soluble, and soluble. In a narrow sense, slightly soluble is less soluble than soluble and more soluble than poorly soluble.

<Highly soluble component>
The (B) highly soluble component is the (B') crack-promoting component. The (B') crack-promoting component contains a hydrocarbon and further contains a hydroxy group (-OH) and / or a carbonyl group (-C (= O)-). When the (B') crack-promoting component is a polymer, one of the constituent units contains a hydrocarbon for each unit, and further has a hydroxy group and / or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and enone, and carboxylic acid is preferable.

There is no intention to limit the scope of rights and it is not bound by theory, but when the treatment liquid is dried to form a treatment film on the substrate and the release liquid peels off the treatment film, (B) the highly soluble component is the treatment film. It is thought that it creates a part that triggers peeling. For this reason, it is preferable that the (B) highly soluble component has a higher solubility in the stripping solution than the (A) poorly soluble component. A ring-shaped hydrocarbon can be mentioned as an embodiment in which the (B') crack-promoting component contains a ketone as a carbonyl group. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

As a more specific embodiment, (B) highly soluble component (1 to 4 is preferably) the following chemical formula 8 structural units from 1 to 6 comprise becomes as, each of the structural units is a linking group (linker) L ₁ It is a compound bound by. Here, the linker L ₁ may be a single bond or C _{1 to 6} alkylene. The C _{1 to 6} alkylenes are not limited to divalent groups by linking structural units as linkers. It is preferably 2 to 4 valent. The C _{1 to 6} alkylene may be either linear or branched.

Cy ₁ is a C _5-30 hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. As a preferred embodiment, the linker _{L 1} is linked a plurality of Cy _1.
R ₁ is independently C _1-5 alkyl, preferably methyl, ethyl, propyl, or butyl. The C _{1 to 5} alkyl may be linear or branched.

n _b1 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. n _b1'is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.
The following chemical formula 9 is a chemical formula in which the structural unit described in the chemical formula 8 is represented by using _{the linker L 9.} The linker L ₉ represents a single bond, methylene, is preferably ethylene or propylene.

Although there is no intention to limit the scope of rights, as preferable examples of (B) highly soluble component, 2,2-bis (4-hydroxyphenyl) propane, 2,2'-methylenebis (4-methylphenol), 2, 6-bis [(2-Hydroxy-5-methylphenyl) methyl] -4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di- Examples thereof include tert-butylhydroquinone and 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. These may be obtained by polymerization or condensation.

As an example, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol represented by the following chemical formula 10 will be taken up and described. The compound (B), the has three structural units of formula 8, the structural unit is bonded by a linker L _{1 (methylene).} n _b1 = n _b1' = 1 and R ₁ is methyl.

(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. (B) When the highly soluble component is a resin, polymer or polymer, the molecular weight is represented by the weight average molecular weight (Mw).
(B) The highly soluble component can be obtained by synthesis or purchase. Supply destinations include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

In the treatment solution, the (B) highly soluble component is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, as compared with the mass of the (A) low solubility component. In the treatment solution, the (B) highly soluble component is more preferably 1 to 30% by mass as compared with the mass of the (A) low soluble component.
<Solvent>
The solvent (C) preferably contains an organic solvent. (C) The solvent may be volatile. Being volatile means that it is more volatile than water. For example, (C) the boiling point of the solvent at 1 atm is preferably 50 to 250 ° C. The boiling point of the solvent at 1 atm is more preferably 50 to 200 ° C, even more preferably 60 to 170 ° C. The boiling point of the solvent at 1 atm is even more preferably 70 to 150 ° C. It is also permissible for the solvent (C) to contain a small amount of pure water. The amount of pure water contained in the solvent (C) is preferably 30% by mass or less as compared with the whole solvent (C). The pure water contained in the solvent is more preferably 20% by mass or less, still more preferably 10% by mass or less. The pure water contained in the solvent is even more preferably 5% by mass or less. It is also a preferable form that the solvent does not contain pure water (0% by mass). The pure water is preferably DIW.

