JP7292192B2 - SUBSTRATE PROCESSING METHOD, SUBSTRATE PROCESSING APPARATUS, AND RECIPE SELECTION METHOD - Google Patents

Description

The present invention relates to a substrate processing method and substrate processing apparatus for processing a substrate, and a recipe selection method for selecting a recipe for performing the substrate processing method. Substrates to be processed include, for example, semiconductor wafers, liquid crystal display device substrates, FPD (Flat Panel Display) substrates such as organic EL (Electroluminescence) display devices, optical disk substrates, magnetic disk substrates, and magneto-optical disk substrates. Substrates, substrates for photomasks, ceramic substrates, substrates for solar cells, etc. are included.

In the manufacturing process of semiconductor devices, various contaminants adhering to substrates, residues such as processing solutions and resists used in previous processes, various particles, etc. (hereinafter collectively referred to as "objects to be removed") are removed. process is performed.
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 complex. Therefore, it is becoming difficult to remove the object to be removed with DIW or a chemical solution while suppressing damage to the concave-convex pattern.
Therefore, by supplying a processing liquid to the surface of the substrate and solidifying the processing liquid on the substrate to form a holding layer that holds the removal target existing on the substrate, and then supplying a stripping liquid 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 (see Patent Document 1).

JP 2019-62171 A

The removal force with which the retention 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 where different materials are exposed on the surface of the substrate, simply forming a specific holding layer on the surface of the substrate and peeling off the holding layer from the surface of the substrate sufficiently removes the object to be removed. It may not be possible to remove it. Depending on the substance exposed from the surface of the substrate, it is necessary to perform appropriate processing to remove the object to be removed.

SUMMARY OF THE INVENTION Accordingly, 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 a substrate having regions where different substances are exposed. 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 state of the surface 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 processing method comprises a pretreatment liquid supplying step of supplying a pretreatment liquid to the surface of the substrate, and solidifying or hardening the pretreatment liquid supplied to the surface of the substrate so as to exist on the surface of the substrate. A pretreatment film forming step of forming a pretreatment film for holding a first removal target on the surface of the substrate, and a state in which the first removal target is held by supplying a stripping solution to the surface of the substrate a pretreatment film stripping step of stripping the pretreatment film from the surface of the substrate; a processing liquid supply step of supplying a processing liquid to the surface of the substrate after the pretreatment film stripping step; a processing film forming step of solidifying or hardening the supplied processing liquid to form a processing film holding the first object to be removed present on the surface of the substrate on the surface of the substrate; and a processing film stripping step of supplying a liquid to strip the processing film holding the first object to be removed from the surface of the substrate.

The removal force of the treatment film to remove the first object to be removed existing in the second region is greater than the removal force of the pretreatment film to remove the first object to be removed existing in the second region. is high, and the pretreatment film removes the first object to be removed existing in the first region more than the removal force with which the treatment film removes the first object to be removed existing in the first region Powerful.
According to this method, the first object to be removed from the surface of the substrate is removed by peeling off the pretreatment film having a high removal force for removing the first object to be removed existing in the first region. After that, the first object to be removed from the surface of the substrate is removed by peeling the treatment film having a high removal force for removing the first object to be removed existing in the second region. That is, the removal of the first object to be removed is performed in two stages using the pretreatment film and the treatment film having different areas with high removal power for removing the first object to be removed.

Therefore, even if the substrate has a surface with regions where different substances are exposed, the first object to be removed can be removed efficiently.
In one embodiment of the present invention, the removal force for removing the first object to be removed is such that the first object to be removed existing in the first region or the second region is held by the treatment film or the pretreatment film. and a releasability representing the ease with which the treatment film or the pretreatment film is removed while holding the first object to be removed. The treatment film has higher releasability than the treatment film, and the treatment film has higher holding power than the pretreatment film in the second region.

Therefore, in the first region, most of the first removal target can be removed by stripping the pretreatment liquid film, and in the second region, most of the first removal target is removed by stripping of the treatment film. be able to. Therefore, even if the substrate has a surface with regions where different substances are exposed, the first object to be removed can be removed efficiently.
In one embodiment of the invention, the first region is an exposed region where metal is exposed, and the second region is a non-exposed region other than the exposed region. The treatment film has a higher removal force for removing the first object to be removed existing in the non-exposed region than the pretreatment film removes the first object to be removed existing in the non-exposed region. The pretreatment film removes the first object to be removed existing in the exposed region more than the treatment film removes the first object to be removed existing in the exposed region.

According to this method, the peeling of the pretreatment film, which has a relatively high removal force for removing the first object to be removed existing in the exposed region, is compared with the removal force for removing the first object to be removed existing in the non-exposed region. The first object to be removed is removed from the surface of the substrate by performing both the stripping of the treated film and the removal of the highly processed film. Therefore, the first object to be removed can be efficiently removed from the substrate having a surface with exposed regions and non-exposed regions.

In one embodiment of the present invention, the substrate processing method includes, after the process film stripping step, supplying a removing liquid to the surface of the substrate to remove a residue of the process film remaining on the surface of the substrate. A residue removal step is further included. According to this method, even if a residue of the processing film adheres to the surface of the substrate after the processing film is stripped by the stripping liquid, the residue can be removed by the removing liquid.

In one embodiment of the present invention, the step of stripping the processing film includes stripping a portion of the processing film covering the non-exposed region without stripping a portion of the processing film covering the exposed region. The processing film residue removing step includes a step of removing a portion of the processing film covering the exposed region by dissolving it in the removing liquid.
Even if a portion of the treated film covering the exposed region remains on the exposed region without being peeled off by supplying the stripping liquid to the surface of the substrate, the portion can be dissolved in the removing liquid and removed from the exposed region. can.

When the portion of the treatment film covering the exposed region is dissolved in the removal liquid, there is a risk that the first object to be removed, released from the holding by the portion of the treatment film covering the exposed region, will reattach to the exposed region. Therefore, if the pretreatment film having a relatively high removal force for removing the first removal object present in the exposed area is removed from the exposed area by peeling, the treated film is formed. Most of the first object to be removed has been removed from the exposed area before being removed.

Therefore, even with a configuration in which the portion of the treatment film covering the exposed region is dissolved in the removal liquid and removed from the exposed region, it is possible to sufficiently suppress the first object to be removed from remaining in the exposed region.
In one embodiment of the present invention, the treatment film forming step includes a separation target film that holds the first object to be removed existing in the non-exposed region of the surface of the substrate and covers the non-exposed region; forming the treatment film on the surface of the substrate, the treatment film having a protective film covering and protecting exposed areas. The substrate processing method further includes a cleaning step of supplying a cleaning liquid to the surface of the substrate after the process film stripping step, and removing a second object to be removed existing on the surface of the substrate with the cleaning liquid. .

According to this method, the treatment liquid supplied to the surface of the substrate is solidified or hardened to form a film to be peeled covering the non-exposed area of the surface of the substrate and a protective film covering the exposed area of the surface of the substrate. is formed.
By supplying the stripping solution to the surface of the substrate on which the film to be stripped and the protective film are formed, the film to be stripped is stripped from the surface of the substrate while holding the first object to be removed. Therefore, the first object to be removed is removed from the surface of the substrate. On the other hand, the second object to be removed remains on the surface of the substrate.

After that, the cleaning liquid removes the second object to be removed from the surface of the substrate, and then the removal 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 altering (for example, oxidizing) the metal exposed on the surface of the substrate, the second removal object can be removed without altering the metal. can.

Therefore, it is possible to efficiently remove a plurality of types of objects to be removed (the first object to be removed and the 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 includes, after the process film stripping step, supplying a removing liquid to the surface of the substrate to remove a residue of the process film remaining on the surface of the substrate. A residue removal step is further included. The process film residue removing step includes a step of removing the protective film as the residue.

According to this method, even if a residue of the processing film adheres to the surface of the substrate after the processing film is stripped by the stripping liquid, the residue can be removed by the removing liquid. The protective film that remains on the substrate without being stripped off by the stripping solution is also dissolved by the stripping solution and removed from the exposed region.
Further, since the treatment film is formed after the pretreatment film, which has a relatively high removal force for removing the first removal object existing in the exposed region, is removed from the exposed region by peeling, the pretreatment film is formed before the treatment film is formed. , most of the first object to be removed has been removed from the exposed area. Therefore, even when the protective film is dissolved in the removal liquid and removed from the exposed region, it is possible to sufficiently prevent the first object to be removed from remaining in the exposed region.

In one embodiment of the present invention, the first object to be removed and the second object to be removed are residues produced by dry etching.
In a back-end process (BEOL: Back End of the Line) for forming multiple metal layers 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 a non-exposed region other than the exposed region are formed on the surface of the substrate.

A reaction product between an etching gas such as CF _x (for example, carbon tetrafluoride (CF ₄ )) used in the dry etching process and a portion forming the non-exposed region on the substrate becomes a residue after the dry etching process. , attached to the surface of the substrate. The portion forming the non-exposed region on the surface of the substrate includes the surface of a Low-k film (low dielectric constant interlayer insulating film), an oxide film, a metal hard mask, and the like.

Specifically, in the non-exposed region of the surface of the substrate, a film-like reaction product (film-like residue) between the etching gas and the low-k interlayer insulating film, an etching gas and the low-k interlayer insulating film, an oxide film, or Granular reactants (granular residue) with the metal hard mask adhere. Granular means spherical, ellipsoidal, polyhedral and the like. Particulate residue also adheres to exposed areas of the surface of the substrate.
Particulate residue can be peeled off by physical force, but film-like residue covers at least part of the non-exposed region and is more difficult to peel off from the surface of the substrate by physical force than the particulate residue. is difficult.

Therefore, if the granular residue as the first object to be removed is removed by peeling off the film to be removed, and the film-like residue as the second object to be removed is removed by dissolving it with a cleaning liquid, it is exposed on the surface of the substrate. It is possible to efficiently remove the object to be removed from the substrate while suppressing alteration of the metal.
Specifically, a film to be peeled and a protective film are formed on the surface of the substrate after dry etching, and a stripping solution is supplied to the surface of the substrate on which the film to be peeled and the protective film are formed, thereby removing the film to be peeled. It is stripped from the surface of the substrate while retaining the particulate residue. As such, particulate residue is removed from the surface of the substrate. On the other hand, a film-like residue remains on the non-exposed areas of the surface of the substrate. After that, the film-like residue is dissolved and removed from the surface of the substrate by the cleaning liquid, and then the protective film is removed from the surface of the substrate by the removal liquid.

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 altering (for example, oxidizing) the metal exposed on the surface of the substrate, the film-like residue can be removed without altering the metal.
In one embodiment of the invention, the treatment liquid comprises a first solute and a first solvent that dissolves the first solute. The first solute has a first high-solubility component and a first low-solubility component that is less soluble in the stripping solution than the first high-solubility component. The treatment film stripping step includes a step of selectively dissolving the first highly soluble component in a solid state in the stripping solution.

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

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

In one embodiment of the present invention, the treatment film stripping step includes a first through hole forming step of partially dissolving the treatment film in the stripping solution to form first through holes in the treatment film.
Therefore, the stripping solution can pass through the treatment film via the first through-holes and quickly reach the vicinity of the interface between the treatment film and the surface of the substrate. Therefore, the stripping liquid can be applied to the interface between the processed film and the substrate to efficiently strip the processed film from 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 invention, the pretreatment liquid comprises a second solute and a second solvent that dissolves the second solute. The second solute has a second high-solubility component and a second low-solubility component that is less soluble in the stripping solution than the second high-solubility component. The pretreatment film stripping step includes a step of selectively dissolving the solid second highly soluble component in the stripping solution.
According to this method, the solid state second highly soluble component in the pretreatment film is selectively dissolved in the stripping solution. "The solid state second highly soluble component is selectively dissolved" does not mean that only the solid state second highly soluble component is dissolved. "The solid state second highly soluble component is selectively dissolved" means that the solid state second highly soluble component is also slightly dissolved, but most of the solid state second highly soluble component is dissolved. is dissolved.

By dissolving the solid state second highly soluble component in the stripping solution, the stripping solution passes through the pretreatment film through the traces of the solid state second highly soluble component. This allows the stripping liquid to act on the contact interface between the pretreatment film and the substrate. On the other hand, the second low-solubility component in the pretreatment film is maintained in a solid state without being dissolved. Therefore, the stripping liquid can act on the contact interface between the solid second low-solubility component and the substrate while holding the first object to be removed with the solid second low-solubility component. As a result, the pretreatment film can be quickly removed from the surface of the substrate, and the first object to be removed 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 stripping step includes a second through hole forming step of partially dissolving the pretreatment film in the stripping solution to form second through holes in the pretreatment film. include.
Therefore, the stripping solution can pass through the pretreatment film via the second through-holes 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 removed from the substrate by applying the stripping liquid to 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 for processing a substrate having a surface having a first region and a second region where different materials are exposed.
The substrate processing apparatus includes a processing liquid supply unit that supplies a processing liquid to the surface of a substrate, a processing film forming unit that solidifies or hardens the processing liquid to form a processing film on the surface of the substrate, and A pretreatment liquid supply unit that supplies a pretreatment liquid, a pretreatment film forming unit that solidifies or hardens the pretreatment liquid to form a pretreatment film on the surface of the substrate, and a stripping liquid that supplies the surface of the substrate. It includes a stripping liquid supply unit, and a controller that controls the pretreatment liquid supply unit, the pretreatment film forming unit, the treatment liquid supply unit, the treatment film forming unit, and the stripping liquid supply unit.

The controller supplies the pretreatment liquid from the pretreatment liquid supply unit toward the surface of the substrate, causes the pretreatment film forming unit to solidify or harden the pretreatment liquid on the surface of the substrate, and A pretreatment film for holding an object to be removed existing on the surface of the substrate is formed on the surface of the substrate, and a stripping solution is supplied from the stripping solution supply unit to the surface of the substrate to hold the object to be removed. After removing the pretreatment film from the surface of the substrate, the treatment liquid is supplied from the treatment liquid supply unit to the surface of the substrate, and the treatment liquid is supplied to the surface of the substrate by the treatment film forming unit. by solidifying or hardening the processing liquid on the surface of the substrate to form a processing film on the surface of the substrate that retains the object to be removed existing on the surface of the substrate, and peeled from the surface of the substrate from the stripping liquid supply unit. It is programmed to supply a liquid to peel off the treatment film holding the object to be removed from the surface of the substrate.

Further, the removal force of the treatment film to remove the object to be removed existing in the second region is higher than the removal force of the pretreatment film to remove the object to be removed existing in the second region. Further, the removal force of the pretreatment film to remove the object to be removed existing in the first region is higher than the removal force of the treatment film to remove the object to be removed existing in the first region.
According to this configuration, the same effects as those of the substrate processing method described above can be obtained.

In another embodiment of the present invention, the removal 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 treatment film or the pretreatment film. and releasability, which indicates how easily the treatment film or the pretreatment film holding the object to be removed is removed. In the first region, the pretreatment film has higher releasability than the treatment film, and in the second region, the treatment film has higher holding power than the pretreatment film.

Therefore, in the first region, most of the substances to be removed can be removed by stripping the pretreatment liquid film, and in the second region, most of the substances to be removed can be removed by stripping the treatment film. Therefore, even if the substrate has a surface where different substances are exposed, 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 comprises: an information acquisition step of acquiring information about the surface of the substrate to be processed; a surface determination step of determining whether the substrate has a surface on which both a non-exposed region where the specific substance is not exposed exists and a substrate has a surface on which only the non-exposed region exists; When the surface determination step determines that only the non-exposed region exists on the surface of the substrate to be processed, a first substrate processing method is performed to remove an object to be removed from the substrate to be processed using a processing liquid. When a first recipe is selected and the surface determination step determines that both the exposed region and the non-exposed region exist on the surface of the substrate to be processed, the removal of the object to be removed from the exposed region. A second substrate processing method comprising removing the object to be removed from the substrate to be processed using a pretreatment liquid having a higher force than the processing liquid, and then removing the object to be removed from the substrate to be processed using a processing liquid. and a recipe selection step of selecting a second recipe for executing the.

It is preferable to process the substrate by different substrate processing methods for a substrate that does not have an exposed region where the specific substance is exposed on the surface and a substrate that has both an exposed region and a non-exposed region on the surface. Specifically, when only the non-exposed region exists on the surface of the substrate to be processed, if the first substrate processing method is executed to remove the object to be removed from the substrate to be processed using a processing liquid, the surface of the substrate can be removed. Objects to be removed can be sufficiently removed.

On the other hand, when there are both an exposed area and a non-exposed area on the surface of the substrate to be processed, it is sufficient to remove the object to be removed from the non-exposed area by simply removing the object to be removed from the substrate to be processed using the processing liquid. Even if it can be removed quickly, 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 non-exposed region exist on the surface of the substrate to be processed, a pretreatment liquid having a higher removal power than the processing liquid to remove the target substance from the specific substance is used. After removing the material, it is necessary to perform a second substrate processing method that removes the material to be removed from the substrate using a processing liquid.

Therefore, when only the non-exposed 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 non-exposed 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 this invention, the pretreatment liquid has a first component and a second component. The second component has a higher removal power than the first component for removing the removal target from the specific substance. In the recipe selection method, when the surface determination step determines that both the exposed region and the non-exposed region exist on the surface of the substrate to be processed, based on the information acquired by the information acquisition step, the The method further includes a type determination step of determining the type of the specific substance exposed from the surface of the substrate to be processed. Then, the recipe selection step sets the concentration of the second component in the pretreatment liquid used in the second substrate processing method according to the type of the specific substance determined by the type determination step. Selecting the second recipe.

According to this method, when both the exposed area and the non-exposed area exist on the surface of the substrate to be processed, the second recipe suitable for removing the material to be removed from the exposed area is selected according to the type of the specific substance. can be selected.

FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus according to a first embodiment of the invention. FIG. 2 is an example of a cross-sectional view of a surface layer of a 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 hardware of a controller provided in the substrate processing apparatus. FIG. 5 is a flowchart for explaining an example of substrate processing by the substrate processing apparatus. FIG. 6A is a schematic diagram for explaining the state of the pretreatment liquid supply step (step S2) of the substrate treatment. FIG. 6B is a schematic diagram for explaining the state of the pretreatment film forming step (step S3) of the substrate treatment. FIG. 6C is a schematic diagram for explaining the state of the pretreatment film forming step (step S3). FIG. 6D is a schematic diagram for explaining the state of the pretreatment film peeling step (step S4) of the substrate processing. FIG. 6E is a schematic diagram for explaining the state of the stripping solution removing step (step S5) of the substrate processing. FIG. 6F is a schematic diagram for explaining the state of the pretreatment film residue removing step (step S6) of the substrate processing. FIG. 6G is a schematic diagram for explaining the processing liquid supply step (step S7) of the substrate processing. FIG. 6H is a schematic diagram for explaining the process film forming step (step S8) of the substrate processing. FIG. 6I is a schematic diagram for explaining the process film forming step (step S8). FIG. 6J is a schematic diagram for explaining the process film stripping step (step S9) of the substrate processing. FIG. 6K is a schematic diagram for explaining the state of the stripping solution removing step (step S10) of the substrate processing. FIG. 6L is a schematic diagram for explaining the process film residue removing step (step S11) of the substrate processing. FIG. 6M is a schematic diagram for explaining the state of the spin-drying step (step S12) of the substrate processing. FIG. 7A is a schematic diagram for explaining the state near the surface of the substrate on which the pretreatment film has been formed by executing the pretreatment film forming step (step S3). FIG. 7B is a schematic diagram for explaining the state near the surface of the substrate during execution of the pretreatment film stripping step (step S4). FIG. 7C is a schematic diagram for explaining the state near the surface of the substrate on which the treated film is formed by executing the treated film forming step (step S8). FIG. 7D is a schematic diagram for explaining the state near the surface of the substrate during execution of the process film stripping step (step S9). FIG. 7E is a schematic diagram for explaining the state near the surface of the substrate after the residue of the processing film has been removed by executing the processing film residue removing step (step S11). FIG. 8A is a schematic diagram for explaining how the pretreatment film is peeled off from the substrate. FIG. 8B is a schematic diagram for explaining how the pretreatment film is peeled off from the substrate. FIG. 8C is a schematic diagram for explaining how the pretreatment film is peeled off from the substrate. FIG. 9A is a schematic diagram for explaining how the treated film is peeled off from the substrate. FIG. 9B is a schematic diagram for explaining how the treated film is peeled off from the substrate. FIG. 9C is a schematic diagram for explaining how the treated film is peeled off from the substrate. FIG. 10A is a schematic diagram for explaining how an exposed area covering portion covering an exposed area where a metal film is exposed on the surface of the substrate is removed from the substrate. FIG. 10B is a schematic diagram for explaining how the exposed area covering portion is removed from the substrate. FIG. 10C is a schematic diagram for explaining how the exposed area 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 a substrate processing apparatus according to a second embodiment of the invention. FIG. 12 is an example of a cross-sectional view of a surface layer of a substrate processed by the substrate processing apparatus according to the second embodiment. FIG. 13 is a flowchart for explaining an example of substrate processing by the substrate processing apparatus according to the second embodiment. FIG. 14A is a schematic diagram for explaining the state of the cleaning step (step S20) of substrate processing according to the second embodiment. FIG. 14B is a schematic diagram for explaining the appearance of the cleaning liquid removing step (step S21) in substrate processing according to the second embodiment. FIG. 15A is a schematic diagram for explaining the appearance of the vicinity of the surface of the substrate on which the pretreatment film is formed by executing the pretreatment film forming step (step S3) in the substrate processing according to the second embodiment. FIG. 15B is a schematic diagram for explaining the state near the surface of the substrate during execution of the pretreatment film peeling step (step S4) in the substrate processing according to the second embodiment. FIG. 15C is a schematic diagram for explaining the state of the vicinity of the surface of the substrate on which the processing film is formed by executing the processing film forming step (step S12) in the substrate processing according to the second embodiment. FIG. 15D is a schematic diagram for explaining the state near the surface of the substrate during execution of the process film peeling step (step S13) in the substrate processing according to the second embodiment. FIG. 15E is a schematic diagram for explaining the state near the surface of the substrate during execution of the cleaning step (step S20) of substrate processing according to the second embodiment. FIG. 16 shows changes in particle removal power from a copper film caused by changing the ratio of the first component and the second component of the highly soluble components 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 diagram of a first moving nozzle, a third moving nozzle, and surrounding members of a processing unit provided in a substrate processing apparatus according to a third embodiment of the present invention. FIG. 18 is a flow chart for explaining an example of recipe selection processing executed to select a recipe in the substrate processing apparatus according to the third embodiment. FIG. 19 is a flowchart for explaining another example of recipe selection processing in the substrate processing apparatus according to the third embodiment.

Embodiments of the present invention will be described below with reference to the accompanying drawings.
<First embodiment>
FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment of the invention.
The substrate processing apparatus 1 is a single-wafer type apparatus 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 plurality of processing units 2 for processing substrates W with a fluid, a load port LP on which a carrier C accommodating a plurality of substrates W to be processed by the processing units 2 is mounted, and a load port LP. , and a controller 3 for controlling the substrate processing apparatus 1 .
The transport robot IR transports the substrate W between the carrier C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing unit 2 . A plurality of processing units 2 have, for example, the same configuration. Although details will be described later, the processing fluid supplied to the substrate W in the processing unit 2 includes a rinsing liquid, a processing liquid, a pretreatment liquid, a stripping liquid, a cleaning liquid, a removing liquid, a heating medium, an inert gas (gas), and the like. is included.

Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed within the chamber 4 and performs processing on the substrate W within the processing cup 7 . The chamber 4 is formed with an entrance (not shown) through which the substrate W is loaded and unloaded by the transport robot CR. The chamber 4 is provided with a shutter unit (not shown) that opens and closes this entrance.

FIG. 2 is an example of a cross-sectional view of a surface layer of the substrate W processed by the substrate processing apparatus 1. As shown in FIG. The surface layer of the substrate W is a portion of the substrate W near the surface.
A fine uneven pattern 160 is formed on the surface of the unprocessed substrate W before being processed by the processing unit 2 . The uneven pattern 160 includes fine convex structures 161 formed on the surface of the substrate W and concave portions (grooves) 162 formed between adjacent structures 161 . The 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 (projections) and the surface of the recesses 162 form an uneven pattern surface 165 . A patterned surface 165 is included in the surface of the substrate W. FIG. The pattern surface 165 of the substrate W has regions 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 exposed regions 170 where the surface of the metal film 163 is exposed and non-exposed regions 171 where the metal film 163 is not exposed. The non-exposed region 171 is a region other than the exposed region 170 on the patterned surface 165 of the substrate W. As shown in FIG.