Examples of the organic solvent include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and ethylene glycol mono such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Alkyl ether acetates, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Alkyl ether acetates, 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, N, N-dimethylacetamide, N -Amids such as methylpyrrolidone, lactones such as γ-butyrolactone and the like can be mentioned. These organic solvents can be used alone or in admixture of two or more.

In a preferred embodiment, the organic solvent contained in (C) solvent is selected from IPA, PGME, PGEE, EL, PGMEA, or any combination thereof. When the organic solvent is a combination of two kinds, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
The solvent (C) is 0.1 to 99.9% by mass as compared with the total mass of the treatment liquid. The solvent (C) is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass, as compared with the total mass of the treatment liquid. The solvent (C) is further preferably 80 to 99% by mass, and even more preferably 85 to 99% by mass, as compared with the total mass of the treatment liquid.

<Other additives>
The treatment liquid of the present invention may further contain (D) other additives. In one aspect of the invention, (D) the other additive comprises a surfactant, an acid, a base, an antibacterial agent, a bactericidal agent, a preservative, or an antifungal agent (preferably a surfactant). Any combination of these may be included.

As one aspect of the present invention, the mass of (A) other additives (in the case of a plurality of them, the sum thereof) is 0 to 100 mass (preferably 0) as compared with the mass of the (A) low-solubility component in the treatment liquid. It is 10% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass, still more preferably 0 to 1% by mass). It is also one of the aspects of the present invention that the treatment liquid does not contain (D) other additives (0% by mass).

<Corrosion prevention component>
Examples of the (E) corrosion-preventing component include uric acid, caffeine, buterin, adenine, glyoxylic acid, glucose, fructose, mannose and the like, in addition to BTA.
<Details of pretreatment liquid>
Hereinafter, each component in the pretreatment liquid used in the above-described embodiment will be described. The (A) low-solubility component, (C) solvent, (D) other additives, and (E) corrosion-preventing component contained in the pretreatment solution can be selected from those that can be used for the treatment membrane. ..

The (B) highly soluble component contained in the pretreatment solution is different from that contained in the treatment solution. The (B) highly soluble component contained in the pretreatment solution includes the first component selected from those exemplified as the highly soluble component contained in the treatment solution, and the following (B-1) and (B-). It is composed of a second component selected from 2). As a supplement, the above-mentioned treatment solution contains only the first component (B) as a highly soluble component.

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

R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently hydrogen or _{alkyl of C 1-5} , preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen. It is methyl or ethyl, more preferably methyl or ethyl.
Linker L ₂₁ and Linker L ₂₂ are independently composed of C _{1 to 20} alkylene, C _{1 to 20} cycloalkylene, C _{2 to 4} alkenylene, C _{2 to 4} alkinylene, or C _{6 to 20} arylene. is there. These groups may be substituted with _{C 1-5 alkyl or hydroxy.} Here, alkenylene means a divalent hydrocarbon having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. Linker L ₂₁ and linker L ₂₂ are preferably C _2-4 alkylene, acetylene (C ₂ alkynylene) or phenylene, more preferably C _2-4 alkylene or acetylene, and even more preferably acetylene. ..

n _b2 is 0, 1 or 2, preferably 0 or 1, more preferably 0.
Although there is no intention to limit the scope of rights, as a preferable example of (B-1), 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5- Examples include diols. As another form, 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiin-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy- 2-Butene and 1,4-benzenedimethanol are also mentioned as preferable examples of (B-1).

(B-2) is a polymer containing 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, more preferably 700 to 3,000.

Here, R ₂₅ is −H, −CH ₃ , or −COOH, preferably −H, or −COOH. It is also permissible for one (B-2) polymer to contain two or more structural units, each represented by Chemical Formula 12.
Although not intended to limit the scope of rights, preferred examples of the (B-2) polymer include acrylic acid, maleic acid, or a polymer of a combination thereof. Polyacrylic acid and acrylic acid maleic acid copolymers are more suitable examples.

In the case of copolymerization, it is preferably random copolymerization or block copolymerization, and more preferably random copolymerization.
As an example, the acrylic acid maleic acid copolymer represented by the following chemical formula 13 will be described. The copolymer is contained in (B-2) and has two structural units represented by the chemical formula 12. In one structural unit, R ₂₅ is −H, and in another structural unit, R ₂₅ is −COOH. Is.