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

FIG. 3 is a schematic diagram for explaining a configuration example of the processing unit 2. As shown in FIG. The processing unit 2 includes a spin chuck 5 , a facing member 6 , a processing cup 7 , a first moving nozzle 9 , a second moving nozzle 10 , a third moving nozzle 11 , a central nozzle 12 , and a bottom nozzle 13 . including.
The spin chuck 5 rotates the substrate W around a vertical rotation axis A1 (vertical axis) passing through the center of the substrate W while holding the substrate W horizontally. The spin chuck 5 includes multiple 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. A plurality of chuck pins 20 for gripping the peripheral edge of the substrate W are arranged on the upper surface of the spin base 21 at intervals in the circumferential direction of the spin base 21 . The spin base 21 and the plurality of chuck pins 20 constitute a substrate holding unit that holds the substrate W horizontally. A substrate holding unit is also called a substrate holder.

The rotation shaft 22 extends vertically along the rotation axis A1. The upper end of the rotating shaft 22 is connected to the center of the lower surface of the spin base 21 . The spin motor 23 applies rotational force to the rotating shaft 22 . As the rotating shaft 22 is rotated by the spin motor 23, the spin base 21 is rotated. Thereby, 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 opposing member 6 is formed in a disc shape having a diameter substantially equal to or larger than that of the substrate W. As shown in FIG. The facing member 6 has a facing surface 6a that faces the upper surface of the substrate W (upper surface). 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 opposing member 6 on the side opposite to the opposing surface 6a. A communicating hole 6b penetrating vertically through the opposing member 6 is formed in a portion of the opposing member 6 that overlaps the rotation axis A1 in plan view. The communication hole 6 b communicates with the internal space 60 a of the hollow shaft 60 .

The facing member 6 blocks 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 facing member 6 is also called a blocking plate.
The processing unit 2 further includes an opposing member lifting unit 61 that drives the opposing member 6 to move up and down. The opposing member elevating unit 61 can vertically position the opposing member 6 at any position (height) from the lower position to the upper position. The lower position is the position where the facing surface 6a is closest to the substrate W within the movable range of the facing member 6. As shown in FIG. The upper position is the position where the facing surface 6a is farthest away from the substrate W within the movable range of the facing member 6 . The transfer robot CR can access the spin chuck 5 for loading and unloading the substrate W when the facing member 6 is positioned at the upper position.

The opposing 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 drives the ball screw mechanism. including The facing member lifting unit 61 is also called a facing member lifter (blocking plate lifter).
The processing cup 7 includes a plurality of guards 71 for receiving the liquid splashing outward from the substrate W held by the spin chuck 5, a plurality of cups 72 for receiving the liquid guided downward by the plurality of guards 71, and a plurality of cups 72 for receiving the liquid. It includes a cylindrical outer wall member 73 surrounding a guard 71 and a plurality of cups 72 .

This embodiment shows an example 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 upwardly open annular groove.

The first guard 71A is arranged to surround the spin base 21 . The second guard 71B is arranged outside the first guard 71A in the radial direction of rotation of the substrate W so as to surround the spin base 21 .
The first guard 71A and the second guard 71B each have a substantially cylindrical shape. The upper end of each guard 71 is slanted inward toward the spin base 21 .

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

Liquid splashing from the substrate W is received by the first guard 71A when both the first guard 71A and the second guard 71B are positioned at the upper position. When the first guard 71A is positioned at the lower position and the second guard 71B is positioned at the upper position, liquid splashing from the substrate W is received by the second guard 71B. When both the first guard 71A and the second guard 71B are positioned at the lower position, the transport robot CR can access the spin chuck 5 for loading and unloading the substrate W. As shown in FIG.

The guard lifting unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first guard 71A, a first motor (not shown) that provides driving force to the first ball screw mechanism, and a second ball screw mechanism (not shown). It includes a second ball screw mechanism (not shown) coupled to guard 71B and a second motor (not shown) that provides driving force to the second ball screw mechanism. The guard lifting unit 74 is also called 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 horizontally and vertically by a first nozzle moving unit 35 . The first moving nozzle 9 can move horizontally between a center position and a home position (retracted position). The first moving nozzle 9 faces the rotation center of the upper surface of the substrate W when positioned at the center position. The rotation center of the upper surface of the substrate W is the position where the upper surface of the substrate W intersects with the rotation axis A1.

When positioned at the home position, the first moving nozzle 9 does not face the upper surface of the substrate W, and is positioned outside the processing cup 7 in plan view. The first moving nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.
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 along the vertical direction, and a rotating shaft (not shown). and a rotary shaft drive unit (not shown) that raises and lowers and rotates the driving shaft.

The rotating shaft driving unit swings the arm by rotating the rotating shaft around a vertical rotating axis. Further, the rotary shaft drive unit moves the arm up and down by moving the rotary shaft vertically. The first moving nozzle 9 moves horizontally and vertically as the arm swings and moves up and down.
The first moving nozzle 9 is connected to a processing liquid pipe 40 that guides the processing liquid. When the processing liquid valve 50 interposed in the processing liquid pipe 40 is opened, the processing liquid is discharged downward from the first moving nozzle 9 in a continuous flow.

The processing 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 part of the solvent. The processing liquid solidifies or hardens on the substrate W to form a solid processing film that holds the removal target 103 present on the substrate W. FIG.
Here, "solidification" refers to solidification of the solute due to, for example, forces acting between molecules or atoms as the solvent volatilizes. "Curing" refers to the hardening of the solute due to chemical changes such as polymerization and cross-linking, for example. Thus, "solidifying or hardening" refers to the solute "hardening" due to various factors.

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

As the low-solubility component and the high-solubility component contained in the treatment liquid discharged from the first moving nozzle 9, substances having different solubilities in the stripping liquid can be used. The low-soluble component contained in the treatment liquid discharged from the first moving nozzle 9 is, for example, novolak. A highly soluble component contained in the treatment liquid discharged from the first moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane. The treatment liquid is also called a polymer-containing liquid, and the treatment film is also called a polymer film.

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

The details of the solvent, the low-soluble component, the high-soluble component, and the anti-corrosion 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 (stripping liquid supply unit) that supplies (discharges) stripping liquid such as aqueous ammonia 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 processing film holding the object 103 to be removed from the upper surface of the substrate W. FIG. Specifically, in the treatment film, only the portion covering the non-exposed region 171 is peeled off from the substrate W by the peeling liquid.

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

The second nozzle moving unit 36 has a configuration similar to that of the first nozzle moving unit 35 . That is, the second nozzle moving unit 36 includes, for example, an arm (not shown) coupled to the second moving nozzle 10 and extending horizontally, and a rotating shaft (not shown) coupled to the arm and extending along the vertical direction. and a rotating shaft driving unit (not shown) for raising and lowering the rotating shaft and rotating the rotating shaft.

The stripping liquid discharged from the second moving nozzle 10 is a liquid that dissolves the highly soluble components contained in the solute of the processing liquid more easily than the low soluble components contained in the solute of the processing liquid. The stripping liquid discharged from the second moving nozzle 10 is not limited to aqueous ammonia.
The stripping liquid discharged from the second moving nozzle 10 may be, for example, an alkaline aqueous solution (alkaline liquid) other than aqueous ammonia. Specific examples of alkaline aqueous solutions other than ammonia water include TMAH (tetramethylammonium hydroxide) aqueous solution and choline aqueous solution, and any 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 an upper stripping liquid pipe 41 that guides the stripping liquid to the second moving nozzle 10 . When the upper stripping liquid valve 51 interposed in the upper stripping liquid pipe 41 is opened, the stripping liquid is discharged downward from the outlet 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 horizontally and vertically by a third nozzle moving unit 37 . The third moving nozzle 11 can move horizontally between the center position and the home position (retracted position).

The third moving nozzle 11 faces the center of rotation of the upper surface of the substrate W when positioned at the center position. When positioned at the home position, the third moving nozzle 11 does not face the upper surface of the substrate W, but is positioned outside the processing cup 7 in plan view. The third moving nozzle 11 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.
The third nozzle moving unit 37 has a configuration similar to that of the first nozzle moving unit 35 . That is, the third nozzle moving unit 37 includes, for example, an arm (not shown) coupled to the third moving nozzle 11 and extending horizontally, and a rotating shaft (not shown) coupled to the arm and extending along the vertical direction. and a rotating shaft driving unit (not shown) for raising and lowering the rotating shaft and rotating 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 part of the solvent. The pretreatment liquid solidifies or cures on the substrate W to form a pretreatment film that retains the removal target object 103 existing on the substrate W. FIG.
The solute contained in the pretreatment liquid ejected from the third moving nozzle 11 includes a low-soluble component and a high-soluble component.

When 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. Although details will be described later, the corrosion-preventing component is, for example, BTA.
The low-solubility component and the high-solubility component contained in the pretreatment liquid can use substances having different solubilities in the stripping liquid. The low-soluble 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 liquid 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). The pretreatment liquid is also called a polymer-containing liquid, and the pretreatment film is also called a polymer film.

The solvent contained in the pretreatment liquid ejected from the third moving nozzle 11 may be any liquid that dissolves the low-soluble component and the high-soluble component. The solvent contained in the pretreatment liquid is preferably a liquid compatible with (miscible with) the stripping liquid.
The solvent contained in the pretreatment liquid is called a second solvent, and the solute contained in the pretreatment liquid is called a second solute. A low-solubility component contained in the treatment liquid is referred to as a second low-solubility component, and a high-solubility component contained in the treatment liquid is referred to as a second high-solubility component.

Details of the solvent, the low-soluble component, the high-soluble component, and the anti-corrosion 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 non-exposed region 171 are removed from the substrate W by the remover.
The removal force with which the polymer film such as the treatment film or the pretreatment film removes the object 103 to be removed varies depending on whether the object 103 is removed from the exposed region 170 or from the non-exposed region 171 . and markedly different.

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

Although the pretreatment film exhibits high retention of material to be removed in both the unexposed regions 171 and the exposed regions 170, the treated film has even higher removal than the pretreated film in both the non-exposed regions 171 and the exposed regions 170. Exhibits object holding power. On the other hand, the pretreatment film has higher releasability than the treatment film in the exposed region 170 . Therefore, in the exposed region 170 , the pretreatment film exerts a higher removing force than the treated film, and in the non-exposed region 171 , the treated film exerts a higher removing force than the pretreated film.

Specifically, the removal force of the treatment film to remove the object 103 to be removed existing in the non-exposed region 171 is higher than the removal force of the pretreatment film to remove the object 103 to be removed existing in the non-exposed region 171 . The removal force of the pretreatment film to remove the object 103 to be removed existing in the exposed region 170 is higher than the removal force of the treatment film to remove the object 103 to be removed existing in the exposed region 170 .
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 outlet of the third moving nozzle 11 in a continuous flow.

The central nozzle 12 is accommodated in the internal space 60a of the hollow shaft 60 of the opposing member 6. As shown in FIG. A discharge port 12a provided at the tip of the central nozzle 12 faces the central region of the upper surface of the substrate W from above. The central region of the upper surface of the substrate W is the region including the center of rotation of the substrate W and its periphery on the upper surface of the substrate W. As shown in FIG.
The central nozzle 12 includes a plurality of tubes (a first tube 31, a second tube 32 and a third tube 33) for discharging fluid downward, and a tubular casing 30 surrounding the plurality of tubes. A plurality of tubes and casings 30 extend vertically along the rotation axis A1. The outlet 12 a of the central nozzle 12 is also the outlet of the first tube 31 , the outlet of the second tube 32 , and the outlet of the third tube 33 .

The first tube 31 (central nozzle 12) is an example of a rinse liquid supply unit that supplies a rinse liquid such as DIW to the upper surface of the substrate W. As shown in FIG. The second tube 32 (central nozzle 12) is an example of a removing liquid supply unit that supplies a removing liquid such as IPA to the upper surface of the substrate W. As shown in FIG. The third tube 33 (central nozzle 12 ) is an example of a gas supply unit that supplies gas such as nitrogen gas (N ₂ ) between the upper surface of the substrate W and the opposing surface 6 a of the opposing member 6 . The central nozzle 12 is a rinse liquid nozzle, a remover liquid nozzle, and a gas nozzle.

The first tube 31 is connected to an 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 discharged in a continuous flow from the first tube 31 (central nozzle 12) toward the central region of the upper surface of the substrate W. .
Examples of the rinsing liquid include DIW, carbonated water, electrolyzed ion water, hydrochloric acid water with a dilution concentration (for example, about 1 ppm to 100 ppm), ammonia water with a dilution concentration (for example, about 1 ppm to 100 ppm), reduced water (hydrogen water), and the like. mentioned.

The second tube 32 is connected to a removing liquid pipe 44 that guides the removing liquid to the second tube 32 . When the removing liquid valve 54 interposed in the removing liquid pipe 44 is opened, the removing liquid is discharged from the second tube 32 (central nozzle 12) toward the central region of the upper surface of the substrate W in a continuous flow.
The removal liquid discharged from the second tube 32 removes the portion of the processing film that was not removed from the upper surface of the substrate W by the remover, and the portion of the pretreatment film that was not removed from the upper surface of the substrate W by the remover. It is a liquid for The removal liquid is preferably a liquid with higher volatility than the rinse liquid. The removal liquid discharged from the second tube 32 preferably has compatibility with the rinse liquid.

The removal 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. and the like.

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

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

The lower surface nozzle 13 is inserted into a through hole 21 a that opens at the center of the upper surface of the spin base 21 . The ejection port 13 a 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 bottom surface of the substrate W is the region including the center of rotation of the substrate W on the bottom surface of the substrate W. As shown in FIG.

One end of a common pipe 80 that commonly guides the rinsing liquid, stripping liquid, and heat medium to the lower nozzle 13 is connected to the lower nozzle 13 . At the other end of the common pipe 80, there are a lower rinse liquid pipe 81 that guides the rinse liquid to the common pipe 80, a lower remover pipe 82 that guides the remover solution to the common pipe 80, and a heat medium to the common pipe 80. A guiding heat medium pipe 83 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 stripping liquid valve 87 interposed in the lower stripping liquid pipe 82 is opened, the stripping 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 bottom surface nozzle 13 toward the central area of the bottom 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. As shown in FIG. Further, the bottom surface nozzle 13 is an example of a bottom stripping liquid supply unit that supplies the stripping liquid to the bottom surface of the substrate W. As shown in FIG. Further, the lower surface nozzle 13 is an example of a heat medium supply unit that supplies the substrate W with a heat medium for heating the substrate W. As shown in FIG. The lower surface nozzle 13 is also a substrate heating unit that heats the substrate W. As shown in FIG.

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

FIG. 4 is a block diagram showing the hardware of the controller 3. As shown in FIG. The controller 3 is a computer including a computer main body 3a and peripheral devices 3d connected to the computer main body 3a. The computer main body 3a includes a CPU 3b (central processing unit) that executes various commands, 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 medium RM, and a communication device 3g that communicates with other devices such as a host computer.

Controller 3 is connected to input device 3A, display device 3B, and alarm device 3C. The input device 3</b>A is operated when an operator such as a user or a person in charge of maintenance inputs information to the substrate processing apparatus 1 . Information is displayed on the screen of the display device 3B. The input device 3A may be any one of a keyboard, pointing device, and touch panel, or may be a device other than these. The substrate processing apparatus 1 may be provided with a touch panel display that serves as both the input device 3A and the display device 3B. The alarm device 3C issues an alarm using one or more of light, sound, characters, 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 medium RM to the auxiliary storage device 3e through the reading device 3f, or may be stored in the host computer. 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 removable media RM are nonvolatile memories that retain data even when power is not supplied. The auxiliary storage device 3e is, for example, a magnetic storage device such as a hard disk drive. The removable medium RM is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a tangible recording medium that is not temporary.

The auxiliary storage device 3e stores a plurality of recipes R. The recipe R is information that defines the processing content, processing conditions, and processing procedure of the substrate W. FIG. The plurality of recipes R differ from each other in at least one of the processing content of the substrate W, the processing conditions, and the processing procedure.
The controller 3 controls the substrate processing apparatus 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 apparatus 1 . In other words, controller 3 is programmed to perform the following steps.

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

First, an unprocessed substrate W is transferred from the carrier C to the processing unit 2 by the transfer robots IR and CR (see FIG. 1) and transferred to the spin chuck 5 (step S1). Thereby, the substrate W is horizontally held by the spin chuck 5 (substrate holding step). The substrate W is held by the spin chuck 5 so that the pattern surface 165 faces upward. When the substrate W is loaded, the facing member 6 is retracted to the upper position.

The holding of the substrate W by the spin chuck 5 is continued until the spin dry process (step S12) is completed. The guard lifting unit 74 moves the first guard 71A and the second guard so that at least one guard 71 is positioned at the upper position from the start of the substrate holding process to the end of the spin dry process (step S12). Adjust the height position of 71B.
Next, after the transfer robot CR is withdrawn from 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 . Thereby, the horizontally held substrate W is rotated (substrate rotation step).

The third nozzle moving unit 37 moves the third moving nozzle 11 to the processing position while the opposing member 6 is positioned 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 substrate W in the rotating state (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 continues for a predetermined period of time, eg, 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, a pretreatment film forming step (step S3) is performed. 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) holding the removal target object 103 present on the substrate W is formed on the substrate W. formed on the top surface.

In the pretreatment film forming step, first, a pretreatment liquid thinning step (pretreatment liquid spin-off step) for thinning the liquid film 201 of the pretreatment liquid on the substrate W is performed. 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 process, the supply of the pretreatment liquid to the upper surface of the substrate W is stopped so that the liquid film 201 on the substrate W has an appropriate thickness. Part of the pretreatment liquid is removed from the upper surface of the substrate W by centrifugal force in this state.

Even after the third moving nozzle 11 has moved to the home position, the opposing member 6 is maintained at 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 speed 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 pretreatment liquid thinning step. The pretreatment liquid thinning process is performed 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 is performed to partially evaporate (volatilize) the solvent from the liquid film 201 of the pretreatment liquid. In the pretreatment liquid solvent evaporation step, the liquid film 201 on the substrate W is heated in order to partially evaporate the solvent of the pretreatment liquid on the substrate W. FIG.
Specifically, as shown in FIG. 6C, the facing member lifting unit 61 moves the facing member 6 to the close position between the upper position and the lower position. The proximate position may be the down position. The close position is a position where the distance from the upper surface of the substrate W to the opposing surface 6a is, for example, 1 mm.

Then the gas valve 55 is opened. Thereby, the 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 blowing the gas onto the liquid film 201 on the substrate W, evaporation (volatilization) of the solvent in the liquid film 201 is promoted (pretreatment liquid solvent evaporation process, pretreatment liquid solvent evaporation promotion process). Therefore, the time required to form the pretreatment film 200 (see FIG. 7A) can be shortened. The central nozzle 12 functions as an evaporation unit (evaporation acceleration 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 bottom surface nozzle 13 toward the central region of the bottom surface of the substrate W in the rotating state (heat medium supply process, heat medium discharge process). The heat medium supplied from the bottom surface nozzle 13 to the bottom surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire bottom surface of the substrate W. FIG. The supply of the heat medium to the substrate W continues for a predetermined time, eg, 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 heating medium to the lower surface of the substrate W, the liquid film 201 on the substrate W is heated through the substrate W. As shown in FIG. This promotes the evaporation (volatilization) of the solvent in the liquid film 201 (pretreatment liquid solvent evaporation process, pretreatment liquid solvent evaporation promotion process). Therefore, the time required to form the pretreatment film 200 (see FIG. 7A) can be shortened. The lower surface nozzle 13 functions as an evaporation unit (evaporation acceleration unit) that evaporates (evaporates) the solvent in the pretreatment liquid.

By performing the pretreatment liquid film thinning step and the pretreatment liquid film solvent evaporation step, the pretreatment liquid is solidified or cured to form a pretreatment film 200 (see FIG. 7A) on the substrate W. . Thus, the substrate rotation unit (spin motor 23), the central nozzle 12 and the bottom nozzle 13 form a pretreatment film forming unit (film formation unit) that solidifies or hardens the pretreatment liquid to form the pretreatment film 200 (solid film). formation unit).

In the pretreatment liquid solvent evaporation step, the substrate W is preferably heated such 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 film 200 . Therefore, in the subsequent pretreatment film stripping step (step S4), the stripping solution is more easily absorbed into the pretreatment film 200 compared to the case where no solvent remains in the pretreatment film 200 .

Next, a pretreatment film stripping step (step S4) for stripping the pretreatment film 200 is performed. Specifically, the heat medium valve 88 is closed. Thereby, 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 opposing member 6 is positioned at the upper position. The processing position of the second moving nozzle 10 is, for example, the central position.

Then, the upper stripping liquid valve 51 is opened while the second moving nozzle 10 is positioned at the processing position. As a result, as shown in FIG. 6D, the stripping liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the substrate W in the rotating state (upper stripping liquid supply step, upper stripping liquid discharging step). 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 discharged outside the substrate W together with the peeling liquid. In the pretreatment film peeling process, the substrate W is rotated at a predetermined pretreatment film peeling rotation speed, for example, 800 rpm.

At the same time when the upper stripping liquid valve 51 is opened, the lower stripping liquid valve 87 is opened. As a result, the stripping liquid is supplied (discharged) from the bottom nozzle 13 toward the central region of the bottom surface of the substrate W in the rotating state (lower stripping liquid supply process, lower stripping liquid discharging process). 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. In addition, the pretreatment liquid scattered from the substrate W may rebound from the guard 71 and adhere to the lower surface of the substrate W. As shown in FIG. Even in such a case, as shown in FIG. 6C, since the heating medium is supplied to the lower surface of the substrate W in the pretreatment film forming step, the flow of the heating medium causes the pretreatment liquid to flow from the lower surface of the substrate W. can be eliminated.

Furthermore, 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 stripping liquid is being supplied to the top surface of the substrate W in the pretreatment film stripping step (step S4), the stripping liquid is supplied (discharged) to the bottom surface of the substrate W from the bottom nozzle 13. Therefore, even if solids of the pretreatment liquid are formed on the bottom surface of the substrate W, the solids can be separated from the bottom surface of the substrate W and removed.

After the pretreatment film stripping step (step S4), a stripping liquid removing step (step S5) is performed to remove (rinse) the stripping liquid from the substrate W by supplying a rinse liquid. Specifically, the upper stripping liquid valve 51 and the lower stripping liquid valve 87 are closed. Thereby, the supply of the stripping liquid to the upper and lower surfaces 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 opposing member elevating unit 61 moves the opposing member 6 to the processing position.

Then, the upper rinse liquid valve 53 is opened while the opposing member 6 is positioned at the processing position. As a result, the rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the substrate W in the rotating state (upper rinse liquid supply process, upper rinse liquid discharge process).
In the stripping solution removing step, the substrate W is rotated at a predetermined stripping solution removing rotation speed, for example, 800 rpm. The processing position is a position spaced above the upper surface of the substrate W from the proximity position. When the facing member 6 is positioned 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 due to 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).
At the same time when 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 substrate W in the rotating state (lower rinse liquid supply process, lower rinse liquid discharge process). As a result, the stripping liquid adhering to the bottom surface of the substrate W is washed away with the rinse liquid. The supply of the rinsing liquid to the upper and lower surfaces of the substrate W continues for a predetermined time, eg, 35 seconds.

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

The removal 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 shown in FIG. As a result, the rinse liquid on the upper surface of the substrate W is replaced with the remover liquid. The removal 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. FIG.
Next, a processing liquid supply step (step S7) of supplying the processing liquid onto the upper surface of the substrate W is performed. Specifically, the first nozzle moving unit 35 moves the first moving nozzle 9 to the processing position while the opposing member 6 is positioned 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 substrate W in the rotating state (processing liquid supply process, processing liquid discharge process). . As a result, a liquid film 101 (processing liquid film) of the processing liquid is formed on the substrate W (processing liquid film forming step).

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

In the process film forming process, first, a process liquid thinning process (process liquid spin-off process) for thinning the liquid film 101 of the process liquid on the substrate W is performed. Specifically, the processing 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 processing liquid thinning process, the supply of the processing liquid to the upper surface of the substrate W is stopped so that the thickness of the liquid film 101 on the substrate W becomes appropriate. Part of the processing liquid is expelled from the upper surface of the substrate W by centrifugal force. Even after the first moving nozzle 9 has moved to the home position, the facing member 6 is maintained at the upper position.