<Peeling experiment>
Changes in the peeling state of the polymer film from the copper film and the particle removing power by changing the ratio of the first component and the second component of the highly soluble component in the polymer-containing liquid used as the treatment liquid and the pretreatment liquid. In order to verify the above, a peeling experiment was conducted to peel off the polymer film from the copper film. The polymer membrane is a solid membrane formed by evaporation of at least a part of the solvent in the polymer-containing liquid.

First, a small piece-shaped substrate (small piece substrate) having particles such as _{SiO 2 adhered to the surface is prepared.} The small piece substrate used was a quadrangular substrate having a side of 3 cm when viewed from the normal direction of the main surface and having a copper film formed on the entire surface.
The small piece substrate was placed on a rotatable mounting table, and the polymer-containing liquid was supplied to the surface of the small piece substrate to form a polymer film. Then, while rotating the mounting table, diluted ammonia water (dNH ₄ OH 1:68) was supplied to the surface (main surface) of the small piece substrate to peel off the polymer film. Then, the surface of the small piece substrate was rinsed with carbonated water, and then IPA was supplied to the surface of the small piece substrate to remove the residue of the polymer film. After removing the residue of the polymer film, the small piece substrate was rotated at high speed for spin drying. Then, the degree of particle removal (removal power) was confirmed using a scanning electron microscope (SEM).

FIG. 16 is a table for explaining the results of the peeling experiment. In FIG. 16, the ratio of the first component and the second component of the highly soluble component in the polymer-containing solution is shown as the addition amount. FIG. 16 shows the degree of particle removal when the ratios of the first component and the second component and the addition amount are changed.
A "D" is given as an evaluation of the removing power to the combination of the addition amount of the first component and the addition amount of the second component that cannot be removed by the particles. In addition, in FIG. 16, there was no combination in which the evaluation of the removing force was “D”. Similarly, "C" is given as an evaluation of the removing power to the combination of the addition amount of the first component and the addition amount of the second component from which the particles are partially removed. "B" is given as an evaluation of the removing power to the combination of the addition amount of the first component and the addition amount of the second component from which the particles can be largely removed. When the particles can be removed, "A" is given as an evaluation of the removing power. Then, when the particles can be sufficiently removed, "AA" is given as an evaluation of the removing power.

For example, when the addition amount of the first component is 0.1 and the addition amount of the second component is 0.5, the ratio of the second component to the first component in the polymer-containing liquid is 5: 1. Means that Further, when the addition amounts of the first component and the second component are both 0.5, the ratio of the second component to the first component in the polymer-containing liquid is 1: 1. The ratio of the second component to the first component in the polymer-containing liquid when the addition amounts of the first component and the second component are both 3.0 is also 1: 1. The ratio of the highly soluble component (total amount of the first component and the second component) in the polymer-containing liquid when the addition amounts of the first component and the second component are both 3.0 is the ratio of the first component and the second component. It means that it is 6 times the ratio of the highly soluble component (total amount of the first component and the second component) in the polymer-containing liquid when both of the addition amounts are 0.5.

As shown in FIG. 16, when the addition amount of the second component is 0, the evaluation of the removing power is “C”, and when the addition amount of the first component is 0, the evaluation of the removing power is “B”. Met.
When the addition amount of the second component is smaller than the addition amount of the first component or when the addition amount of the second component is the same as the addition amount of the first component, the evaluation of the removing power is "B". There were many.
For example, when the addition amount of the second component was 0.5 and the addition amount of the first component was 1.0, the evaluation of the removing power was "B". Even when the addition amounts of the second component and the first component were both 0.5, the evaluation of the removing power was "B". Even when the addition amounts of the second component and the first component were both 1.0, the evaluation of the removing power was "B". When both the amount of the first component added and the amount of the second component added were 3.0, the evaluation of the removing power was "A".