In the processing liquid thinning step, the spin motor 23 changes the rotation speed of the substrate W to a predetermined processing liquid thinning speed. The treatment liquid thinning speed 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 processing liquid thinning step. The treatment liquid thinning process is performed 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 is performed to evaporate (volatilize) part of the solvent from the treatment liquid film 101 . In the process liquid solvent evaporation step, the liquid film 101 on the substrate W is heated in order to partially evaporate the solvent of the process liquid on the substrate W. FIG.
Specifically, as shown in FIG. 6I, the facing member lifting unit 61 moves the facing member 6 to the close position.

Then the gas valve 55 is opened. Thereby, the 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 blowing the gas onto the liquid film 101 on the substrate W, evaporation (volatilization) of the solvent in the liquid film 101 is promoted (treatment liquid solvent evaporation process, treatment liquid solvent evaporation promotion process). Therefore, the time required to form the treatment film 100 (see FIG. 7C) can be shortened. Also in the treatment film forming process, the central nozzle 12 functions as an evaporation unit (evaporation promotion unit) that evaporates 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 bottom surface nozzle 13 toward the central region of the bottom surface of the substrate W in the rotating state (heat medium supply process, heat medium discharge process). The heat medium supplied from the bottom surface nozzle 13 to the bottom surface of the substrate W receives centrifugal force and spreads radially, and spreads over the entire bottom surface of the substrate W. FIG. The supply of the heat medium to the substrate W continues for a predetermined time, eg, 60 seconds. In the process liquid solvent evaporation step, the substrate W is rotated at a predetermined evaporation rotation speed, eg, 1000 rpm.

The liquid film 101 on the substrate W is heated through the substrate W by supplying the heating medium to the lower surface of the substrate W. As shown in FIG. As a result, the evaporation (volatilization) of the solvent in the liquid film 101 is promoted (treatment liquid solvent evaporation process, treatment liquid solvent evaporation promotion process). Therefore, the time required to form the treatment film 100 (see FIG. 7C) can be shortened. Also in the treatment film forming process, the bottom nozzle 13 functions as an evaporation unit (evaporation acceleration unit) that evaporates (volatilizes) the solvent in the treatment liquid.

The treatment liquid is solidified or hardened by executing the treatment liquid thinning process and the treatment liquid solvent evaporation process. As a result, the processing film 100 holding the object to be removed 103 is formed over the entire upper surface of the substrate W. Next, as shown in FIG. Thus, the substrate rotating unit (spin motor 23), the central nozzle 12, and the bottom nozzle 13 are treated film forming units (film forming units) that form the treated film 100 (solid film) by solidifying or hardening the treatment liquid. constitutes

In the processing liquid solvent evaporation step, the substrate W is preferably heated such that the temperature of the processing liquid on the substrate W is less 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 film 100 . This makes it easier for the stripping solution to blend into the processing film 100 in the subsequent processing film stripping step (step S9), compared to the case where the solvent does not remain in the processing film 100 .

Next, a process film stripping step (step S9) is performed for stripping the process film 100 with a stripping solution. Specifically, the heat medium valve 88 is closed. Thereby, 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 opposing member 6 is positioned at the upper position.

Then, the upper stripping liquid valve 51 is opened while the second moving nozzle 10 is positioned at the processing position. As a result, as shown in FIG. 6J, the stripping liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the substrate W in the rotating state (upper stripping liquid supply step, upper stripping liquid discharging step). 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 discharged outside the substrate W together with the peeling liquid. In the process film stripping process, the substrate W is rotated at a predetermined process film stripping rotation speed, for example, 800 rpm.

At the same time when the upper stripping liquid valve 51 is opened, the lower stripping liquid valve 87 is opened. As a result, the stripping liquid is supplied (discharged) from the bottom nozzle 13 toward the central region of the bottom surface of the substrate W in the rotating state (lower stripping liquid supply process, lower stripping liquid discharging process). 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 in 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, the processing liquid can be removed from the bottom surface of the substrate W by the flow of the heat medium supplied to the bottom surface of the substrate W, as shown in FIG. 6I.

Furthermore, like 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, since the stripping liquid is supplied (discharged) to the bottom surface of the substrate W as shown in FIG. 6J, the solid can be stripped from the bottom surface of the substrate W and removed.
After the treatment film stripping step (step S9), a stripping solution removing step (step S10) is performed to remove (rinse) the stripping solution from the substrate W by supplying a rinse solution. Specifically, the upper stripping liquid valve 51 and the lower stripping liquid valve 87 are closed. As a result, the supply of the stripping liquid to the upper and lower surfaces 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 opposing member elevating unit 61 moves the opposing member 6 to the processing position.

Then, the upper rinse liquid valve 53 is opened while the opposing member 6 is positioned at the processing position. As a result, the rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the substrate W in the rotating state (upper rinse liquid supply process, upper rinse liquid discharge process).
In the stripping solution removing step, the substrate W is rotated at a predetermined stripping solution removing rotation speed, for example, 800 rpm. The processing position is a position spaced 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 due to 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).

At the same time when 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 substrate W in the rotating state (lower rinse liquid supply process, lower rinse liquid discharge process). As a result, the stripping liquid adhering to the bottom surface of the substrate W is washed away with the rinse liquid. The supply of the rinsing liquid to the upper and lower surfaces of the substrate W continues for a predetermined time, eg, 35 seconds.

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

The removal 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 shown in FIG. As a result, the rinse liquid on the upper surface of the substrate W is replaced with the remover liquid. The removal liquid supplied to the upper surface of the substrate W dissolves the residue of the processing film 100 remaining on the upper surface of the substrate W, and then is discharged from the peripheral edge of the upper surface of the substrate W. FIG.
Next, a spin dry process (step S12) is performed to dry the upper surface of the substrate W by rotating the substrate W at high speed. Specifically, the removal liquid valve 54 is closed. Thereby, the supply of the removing liquid to the upper surface of the substrate W is stopped. Then, as shown in FIG. 6M, the opposing member elevating unit 61 moves the opposing member 6 to the drying position below the processing position. When the opposing member 6 is located at the drying position, the distance between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is 1.5 mm, for example. Then the gas valve 55 is opened. Thereby, the gas is supplied to the space between the upper surface of the substrate W and the facing surface 6 a 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 dry process is rotated at a drying speed, eg, 1500 rpm. The spin dry process is performed for a predetermined time, eg, 30 seconds. Thereby, 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 process, the supply of gas to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6 accelerates the evaporation of the removing liquid.

Then, the spin motor 23 stops the substrate W from rotating. The guard lifting unit 74 moves the first guard 71A and the second guard 71B to the lower position. Gas valve 55 is closed. Then, the facing member elevating unit 61 moves the facing member 6 to the upper position.
The transport robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S13). The substrate W is transferred from the transport robot CR to the transport robot IR and stored in the carrier C by the transport robot IR.

In the spin-drying process of the 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 with the remover 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. As shown in FIG. That is, since the spin-drying process is performed after being replaced with IPA, which has a lower surface tension than DIW, the uneven pattern 160 (see FIG. 2) on the upper surface of the substrate W is affected when the upper surface of the substrate W is dried. can reduce the surface tension.

Next, the state of the vicinity of the upper surface of the substrate W during substrate processing will be described. 7A to 7E are schematic diagrams for explaining the state of the vicinity of the upper surface of the substrate W during substrate processing.
FIG. 7A is a schematic diagram for explaining the state of the vicinity of the upper surface of the substrate W on which the pretreatment film 200 is formed by executing the pretreatment film forming step (step S3). The pretreatment film 200 holds the removal target 103 as shown in FIG. 7A.

When the stripping solution is supplied to the top surface of the substrate W on which the pretreatment film 200 is formed, the stripping action of the stripping solution removes the pretreatment film 200 from the top surface of the substrate W together with the object to be removed 103 as shown in FIG. 7B. peeled off. The pretreatment film 200 splits into film pieces 205 when separated from the upper surface of the substrate W. As shown in FIG.
After the pretreatment film 200 is removed, the stripping solution is continuously supplied to the upper surface of the substrate W, so that the split film pieces 205 of the pretreatment film 200 are removed from the substrate W together with the stripping solution. As a result, the film piece 205 of the pretreatment film 200 holding the object 103 to be removed is removed from the upper surface of the substrate W. FIG.

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

After that, as shown in FIG. 7C, a treatment film 100 that holds the removal target 103 is formed. Since the treatment film 100 has a higher object-to-be-removed holding force than the pretreatment film 200 to hold the object-to-be-removed 103 existing in the non-exposed region 171 , it can hold the object-to-be-removed 103 . When the stripping solution is supplied to the top surface of the substrate W on which the processing film 100 is formed, the processing film 100 is stripped from the top surface of the substrate W together with the object to be removed 103 by the stripping action of the stripping solution, as shown in FIG. 7D. be. The treatment film 100 splits into film pieces 105 when peeled off from the upper surface of the substrate W. As shown in FIG.

The treatment film 100 has a high removal power for removing the removal target 103 present in the non-exposed region 171 . Therefore, in the pretreatment film stripping step (step S4), even if the object to be removed 103 that could not be removed by the pretreatment film 200 exists on the non-exposed region 171 (see FIG. 7B), the treatment film stripping process is performed. The object to be removed 103 can be removed from the substrate W by executing the step (step S9).

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

Next, how the pretreatment film 200 is peeled off will be described with reference to FIGS. 8A to 8C.
The pretreatment film 200 holds the removal target 103 as shown in FIG. 8A. Specifically, the pretreatment film 200 has a high-solubility solid 210 (second high-solubility component in solid state) and a low-solubility solid 211 (second low-solubility component in solid state). High solubility solids 210 and low solubility solids 211 are formed by evaporation of at least a portion of the solvent contained in the pretreatment liquid.

In the pretreatment film 200, a highly soluble solid 210 and a low soluble solid 211 are mixed in a single layer. Strictly speaking, in the pretreatment film 200, the highly soluble solids 110 and the lowly soluble solids 111 are not evenly distributed throughout the pretreatment film 200, and the highly soluble solids 210 are unevenly distributed. There are portions and portions where the low-soluble solids 211 are unevenly distributed.
The pretreatment film 200 has a mixed structure in a single layer regardless of the region (location) on the upper surface of the substrate W where the pretreatment film 200 is formed. In other words, the pretreatment film 200 has a mixed structure within a single layer in both the exposed region 170 and the non-exposed region 171 .

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

The solubility of the low-solubility component in the stripping liquid is low, and the low-solubility solid 211 is hardly dissolved by the stripping liquid. Therefore, the low-soluble solid 211 is only slightly dissolved near the surface by the stripping liquid. Therefore, the stripping liquid reaching the vicinity of the upper surface (pattern surface 165 ) of the substrate W through the through-holes 202 slightly dissolves the portion of the low-dissolving solid 211 in the vicinity of the upper surface of the substrate W. As a result, as shown in the enlarged view of FIG. 8B, the stripping liquid gradually dissolves the low-solubility solid 211 near the upper surface of the substrate W, while the gap G2 between the pretreatment film 200 and the upper surface of the substrate W is removed. (stripping solution entering step).

Then, for example, the pretreatment film 200 splits starting from the periphery of the through-hole 202 to form film pieces 205, and as shown in FIG. It is peeled off from the substrate W in this state (pretreatment film splitting step, peeling step). Then, by continuing the supply of stripping solution, the pretreatment film 200 formed into film pieces 205 is washed away (extruded out of the substrate W) while holding the object 103 to be removed. is removed from the upper surface of the object (removal object removal step).

How the treatment film 100 is peeled off will be described in detail with reference to FIGS. 9A to 9C. 9A to 9C are schematic diagrams for explaining how the portion of the treatment film 100 covering the non-exposed region 171 (the non-exposed region covering portion 131) is peeled off from the non-exposed region 171. FIG.
The treatment film 100 holds a removal target 103 as shown in FIG. 9A. Specifically, the portion of the treated film 100 that covers the non-exposed region 171 is composed of a highly soluble solid 110 (first highly soluble component in solid state) and a low soluble solid 111 (first low soluble component in solid state). ) and The highly soluble solids 110 and the lowly soluble solids 111 are formed by evaporating at least part of the solvent contained in the treatment liquid.

In the non-exposed area covering portion 131, the high solubility solid 110 and the low solubility solid 111 are mixed in a single layer. Strictly speaking, in the non-exposed area covering portion 131, the highly soluble solids 110 and the lowly soluble solids 111 are not evenly distributed over the entire treatment film 100, and the highly soluble solids 110 are unevenly distributed. and a portion where the low-soluble solid 111 is unevenly distributed.