When the amount of the second component added was larger than the amount of the first component added, the evaluation of the removing power was "A" or "AA" in all the experimental results.
From the above results, the polymer film containing the first component and the second component as the highly soluble component removes particles from the copper film (metal film) more than the polymer film containing only the first component as the highly soluble component. It is inferred that the removing power is high. When a polymer film is used to remove particles from the copper film, it is suggested that it is preferable to prepare the polymer-containing liquid so that the content of the second component is higher than that of the first component.

<Third Embodiment>
FIG. 17 is a schematic view of the first moving nozzle 9 and the third moving nozzle 11 of the processing unit 2 provided in the substrate processing device 1Q according to the third embodiment of the present invention, and the members around them. In FIG. 17, the same reference numerals as those in FIGS. 1 and the like are added to the configurations equivalent to the configurations shown in FIGS. 1 to 16 described above, and the description thereof will be omitted. Similarly, in FIG. 18, which will be described later, the same reference numerals as those in FIG. 1 and the like are added, and the description thereof will be omitted.

With reference to FIG. 17, the substrate processing apparatus 1Q according to the third embodiment is the substrate processing apparatus 1 according to the first embodiment (see FIG. 3) and the substrate processing apparatus 1P according to the second embodiment (see FIG. 11). ), The substrate processing apparatus 1Q according to the third embodiment can adjust the concentration of the highly soluble component contained in the treatment solution or the pretreatment solution.
In the first moving nozzle 9, a first component liquid which is a mixed liquid of a first component of a highly soluble component and a solvent and a low soluble component liquid which is a mixed liquid of a low soluble component and a solvent are contained in the first moving nozzle 9. A treatment solution prepared by mixing is supplied.

Specifically, the low-solubility component liquid pipe 140 and the first component liquid pipe 141 are commonly connected to the other end of the treatment liquid pipe 40 whose one end is connected to the first moving nozzle 9. The low-soluble component liquid pipe 140 is connected to the low-soluble component liquid supply source, and the first component liquid pipe 141 is connected to the first component liquid supply source.
The low-soluble component liquid pipe 140 is interposed with a low-soluble component liquid valve 150 that adjusts the flow rate of the low-soluble component liquid supplied from the low-soluble component liquid pipe 140 to the treatment liquid pipe 40. The first component liquid pipe 141 is interposed with a first component liquid valve 151 that adjusts the flow rate of the first component liquid supplied from the first component liquid pipe 141 to the processing liquid pipe 40.

By changing the opening degree of the low-solubility component liquid valve 150 and the first component liquid valve 151, the concentration of the first component in the treatment liquid flowing through the treatment liquid pipe 40 can be changed.
The third moving nozzle 11 contains a first component liquid which is a mixture of a first component of a highly soluble component and a solvent, and a second component liquid which is a mixture of a second component of a highly soluble component and a solvent. A pretreatment liquid prepared by mixing the low-soluble component liquid and the low-soluble component liquid, which is a mixed liquid of the low-solubility component and the solvent, is supplied.

Specifically, the low-solubility component liquid pipe 142, the first component liquid pipe 143, and the second component liquid pipe 144 are commonly used at the other end of the pretreatment liquid pipe 42 having one end connected to the third moving nozzle 11. It is connected. The low-solubility component liquid pipe 142 is connected to the 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.

The low-soluble component liquid pipe 142 is interposed with a low-soluble component liquid valve 152 that adjusts the flow rate of the low-soluble component liquid supplied from the low-soluble component liquid pipe 142 to the pretreatment liquid pipe 42. .. The first component liquid pipe 143 is interposed with a first component liquid valve 153 that adjusts the flow rate of the first component liquid supplied from the first component liquid pipe 143 to the pretreatment liquid pipe 42. The second component liquid pipe 144 is interposed with a second component liquid valve 154 that adjusts the flow rate of the second component liquid supplied from the second component liquid pipe 144 to the pretreatment liquid pipe 42.

By changing the opening degree 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 second component in the pretreatment liquid flowing through the pretreatment liquid pipe 42 The concentration of the component can be changed.
In the substrate processing apparatus 1Q, a recipe selection process for selecting a recipe R based on information about the upper surface of the substrate W is executed before the substrate processing is performed on the substrate W.

The plurality of recipes R stored in the auxiliary storage device 3e shown in FIG. 4 include a first recipe R1 and a second recipe R2 having different processing contents.
The first recipe R1 is a recipe R for executing a first substrate processing method for removing an object to be removed from the substrate W using a processing liquid. The first substrate processing method is a substrate processing method in which the pretreatment liquid supply step (step S2) to the pretreatment membrane residue removal step (step S6) are omitted in the substrate treatment according to the first embodiment or the second embodiment. .. That is, in the first substrate processing method, the removal target object 103 (first removal target object 203) is not removed using the pretreatment liquid, and the removal target object 103 (first removal target object 203) using the treatment liquid is not performed. Is only removed.

In the second recipe R2, after removing the object to be removed 103 (the first object to be removed 203) from the substrate W using the pretreatment liquid, the object to be removed 103 (the first object to be removed 203) is removed from the substrate W using the treatment liquid. This is a recipe for executing the second substrate processing method for removing 203). The second substrate processing method is the substrate processing according to the first embodiment or the substrate processing according to the second embodiment.
The second recipe 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 treatment method is set according to the type of the specific substance. Specifically, in each second recipe, the low-solubility component liquid valve 152, the first component liquid valve 153, and the second component liquid when the pretreatment liquid is supplied to the upper surface of the substrate W according to the type of the specific substance. The opening degree of the valve 154 is set.

FIG. 18 is a flow chart for explaining an example of the recipe selection process. First, the controller 3 acquires information about the surface of the substrate W (processed substrate) to be processed (information acquisition step: step S30). The information about the surface of the substrate W may be acquired based on the information input by the user using the input device 3A, or is configured to read the information from a sign such as a bar code set on the substrate W. May be good.

After step S30, the controller 3 determines that the substrate W has both the exposed region 170 and the unexposed region 171 based on the information about the surface of the substrate W acquired in the information acquisition step, and the non-exposed region. It is determined which of the substrates has a surface on which only 171 is present (surface determination step: step S31).
In step S31, when the controller 3 determines that the substrate W is a substrate having a surface in which only the unexposed region 171 exists (step S31: NO), the controller 3 selects the first recipe R1 (recipe selection step: 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.

On the other hand, if the controller 3 determines in step S31 that the substrate W is a substrate having a surface on which both the exposed region 170 and the unexposed region 171 exist (step S31: YES), the controller 3 acquires the substrate W in the information acquisition step. The type of the specific substance exposed from the surface of the substrate W is determined based on the information about the surface of the substrate W (type determination step: step S33). After step S33, the controller 3 selects the second recipe R2 based on the type of specific substance exposed from the surface of the substrate W (recipe selection step: 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.

According to the third embodiment, when only the unexposed area 171 exists on the upper surface of the substrate W, the first recipe R1 for executing the first substrate processing method is selected, and the exposed area 170 and the exposed area 170 on the upper surface of the substrate W. If both of the unexposed areas 171 are present, the second recipe R2 that executes the second substrate processing method is selected. Therefore, an appropriate substrate processing method can be executed according to the state of the upper surface of the substrate W.

When both the exposed region 170 and the non-exposed region 171 are present on the upper surface of the substrate W, it is suitable for removing the removal target 103 (first removal target 203) from the exposed region 170 according to the type of the specific substance. The second recipe R2 can be selected.
<Other Embodiments>
The present invention is not limited to the embodiments described above, and can be implemented in still other embodiments.

For example, in the treatment film forming step (step S8), the liquid film 101 may be solidified or hardened due to evaporation of the solvent when the liquid film 101 of the treatment liquid is thinned. In such a case, it is necessary to heat the substrate W or spray a gas on the upper surface of the substrate W in order to solidify or cure the liquid film 101 of the treatment liquid after thinning the liquid film 101 of the treatment liquid. There is no.