Referring to FIG. 9B, highly soluble solids 110 are dissolved due to the supply of stripping liquid. That is, the non-exposed area covering portion 131 is partially dissolved. By dissolving the highly soluble solids 110, the through holes 102 are formed in the portions where the highly soluble solids 110 are unevenly distributed in the non-exposed region covering portion 131 (through hole forming step).
The through-holes 102 are particularly likely to be formed in the portion where the highly soluble solid 110 extends in the normal direction T of the pattern surface 165 (also the thickness direction of the treatment film 100). The through-hole 102 has a diameter of, for example, several nanometers in 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-soluble solid 111 is only slightly dissolved near the surface by the stripping liquid. 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-soluble solid 111 in the vicinity of the upper surface of the substrate W. FIG. As a result, as shown in the enlarged view of FIG. 9B, the stripping liquid gradually dissolves the low-solubility solid 111 near the upper surface of the substrate W, while removing the space between the non-exposed area covering portion 131 and the upper surface of the substrate W. It enters the gap G1 (stripping solution entering step).

Then, for example, the non-exposed area covering portion 131 splits starting from the periphery of the through-hole 102 to form film pieces 105, and as shown in FIG. It is peeled from the substrate W while being held (processing film splitting process, peeling process). Then, by continuing the supply of the peeling liquid, the non-exposed region covering portion 131 that has become the film piece 105 is washed away (pushed out of the substrate W) while holding the removal target object 103 . It is removed from the upper surface of the substrate W (removal object removal step).

9A to 9C, the step of partially dissolving the non-exposed region covering portion 131 of the treatment film 100 to form the through hole 102 is an example of the first through hole forming step. The through-hole 102 that is formed is an example of the first through-hole. 8A to 8C, the step of partially dissolving pretreatment film 200 to form through-holes 202 is an example of the second through-hole forming step. 202 is an example of a second through hole.

Next, the removal of the exposed area covering portion 130 covering the exposed area 170 will be described in detail with reference to FIGS. 10A to 10C. 10A to 10C are schematic diagrams for explaining how the exposed area covering portion 130 is removed from the upper surface of the substrate W. FIG.
As described above, most of the objects to be removed 103 are removed from the exposed region 170 by the pretreatment film stripping step (step S4), but the objects to be removed 103 are also exposed when the treatment film 100 is formed. A small amount may be present in region 170 .

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

The highly soluble solids 110 are dissolved in the stripping solution, but the lowly soluble solids 111 are hardly dissolved in the stripping solution. Therefore, when the stripping solution is supplied to the upper surface of the substrate W in the process 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, although the surface of the low-solubility layer 180 is slightly dissolved, it does not expose the metal film 163 and remains in a state of covering the exposed region 170 . Therefore, it is difficult for the peeling liquid to enter between the low-soluble layer 180 and the upper surface of the substrate W. As shown in FIG. Accordingly, the low-solubility layer 180 of the protective film 100B remains on the exposed region 170 without being stripped by the stripping solution. Therefore, the treatment film 100 has lower releasability than the pretreatment 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 process film residue removing step (step S8), the exposed area covering portion 130 is dissolved in the removing liquid. When the exposed area covering portion 130 is dissolved by the removing liquid, the object to be removed 103 is separated from the exposed area 170 and floats in the removing liquid, as shown in FIG. 10C. Therefore, by continuing to supply the removal liquid, the removal target object 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 object to be removed 103 is removed from the upper surface of the substrate W by peeling the pretreatment film 200 having a high removal force for removing the object to be removed 103 existing in the exposed region 170 (first region). be. After that, the object to be removed 103 is removed from the upper surface of the substrate W by peeling off the processing film 100 having a high removal force for removing the object to be removed 103 existing in the non-exposed region 171 (second region). That is, the stripping of the pretreatment film 200 with a relatively high removal force for removing the removal object 103 existing in the exposed region 170 and the treatment with a relatively high removal force for removing the removal object 103 existing in the non-exposed region 171 are performed. Both the stripping of the membrane 100 is performed. More simply, the object 103 to be removed is removed in two stages using the pretreatment film 200 and the treatment film 100 having different areas with high removal power for removing the object 103 to be removed.

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 non-exposed region 171 other than the exposed region 170 exist.
Further, according to the first embodiment, after the processing film stripping step (step S9), the removal liquid is supplied to the upper surface of the substrate W to remove the residue of the processing film 100 remaining on the upper surface of the substrate W. A removal step (step S11) is performed. Therefore, even if a residue of the processing film 100 adheres to the exposed region 170 and the non-exposed region 171 after the processing film 100 is stripped by the stripping liquid, the residue can be removed by the stripping liquid. .

Further, according to the first embodiment, in the treatment film removing step, the non-exposed area covering portion 131 is removed without removing the exposed area covering portion 130 . Then, in the processing film residue removing step, the exposed area covering portion 130 is removed as a residue of the processing film 100 .
Therefore, even if the exposed area covering part 130 is not peeled off by supplying the stripping liquid to the upper surface of the substrate W and remains on the exposed area 170, the exposed area covering part 130 is dissolved in the removing liquid and the exposed area 170 is removed. can be removed from

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

Therefore, even in the configuration in which the exposed area covering part 130 is dissolved in the removing liquid to remove the exposed area covering part 130 from the exposed area 170 , it is possible to sufficiently prevent the object to be removed 103 from remaining in the exposed area 170 . can be done.
Further, according to the first embodiment, in the non-exposed region covering portion 131 of the treatment film 100, the highly soluble solids 110 and the lowly soluble solids 111 are mixed in a single layer. Then, in the treatment film stripping 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 area 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, the vicinity of the interface between the treatment film 100 and the non-exposed region 171 on the surface of the substrate W can be quickly reached.
On the other hand, the low-solubility solid 111 in the non-exposed area covering portion 131 is maintained in a solid state without being dissolved. Therefore, the stripping liquid can act on the contact interface between the low-solubility solid 111 and the substrate W while holding the removal target 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 can be efficiently removed from the upper surface of the substrate W together with the non-exposed region covering portion 131 of the processing film 100 .

Further, according to the first embodiment, the pretreatment film 200 contains a mixture of highly soluble solids 110 and lowly soluble solids 111 . The highly soluble solids 210 in the pretreatment film 200 are selectively dissolved by the stripping solution. By dissolving the highly soluble solids 210 in the stripping liquid, the stripping liquid passes through the pretreatment film 200 through the traces (through holes 202) where the highly soluble solids 210 existed. Thereby, the vicinity of the interface between the pretreatment film 200 and the upper surface of the substrate W can be quickly reached.

On the other hand, the low-solubility solid 211 in the pretreatment film 200 is maintained in a solid state without being dissolved. Therefore, the stripping liquid can act on the contact interface between the low-solubility solid 211 and the substrate W while holding the removal target 103 with 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 can be efficiently removed from the upper surface of the substrate W together with the pretreatment film 200 .

"Highly soluble solids 110, 210 are selectively dissolved" does not mean that only highly soluble solids 110, 210 are dissolved. "Highly soluble solids 110, 210 are selectively dissolved" means that most of the highly soluble solids 110, 210 are dissolved, although the lowly soluble solids 111, 211 are also slightly dissolved. is.
Moreover, the metal film 163 whose surface is exposed in the exposed region 170 is not limited to a copper film. 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. Moreover, the film whose surface is exposed in the exposed region 170 may not 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 if the substrate in which the specific material exposed in the exposed region 170 is a metal other than copper or a nitride is subjected to the substrate processing according to the above-described embodiments, the same effects as those of the above-described embodiments can be obtained.

<Second embodiment>
FIG. 11 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit 2 provided in a substrate processing apparatus 1P according to the second embodiment. In FIG. 11, the same reference numerals as those in FIG. 1 etc. are attached to the same configurations as those shown in FIGS. Similarly, in FIGS. 12 to 15E, which will be described later, the same reference numerals as in FIG.

11, the substrate processing apparatus 1P according to the second embodiment mainly differs from the substrate processing apparatus 1 (see FIG. 3) according to the first embodiment in that In 1P, the substrate processing is performed on the substrate W that has been subjected to the dry etching processing.
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. The substrate W has the first removal object 203 attached to both the non-exposed region 171 and the exposed region 170 . A first removal object 203 is a residue generated by the dry etching process in the previous step. The first object to be removed 203 is granular residue (granular residue). It is a reactant between 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 object to be removed 104 adheres to the non-exposed region 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 part of the non-exposed region 171 . In the example of FIG. 12, the second object to be removed 204 covers the surface of the low dielectric constant interlayer insulating film 161B. The second object to be removed 104 is a reaction product between the etching gas and the low dielectric constant interlayer insulating film 161B.

Referring to FIG. 11 , processing unit 2 according to the second embodiment includes fourth moving nozzle 14 . The fourth moving nozzle 14 is an example of a cleaning liquid nozzle (cleaning liquid supply unit) that continuously supplies (discharges) a cleaning liquid such as SC1 toward the upper surface of the substrate W held by the spin chuck 5 . The cleaning liquid is a liquid for removing from the upper surface of the substrate W by dissolving the second removal object 204 that cannot be separated from the upper surface of the substrate W with the removing liquid.

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

The fourth nozzle moving unit 38 has a configuration similar to that of the first nozzle moving unit 35 . That is, the fourth nozzle moving unit 38 includes, for example, an arm (not shown) coupled to the fourth moving nozzle 14 and extending horizontally, and a rotating shaft (not shown) coupled to the arm and extending along the vertical direction. and a rotating shaft driving unit (not shown) for raising and lowering the rotating shaft and rotating the rotating shaft.

The fourth moving nozzle 14 is connected to a cleaning liquid pipe 46 that guides 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 outlet 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 flowchart for explaining an example of substrate processing by the substrate processing apparatus 1P according to the second embodiment. 14A and 14B are schematic diagrams for explaining each step 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 processing film residue removing step (step S11) are different. ), a cleaning step (step S20) and a cleaning liquid removing step (step S21) are performed.

The cleaning step (step S20) is a step of cleaning the upper surface of the substrate W by removing the second removal object 204 adhering to the upper surface of the substrate W. FIG. 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 rinse liquid.
The cleaning step (step S20) and the cleaning liquid removing step (step S21) will be described in detail below.

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 opposing member elevating unit 61 raises the opposing 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 opposing member 6 is positioned 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 while the fourth moving nozzle 14 is positioned 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 substrate W in the rotating state (cleaning liquid supply process, cleaning liquid discharge process). The cleaning liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W due to centrifugal force. In the cleaning process, the substrate W is rotated at a predetermined cleaning rotation speed. The cleaning rotation speed is, for example, a speed within 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 shown in FIG. As a result, the rinse liquid on the upper surface of the substrate W is replaced with the cleaning liquid.
After the cleaning step (step S20), a cleaning liquid removing step (step S21) is performed. 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 fourth nozzle moving unit 38 moves the fourth moving nozzle 14 to the home position. Then, as shown in FIG. 14B, the opposing member elevating unit 61 moves the opposing member 6 to the processing position.

Then, the upper rinse liquid valve 53 is opened while the opposing member 6 is positioned at the processing position. As a result, the rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the substrate W in the rotating state (upper rinse liquid supply process, upper rinse liquid discharge process). In the cleaning liquid removing process, the substrate W is rotated at a predetermined cleaning liquid removing rotational 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 due to centrifugal force. As a result, the cleaning liquid adhering to the upper surface of the substrate W is washed away with the rinse liquid.
At the same time when 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 substrate W in the rotating state (lower rinse liquid supply process, lower rinse liquid discharge process). As a result, even when the cleaning liquid adheres to the lower surface of the substrate W by going around from the upper surface of the substrate W 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 rinsing liquid to the upper and lower surfaces of the substrate W continues for a predetermined time, eg, 35 seconds.

15A to 15E are schematic diagrams for explaining the state of the vicinity of the upper surface of the substrate W during substrate processing by the substrate processing apparatus 1P.
FIG. 15A is a schematic diagram for explaining the state of the vicinity of the upper surface of the substrate W on which the pretreatment film 200 is formed by executing the pretreatment film forming step (step S3). The pretreatment film 200 retains the first removal object 203 as shown in 15A.