The same applies to the case where the pretreatment film 200 is formed by evaporating the solvent when the liquid film 201 of the pretreatment liquid is thinned in the pretreatment film forming step (step S3). That is, even in such a case, heating of the substrate W and spraying of gas on the upper surface of the substrate W can be omitted.
Further, in the substrate treatment according to the second embodiment, the cleaning liquid removing step (step S21) is executed after the cleaning step (step S20). However, it is also possible to omit the cleaning liquid removing step. Specifically, the cleaning liquid supplied to the substrate W in the cleaning step and the treated membrane residue removing liquid supplied to the substrate W in the treated membrane residue removing step (step S11) executed after the cleaning liquid removing step have compatibility. In some cases, it is not necessary to perform the cleaning liquid removal step.

Further, in the above-described embodiment, in the treatment film peeling step (step S9), the exposed region covering portion 130 remains in the exposed region 170 without being peeled by the peeling liquid. However, in the treatment film peeling step, the exposed region covering portion 130 may be peeled off by the peeling liquid.
In the above-mentioned first to third embodiments, a polymer-containing solution containing only the first component as the highly soluble component is used as the treatment solution, and the first component and the second component are used as the highly soluble component. A polymer-containing solution containing both was used as the pretreatment solution. However, a polymer-containing solution containing both the first component and the second component as a highly soluble component is used as a treatment solution, and a polymer-containing solution containing only the first component as a highly soluble component is used in advance. It may be used as a treatment liquid. In this case, the unexposed region 171 in which the specific substance such as copper is not exposed corresponds to the first region of the present invention, and the exposed region 170 in which the specific substance such as copper is exposed corresponds to the second region of the present invention. To do.

Further, in the first embodiment, the exposed region covering portion 130 is not peeled by the stripping 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 stripping liquid.
Further, in the third embodiment, the second recipe R2 is prepared for each type of specific substance exposed from the substrate W. However, the second recipe R2 is not provided for each type of the specific substance, and a common second recipe R2 may be used regardless of the specific substance. In this case, as shown in FIG. 19, when it is determined in the recipe selection process that the substrate W is a substrate having a surface in which both the exposed region 170 and the unexposed region 171 are present (step S31: YES), The second recipe R2 is selected without determining the type of the specific substance (recipe selection step: step S35).

In addition, various changes can be made within the scope of the claims.

1: Substrate processing device 1P: Substrate processing device 1Q: Substrate processing device 3: Controller 9: First moving nozzle (processing liquid supply unit)
10: Second moving nozzle (stripping liquid supply unit)
11: Third moving nozzle (pretreatment liquid supply unit)
12: Central nozzle (treatment film forming unit, pretreatment film forming unit)
13: Bottom surface nozzle (treatment film forming unit, pretreatment film forming unit)
23: Spin motor (treated film forming unit, pre-treated film forming unit)
100: Treated membrane 102: Through hole (first through hole)
103: Object to be removed (first object to be removed)
110: Highly soluble solid (first highly soluble component in the solid state)
111: Low-solubility solid (first low-solubility component in the solid state)
130: Exposed area covering part (the part of the treated film that covers the exposed area, the protective film)
131: Non-exposed area covering part (the part of the treated film that covers the non-exposed area, the film to be peeled off)
163: Metal film (specific substance, metal)
170: Exposed area (first area, second area)
171: Non-exposed area (second area, first area)
200: Pretreatment membrane 202: Through hole (second through hole)
203: First object to be removed (granular residue)
204: Second object to be removed (film-like residue)
210: Highly soluble solid (second highly soluble component in the solid state)
211: Low-solubility solid (second low-solubility component in the solid state)
W: Substrate

Claims (17)

A substrate processing method for processing a substrate having a surface on which a first region and a second region where different substances are exposed are present.
A pretreatment liquid supply step of supplying the pretreatment liquid to the surface of the substrate, and
A pretreatment film forming step of solidifying or curing the pretreatment liquid supplied to the surface of the substrate to form a pretreatment film on the surface of the substrate that holds the first removal target existing on the surface of the substrate. When,
A pretreatment film peeling step of supplying a stripping liquid to the surface of the substrate to peel the pretreatment film in a state of holding the first removal object from the surface of the substrate.
After the pretreatment film peeling step, a treatment liquid supply step of supplying the treatment liquid to the surface of the substrate and a treatment liquid supply step
A treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate for holding the first removal object existing on the surface of the substrate.
The process includes a treatment film peeling step of supplying a stripping liquid to the surface of the substrate to peel the treated film in a state of holding the first removal object from the surface of the substrate.
The removing force for removing the first removing object existing in the second region is higher than the removing force for removing the first removing object existing in the second region by the pretreated membrane. ,
The removing force for removing the first removal object existing in the first region by the pretreatment membrane is higher than the removing force for removing the first removal object existing in the first region by the treatment membrane. , Substrate processing method. The removing force for removing the first removal target is a holding force for holding the first removal target existing in the first region or the second region on the treated membrane or the pretreated membrane, and the first removing force. It is composed of the peelability indicating the ease of peeling of the treated film or the pretreated film in a state of holding the object to be removed.
In the first region, the pretreated film has higher peelability than the treated film.
The substrate processing method according to claim 1, wherein the treated film has a higher holding power than the pretreated film in the second region. The first region is an exposed region where the metal is exposed.
The second region is a non-exposed region other than the exposed region.
The removing force for removing the first removing object existing in the non-exposed region is higher than the removing force for removing the first removing object existing in the unexposed region by the pretreated membrane. ,
A claim that the pretreatment film removes the first removal object existing in the exposed region is higher than the removal power of the treatment film removing the first removal object existing in the exposed region. Item 2. The substrate processing method according to Item 1 or 2. The substrate according to claim 3, further comprising a treated film residue removing step of supplying a removing liquid to the surface of the substrate to remove the residue of the treated film remaining on the surface of the substrate after the treated film peeling step. Processing method. The treatment film peeling step includes a step of peeling a portion of the treated film that covers the non-exposed region without peeling the portion of the treated film that covers the exposed region.
The substrate treatment method according to claim 4, wherein the treatment film residue removing step includes a step of dissolving a portion of the treated membrane covering the exposed region in the removing liquid to remove the residue. The treatment film forming step holds the first removal target object existing in the non-exposed region on the surface of the substrate, and covers and protects the peelable target film that covers the non-exposed region and the exposed region. Including a step of forming the treated film having a film on the surface of the substrate.
The third aspect of the present invention further includes a cleaning step of supplying a cleaning liquid to the surface of the substrate after the treatment film peeling step to dissolve and remove the second removal object existing on the surface of the substrate by the cleaning liquid. The substrate processing method described. After the treatment film peeling step, a treatment film residue removing step of supplying a removing liquid to the surface of the substrate to remove the residue of the treated film remaining on the surface of the substrate is further included.
The substrate treatment method according to claim 6, wherein the treatment film residue removing step includes a step of removing the protective film as the residue. The substrate processing method according to claim 7, wherein the first removal target and the second removal target are residues generated by dry etching treatment. The first object to be removed is a granular residue.
The substrate processing method according to claim 8, wherein the second removal target is a film-like residue that covers at least a part of the unexposed region on the surface of the substrate. The treatment liquid has a first solute and a first solvent that dissolves the first solute.
The first solute has a first highly soluble component and a first low soluble component that is less soluble in the stripping solution than the first highly soluble component.
The substrate treatment method according to any one of claims 1 to 9, wherein the treatment film peeling step includes a step of selectively dissolving the first highly soluble component in a solid state in the stripping liquid. Any one of claims 1 to 10, wherein the treated film peeling step includes a first through hole forming step of partially dissolving the treated film in the peeling liquid to form a first through hole in the treated film. The substrate processing method described in the section. The pretreatment liquid has a second solute and a second solvent that dissolves the second solute.
The second solute has a second highly soluble component and a second low soluble component that is less soluble in the stripping solution than the second highly soluble component.