When the stripping solution is supplied to the upper surface of the substrate W on which the pretreatment film 200 is formed, as shown in FIG. It is peeled off from the top surface. The pretreatment film 200 splits into film pieces 205 when separated from the upper surface of the substrate W. As shown in FIG.
After the pretreatment film 200 is removed, the stripping solution is continuously supplied to the upper surface of the substrate W, so that the split film pieces 205 of the pretreatment film 200 are removed from the substrate W together with the stripping solution. As a result, the film piece 205 of the pretreatment film 200 holding the first removal object 203 is removed from the upper surface of the substrate W. FIG.

The removal force, retention force, and releasability of the polymer film for the first removal target object 203 present in the target region (exposed region 170 or non-exposed region 171) are the same as the removal targets described in the first embodiment. It is the same as the removal force, retention force, and peelability of the polymer film for the object 103 .
Therefore, the pretreatment film 200 exhibits high retention of the object to be removed in both the non-exposed regions 171 and the exposed regions 170 , while the treated film 100 has the pretreatment film 200 in both the non-exposed regions 171 and the exposed regions 170 . Demonstrates a higher removal target holding power than On the other hand, the pretreatment film 200 has higher releasability than the treatment film 100 in the exposed region 170 .

Therefore, the removal force of the treatment film 100 to remove the first removal object 203 existing in the non-exposed region 171 is greater than the removal force of the pretreatment film 200 to remove the first removal object 203 existing in the non-exposed region 171. is also expensive. The removal force of the pretreatment film 200 to remove the first removal object 203 existing in the exposed region 170 is higher than the removal force of the treatment film 100 to remove the first removal object 203 existing in the exposed region 170 .

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

After that, as shown in FIG. 15C, a treatment film 100 holding the first removal object 203 is formed. Since the treatment film 100 has a higher object-to-be-removed holding force for holding the first object-to-be-removed 203 existing in the non-exposed region 171 than the pretreatment film 200, the treatment film 100 can hold the first object-to-be-removed 203 . When the stripping solution is supplied to the top surface of the substrate W on which the processing film 100 is formed, the processing film 100 is removed from the top surface of the substrate W together with the first object to be removed 203 by the stripping action of the stripping solution, as shown in FIG. 15D. peeled off. The treatment film 100 splits into film pieces 105 when peeled off from the upper surface of the substrate W. As shown in FIG.

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

By supplying a cleaning liquid to the upper surface of the substrate W in the subsequent cleaning step (step S20), the second removal object 204 is dissolved as shown in FIG. 15E. Since the metal film 163 is covered with the exposed area covering portion 130, the metal film 163 is protected from being exposed to the cleaning liquid while the cleaning liquid is being supplied to the upper surface of the substrate W, as shown in FIG. 15E. . That is, the exposed area covering portion 130 functions as a protective film that protects the metal film 163 . In this manner, the second removal object 204 can be removed from the substrate W by supplying the cleaning liquid to the top surface of the substrate W while the metal film 163 exposed from the top surface of the substrate W is properly protected.

In the subsequent protective film removing step (step S8), the exposed region covering portion 130 of the processing film 100 can be dissolved in the removal liquid, and the exposed region covering portion 130 can be smoothly removed from the upper surface of the substrate W.
According to 2nd Embodiment, there exists an effect similar to 1st Embodiment.
Furthermore, according to the second embodiment, the following effects are also obtained.

By supplying the stripping liquid to the upper surface of the substrate W on which the processing film 100 is formed, the substrate W is stripped while the non-exposed area covering portion 131 (film to be stripped) holds the first removal target 203 . 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. FIG. On the other hand, the second object to be removed 204 remains on the upper surface of the substrate W. As shown in FIG.
After that, the second object to be removed 204 is removed from the upper surface of the substrate W with the cleaning liquid, and then the exposed area covering portion 130 (protective film) is removed from the upper surface of the substrate W with the removing liquid.

When the cleaning liquid is supplied to the upper surface of the substrate W, the exposed area 170 where the metal film 163 is exposed on the upper surface of the substrate W is covered with the exposed area covering portion 130 . Therefore, although the cleaning liquid used for removing the second object to be removed 204 has the 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, multiple kinds of objects to be removed (the first object to be removed 203 and the second object to be removed 204) can be efficiently removed from the upper surface of the substrate W while suppressing oxidation of the metal film 163 .
When the exposed area covering portion 130 of the treatment film 100 is dissolved in the removal liquid, the first removal object 203 released from the holding by the exposed area covering portion 130 may reattach to the exposed area 170 . According to the second embodiment, the treatment film 100 is formed after the pretreatment film 200, which has a relatively high removal force for removing the first removal object 203 existing in the exposed region 170, is removed from the exposed region 170 by peeling. be done. Therefore, most of the first removal object 203 is removed from the exposed region 170 before the treatment film 100 is formed.

Therefore, even with the configuration in which the exposed area covering portion 130 is dissolved in the removal liquid and removed from the exposed area 170 , it is possible to sufficiently prevent the first object to be removed 203 from remaining in the exposed area 170 .
Also in the second embodiment, even if the substrate processing 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 performed. It has the same effect as

<Details of treatment liquid>
Each component in the treatment liquid used in the above-described embodiments will be described below.
In the following descriptions such as "C _x-y ", "C _x- C _y " and "C _x " refer to the number of carbons in the molecule or substituent. For example, C _1-6 alkyl means an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

When the polymer has more than one kind of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerizations, random copolymerizations, block copolymerizations, graft copolymerizations, or mixtures thereof. When a polymer or resin is represented by a structural formula, n, m, etc. written together in parentheses indicate the number of repetitions.
<Low solubility component>
(A) the low-solubility component is at least one of novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonates, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof; including. Preferably, (A) the low solubility component may comprise at least one of novolaks, polyhydroxystyrenes, polyacrylic acid derivatives, polycarbonates, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, (A) the low solubility component may comprise at least one of novolac, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. The novolak may be a phenolic novolac.

The treatment liquid may contain one or a combination of two or more of the above preferred examples as (A) the low-solubility component. For example, (A) the low solubility component may contain both novolak and polyhydroxystyrene.
(A) It is a preferred embodiment that the low-soluble component is dried to form a film, and that the film can be peeled off while retaining the object to be removed without being dissolved in the stripping solution. It should be noted that a mode in which a small part of (A) the low-soluble component is dissolved by the stripping solution is allowed.

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

(Asterisks * indicate attachment to adjacent building blocks.)

(R means a substituent such as C _1-4 alkyl. An asterisk * indicates a bond to an adjacent constitutional unit.)

(Me means a methyl group.)
(A) The weight average molecular weight (Mw) of the low-soluble component is preferably 150 to 500,000, more preferably 300 to 300,000, even more preferably 500 to 100,000, and even more preferably is between 1,000 and 50,000.
(A) The low-solubility component can be obtained by synthesis. You can also purchase it. In the case of purchase, examples of supply destinations include the following. It is also possible for the supplier to synthesize the (A) polymer.
Novolak: Showa Kasei Co., Ltd., Asahi Organic Chemicals Co., Ltd., Gunei 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: Nippon Shokubai Polycarbonate: Sigma-Aldrich Polymethacrylic acid derivative: Sigma-Aldrich Compared to the total mass of the treatment liquid, (A) the low-soluble component is 0.1 to 50% by mass, preferably is 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 1 to 10% by mass. That is, the total mass of the treatment liquid is 100% by mass, and (A) the low-soluble component is 0.1 to 50% by mass based on this. That is, "compared to" can be rephrased as "based on." Unless otherwise specified, the same applies to the following.

Solubility can be evaluated by a known method. For example, under the conditions of 20 ° C. to 35 ° C. (more preferably 25 ± 2 ° C.), add 100 ppm of (A) or (B) described below to 5.0% by mass ammonia water in a flask, cover and shake. By shaking with a shaker for 3 hours, it can be determined whether (A) or (B) is dissolved. Shaking may be stirring. Dissolution can also be judged visually. If it does not dissolve, the solubility is less than 100 ppm, and if it dissolves, the solubility is 100 ppm or more. A solubility of less than 100 ppm is defined as insoluble or poorly soluble, and a solubility of 100 ppm or more is defined as soluble. In a broad sense, soluble includes sparingly soluble. Solubility is low in the order of insoluble, sparingly soluble, and soluble. In a narrow sense, sparingly soluble is less soluble than soluble and more soluble than sparingly soluble.

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

Although there is no intention to limit the scope of rights and is not bound by theory, the treatment liquid is dried to form a treatment film on the substrate, and when the stripping solution peels off the treatment film, (B) the highly soluble component is attached to the treatment film. It is thought that the part that triggers peeling is produced. For this reason, (B) the high solubility component preferably has a higher solubility in the stripping solution than the (A) low solubility component. An embodiment in which the crack-promoting component (B') contains a ketone as a carbonyl group includes a cyclic hydrocarbon. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

As a more specific embodiment, (B) the highly soluble component comprises 1 to 6 (preferably 1 to 4) structural units of the following chemical formula 8, and each structural unit is a linking group (linker) L ₁ is a compound that is bound by Here, the linker L ₁ may be a single bond or C _1-6 alkylene. The C _1-6 alkylene is a linker that connects structural units and is not limited to a divalent group. It is preferably divalent to tetravalent. The C _1-6 alkylene may be linear or branched.

Cy ₁ is a C _5-30 hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. In a preferred embodiment, the linker L ₁ connects multiple Cy _1's .
Each R ₁ is independently C _1-5 alkyl, preferably methyl, ethyl, propyl, or butyl. The C _1-5 alkyl may be either linear or branched.

_nb1 is 1, 2 or 3, preferably 1 or 2, more preferably 1; n _b1′ is 0, 1, 2, 3 or 4, preferably 0, 1 or 2;
Chemical formula 9 below is a chemical formula in which the structural unit described in chemical formula 8 is expressed using linker _L9 . Linker _L9 is preferably a single bond, methylene, ethylene, or propylene.

Although not intending to limit the scope of rights, preferred examples of (B) highly soluble components include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2, 6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di- tert-butylhydroquinone, 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 shown in Chemical Formula 10 below will be described. In (B), the same compound has three structural units of chemical formula 8, and the structural units are linked 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 80-10,000. The highly soluble component preferably has a molecular weight of 90-5000, more preferably 100-3000. (B) When the highly soluble component is a resin, polymer or polymer, the molecular weight is represented by weight average molecular weight (Mw).
(B) Highly soluble components can be obtained either by synthesis or by purchase. Suppliers include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

In the treatment liquid, the (B) highly soluble component is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, relative to the mass of (A) the lowly soluble component. In the treatment liquid, (B) the highly soluble component is more preferably 1 to 30% by mass relative to the mass of (A) the lowly soluble component.
<Solvent>
(C) The solvent preferably contains an organic solvent. (C) The solvent may be volatile. Having volatility means having high volatility compared to 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, more preferably 60 to 170°C. Even more preferably, the boiling point of the solvent at 1 atmosphere is 70 to 150°C. (C) The solvent may also contain a small amount of pure water. The amount of pure water contained in the solvent (C) is preferably 30% by mass or less relative to the total amount of the solvent (C). Pure water contained in the solvent is more preferably 20% by mass or less, still more preferably 10% by mass or less. Pure water contained in the solvent is more preferably 5% by mass or less. It is also a preferred form that the solvent does not contain pure water (0% by mass). Pure water is preferably DIW.

Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and ethylene glycol monomethyl ethers 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) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate (PGMEA) and 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 amides such as -methylpyrrolidone, lactones such as γ-butyrolactone, and the like. These organic solvents can be used alone or in combination of two or more.

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

<Other additives>
The treatment liquid of the present invention may further contain (D) other additives. As one aspect of the present invention, (D) other additives comprise surfactants, acids, bases, antibacterial agents, bactericides, antiseptics, or antifungal agents (preferably surfactants), Any combination of these may be included.

As one aspect of the present invention, compared to the mass of (A) the low-soluble component in the treatment liquid, (D) other additives (in the case of more than one, the sum thereof) is 0 to 100 mass (preferably 0 to 10% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass). It is also an aspect of the present invention that the treatment liquid does not contain (D) other additives (0 mass %).

<Corrosion prevention component>
(E) Corrosion-preventing components include, in addition to BTA, uric acid, caffeine, buterin, adenine, glyoxylic acid, glucose, fructose, mannose, and the like.
<Details of pretreatment solution>
Each component in the pretreatment liquid used in the above embodiment will be described below. (A) low-soluble components, (C) solvents, (D) other additives, and (E) corrosion-preventing components contained in the pretreatment liquid can be selected from those that can be used in the treatment film. .