The substrate treatment method according to any one of claims 1 to 11, wherein the pretreatment film peeling step includes a step of selectively dissolving the second highly soluble component in a solid state in the stripping liquid. The pretreatment film peeling step includes a second through hole forming step of partially dissolving the pretreatment film in the peeling liquid to form a second through hole in the pretreatment film, according to claims 1 to 12. The substrate processing method according to any one item. A substrate processing apparatus for processing a substrate having a surface on which a first region and a second region where different substances are exposed are present.
A processing liquid supply unit that supplies the processing liquid to the surface of the substrate,
A treatment film forming unit that solidifies or cures the treatment liquid to form a treatment film on the surface of the substrate.
A pretreatment liquid supply unit that supplies the pretreatment liquid to the surface of the substrate,
A pretreatment film forming unit that solidifies or cures the pretreatment liquid to form a pretreatment film on the surface of the substrate.
A stripping liquid supply unit that supplies the stripping liquid to the surface of the substrate,
The pretreatment liquid supply unit, the pretreatment film forming unit, the treatment liquid supply unit, the treatment film forming unit, and a controller for controlling the release liquid supply unit are included.
The controller
The pretreatment liquid is supplied from the pretreatment liquid supply unit toward the surface of the substrate, and the pretreatment liquid is supplied.
The pretreatment liquid on the surface of the substrate is solidified or cured by the pretreatment film forming unit, and a pretreatment film for holding the object to be removed existing on the surface of the substrate is formed on the surface of the substrate.
The release liquid is supplied from the release liquid supply unit to the surface of the substrate, and the pretreatment film in a state of holding the object to be removed is peeled from the surface of the substrate.
After the pretreatment film is peeled off, the treatment liquid is supplied from the treatment liquid supply unit to the surface of the substrate.
The treatment liquid on the surface of the substrate is solidified or cured by the treatment film forming unit to form a treatment film on the surface of the substrate that holds the object to be removed existing on the surface of the substrate.
It is programmed to supply a stripping liquid from the stripping liquid supply unit to the surface of the substrate to peel the treated film in a state of holding the object to be removed from the surface of the substrate.
The removing force for removing the object to be removed existing in the second region is higher than the removing force for removing the object to be removed existing in the second region by the pretreated membrane.
A substrate processing apparatus in which the pretreatment film has a higher removing force for removing the removal target existing in the first region than the removing force for removing the removal target existing in the first region. .. The removing force for removing the object to be removed includes a holding force for holding the object to be removed existing in the first region or the second region on the treated membrane or the pretreated membrane and holding the object to be removed. It is composed of the peelability indicating the ease of peeling of the treated film or the pretreated film in the state of being in the state.
In the first region, the pretreated film has higher peelability than the treated film.
The substrate processing apparatus according to claim 14, wherein the treated film has a higher holding power than the pretreated film in the second region. It is a recipe selection method for selecting a recipe for performing a substrate processing method for processing a substrate to be processed.
An information acquisition process for acquiring information about the surface of the substrate to be processed, and
Based on the information acquired by the information acquisition step, the substrate to be processed has a surface in which both an exposed region where a specific substance is exposed and an unexposed region where the specific substance is not exposed are present, and a substrate. A surface determination step of determining which of the substrates has a surface in which only the unexposed region exists, and
When the surface determination step determines that only the non-exposed region exists on the surface of the processing target substrate, the first substrate processing method of removing the removal target object from the processing target substrate using the treatment liquid is executed. When the first recipe is selected and the surface determination step determines that both the exposed region and the non-exposed region are present on the surface of the processing target substrate, the removal target is removed from the exposed region. A second substrate treatment method in which the removal target is removed from the treatment target substrate using a pretreatment liquid having a force higher than that of the treatment liquid, and then the removal target is removed from the treatment target substrate using the treatment liquid. A recipe selection method including a recipe selection process for selecting a second recipe to execute. The pretreatment liquid has a first component and a second component, and has
The second component has a higher removing power for removing the object to be removed from the exposed region than the first component.
When the surface determination step determines that both the exposed region and the non-exposed region are present on the surface of the processing target substrate, from the surface of the processing target substrate based on the information acquired by the information acquisition step. A type determination step for determining the type of the specific substance to be exposed is further included.
The recipe selection step sets the concentration of the second component in the pretreatment liquid used in the second substrate treatment method according to the specific substance of the type determined by the type determination step. 2. The recipe selection method according to claim 16, further comprising a step of selecting a recipe.

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