The (B) highly soluble component contained in the pretreatment liquid is different from that contained in the treatment liquid. The (B) highly soluble component contained in the pretreatment liquid includes a first component selected from those exemplified as highly soluble components contained in the treatment liquid, and the following (B-1) and (B- 2) and a second component selected from the above. Supplementally, the treatment liquid described above contains only the first component as (B) the 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 C _1-5 alkyl, 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 each independently C _1-20 alkylene, C _1-20 cycloalkylene, C _2-4 alkenylene, C _2-4 alkynylene, or C _6-20 arylene. be. These groups may be substituted with C _1-5 alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon group 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, even more preferably acetylene .

_nb2 is 0, 1 or 2, preferably 0 or 1, more preferably 0.
Although not intending to limit the scope of rights, preferred examples of (B-1) include 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5- diols. As another form, 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyn-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy- 2-Butene and 1,4-benzenedimethanol are also suitable examples of (B-1).

(B-2) is a polymer containing structural units 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 permissible for one (B-2) polymer to contain two or more structural units each represented by Chemical Formula 12.
Although not intending to limit the scope of rights, preferred examples of the (B-2) polymer include polymers of acrylic acid, maleic acid, or combinations thereof. Polyacrylic acid, maleic acrylic acid copolymers are further preferred examples.

In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.
As an example, a maleic acrylic acid copolymer represented by the following chemical formula 13 will be described. The same copolymer is included in (B-2) and has two types of structural units represented by Chemical Formula 12, wherein R ₂₅ is —H in one structural unit, and R ₂₅ is —COOH in another structural unit. is.

<Peeling experiment>
Changes in the peeling state of the polymer film from the copper film and the particle removal power by changing the ratio of the first component and the second component of the highly soluble components in the polymer-containing liquid used as the treatment liquid and the pretreatment liquid In order to verify the above, a peeling experiment was performed in which the polymer film was peeled off from the copper film. A polymer film is a solid film formed by evaporating at least part of the solvent in the polymer-containing liquid.

First, a small piece-like substrate (small piece substrate) having particles such as SiO ₂ adhered to its surface is prepared. The small substrate used had a square shape with a side of 3 cm when viewed from the normal direction of the main surface, and a copper film was formed over the entire surface.
A small substrate was placed on a rotatable mounting table, and a polymer-containing liquid was supplied to the surface of the small substrate to form a polymer film. After that, 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. After that, 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, spin drying was performed by rotating the small substrate at high speed. After that, a scanning electron microscope (SEM) was used to confirm the degree of particle removal (removal force).

FIG. 16 is a table for explaining the results of peeling experiments. In FIG. 16, the ratio of the first component and the second component of the highly soluble components in the polymer-containing liquid is shown as the amount added. FIG. 16 shows the degree of removal of particles when the proportions and addition amounts of the first component and the second component are changed.
A combination of the added amount of the first component and the added amount of the second component that cannot remove particles is given "D" as an evaluation of the removal power. In addition, in FIG. 16, there was no combination with the evaluation of the removing force being "D". Similarly, the combination of the added amount of the first component and the added amount of the second component from which some of the particles were removed was given "C" as an evaluation of the removing power. A combination of the amount of the first component added and the amount of the second component added that could remove most of the particles was given "B" as an evaluation of the removal power. When particles can be removed, "A" is given as an evaluation of removal power. When the particles are sufficiently removed, "AA" is assigned as the evaluation of the removal power.

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

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

When the added amount of the second component was greater than the added amount of the first component, the evaluation of the removing power was "A" or "AA" in all 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 removal power is high. It was suggested that when using a polymer film to remove particles from a copper film, it is preferable to prepare the polymer-containing liquid so that the content of the second component is greater than that of the first component.

<Third Embodiment>
FIG. 17 is a schematic diagram of the first moving nozzle 9 and the third moving nozzle 11 of the processing unit 2 provided in the substrate processing apparatus 1Q according to the third embodiment of the present invention, and their peripheral members. In FIG. 17, the same reference numerals as those in FIG. 1 etc. are attached to the same configurations as those shown in FIGS. Similarly, in FIG. 18, which will be described later, the same reference numerals as in FIG.

17, the substrate processing apparatus 1Q according to the third embodiment is the substrate processing apparatus 1 (see FIG. 3) according to the first embodiment and the substrate processing apparatus 1P (see FIG. 11) according to the second embodiment. ) in that the substrate processing apparatus 1Q according to the third embodiment can adjust the concentration of the highly soluble components contained in the processing liquid and the pretreatment liquid.
In the first moving nozzle 9, a first component liquid, which is a mixed liquid of a first 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, A processing liquid is supplied which is mixed and prepared.

Specifically, a low-soluble component liquid pipe 140 and a first component liquid pipe 141 are commonly connected to the other end of the treatment liquid pipe 40 , one end of which 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 provided with a low-soluble component liquid valve 150 for adjusting the flow rate of the low-soluble component liquid supplied from the low-soluble component liquid pipe 140 to the treatment liquid pipe 40 . A first component liquid valve 151 is interposed in the first component liquid pipe 141 to adjust 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 degrees of the low-soluble component liquid valve 150 and the first component liquid valve 151, the concentration of the first component in the processing liquid flowing through the processing liquid pipe 40 can be changed.
The third moving nozzle 11 supplies a first component liquid, which is a mixed liquid of the first highly soluble component and the solvent, and a second component liquid, which is a mixed liquid of the second highly soluble component and the solvent. and a low-soluble component liquid, which is a mixed liquid of a low-soluble component and a solvent, are mixed to supply a pretreatment liquid prepared.

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

The low-soluble component liquid pipe 142 is provided with a low-soluble component liquid valve 152 for adjusting the flow rate of the low-soluble component liquid supplied from the low-soluble component liquid pipe 142 to the pretreatment liquid pipe 42 . . A first component liquid valve 153 is interposed in the first component liquid pipe 143 to adjust the flow rate of the first component liquid supplied from the first component liquid pipe 143 to the pretreatment liquid pipe 42 . A second component liquid valve 154 is interposed in the second component liquid pipe 144 to adjust 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 degrees of the low-soluble component liquid valve 152, the first component liquid valve 153, and the second component liquid valve 154, the concentration of the first component in the pretreatment liquid flowing through the pretreatment liquid pipe 42 and the second Concentrations of ingredients can be varied.
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 performed before performing substrate processing on the substrate W. FIG.

A 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 the first substrate processing method for removing the object to be removed from the substrate W using the processing liquid. The first substrate processing method is a substrate processing method in which the pretreatment liquid supplying step (step S2) to the pretreatment film residue removing step (step S6) are omitted from the substrate processing according to the first or 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) is removed using the treatment liquid. is removed only.

The second recipe R2 removes the removal target object 103 (first removal target object 203) from the substrate W using the pretreatment liquid, and then removes the removal target object 103 (first removal target object 203) from the substrate W using the treatment liquid. 203) is a recipe for performing the second substrate processing method for removing the substrate. 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. As shown in FIG. The concentration of the second component contained in the pretreatment liquid is changed according to the type of specific substance. That is, the concentration of the second component in the pretreatment liquid used in the second substrate processing method is set according to the type of specific substance. Specifically, in each second recipe, the low-soluble component liquid valve 152, the first component liquid valve 153, and the second 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 flowchart for explaining an example of recipe selection processing. First, the controller 3 acquires information about the surface of the substrate W to be processed (substrate to be processed) (information acquisition step: step S30). Information about the surface of the substrate W may be obtained based on information input by the user using the input device 3A, or may be configured to read information from a label such as a barcode set on the substrate W. good too.

After step S30, the controller 3 determines whether the substrate W has both the exposed area 170 and the non-exposed area 171 and the non-exposed area based on the information about the surface of the substrate W obtained in the information obtaining step. It is determined which of the substrates has a surface on which only 171 exists (surface determination step: step S31).
In step S31, when the controller 3 determines that the substrate W has a surface on which only the non-exposed region 171 exists (step S31: NO), it 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, in step S31, when the controller 3 determines that the substrate W has a surface on which both the exposed region 170 and the non-exposed region 171 exist (step S31: YES), Based on the obtained information about the surface of the substrate W, the type of the specific substance exposed from the surface of the substrate W is determined (type determining 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 non-exposed region 171 exists on the top surface of the substrate W, the first recipe R1 for performing the first substrate processing method is selected, and the exposed region 170 and the exposed region 170 on the top surface of the substrate W are selected. If both non-exposed regions 171 are present, the second recipe R2 is selected for performing the second substrate processing method. Therefore, an appropriate substrate processing method can be executed according to the state of the upper surface of the substrate W. FIG.

When both the exposed region 170 and the non-exposed region 171 exist on the upper surface of the substrate W, the method is suitable for removing the object to be removed 103 (first object to be removed 203) from the exposed region 170 depending on the type of specific substance. A second recipe R2 can be selected.
<Other embodiments>
The present invention is not limited to the embodiments described above, but can be embodied in other forms.

For example, in the treatment film forming step (step S8), when the treatment liquid film 101 is thinned, the solvent may evaporate, causing the liquid film 101 to solidify or harden. In such a case, in order to solidify or harden the liquid film 101 of the processing liquid after thinning the liquid film 101 of the processing liquid, it is necessary to heat the substrate W or blow gas onto the upper surface of the substrate W. 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, the heating of the substrate W and the blowing of the gas onto the upper surface of the substrate W can be omitted.
Further, in the substrate processing according to the second embodiment, the cleaning liquid removing step (step S21) is performed after the cleaning step (step S20). However, it is also possible to omit the cleaning liquid removal step. Specifically, the cleaning liquid supplied to the substrate W in the cleaning process and the processing film residue removing liquid supplied to the substrate W in the processing film residue removing process (step S11) performed after the cleaning liquid removing process have compatibility. In this case, there is no need to perform the cleaning liquid removal step.

Further, in the above-described embodiment, in the process film stripping step (step S9), the exposed region covering portion 130 remains on the exposed region 170 without being stripped by the stripper. However, the exposed area covering portion 130 may be peeled off with a peeling liquid in the treatment film peeling process.
In the above-described first to third embodiments, a polymer-containing liquid containing only the first component as the highly soluble component is used as the treatment liquid, and the first component and the second component are used as the highly soluble component. A polymer-containing liquid containing both was used as the pretreatment liquid. However, a polymer-containing liquid containing both the first component and the second component as the highly soluble component was used as the treatment liquid, and a polymer-containing liquid containing only the first component as the highly soluble component was used as the pretreatment liquid. You may use it as a processing liquid. In this case, the non-exposed region 171 where the specific substance such as copper is not exposed corresponds to the first region of the present invention, and the exposed region 170 where the specific substance such as copper is exposed corresponds to the second region of the present invention. do.

Further, in the first embodiment, the exposed area covering portion 130 is dissolved by the remover without being peeled off by the remover. However, in the first embodiment, the exposed area covering part 130 may be peeled off together with the non-exposed area covering part 131 by a peeling liquid.
Further, in the third embodiment, the second recipe R2 is prepared for each type of specific substance exposed from the substrate W. As shown in FIG. However, the second recipe R2 may not be provided for each type of 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 has a surface on which both the exposed region 170 and the non-exposed region 171 exist (step S31: YES), The second recipe R2 is selected without determining the type of specific substance (recipe selection step: step S35).

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

Reference Signs List 1: substrate processing apparatus 1P: substrate processing apparatus 1Q: substrate processing apparatus 3: controller 9: first moving nozzle (processing liquid supply unit)
10: Second moving nozzle (stripping solution supply unit)
11: Third moving nozzle (pretreatment liquid supply unit)
12: Central nozzle (treatment film forming unit, pretreatment film forming unit)
13: Bottom nozzle (treatment film forming unit, pretreatment film forming unit)
23: Spin motor (treatment film forming unit, pretreatment film forming unit)
100: treatment film 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 solid state)
111: low-solubility solid (first low-solubility component in solid state)
130: exposed area covering portion (portion covering exposed area in treated film, protective film)
131: non-exposed region covering portion (portion covering the non-exposed region in the treatment film, film to be peeled)
163: Metal film (specific substance, metal)
170: exposed region (first region, second region)
171: non-exposed area (second area, first area)
200: pretreatment film 202: through hole (second through hole)
203: First object to be removed (particulate residue)
204: Second object to be removed (film-like residue)
210: Highly soluble solid (second highly soluble component in solid state)
211: low-solubility solid (second low-solubility component in 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 mutually different substances are exposed, comprising:
a pretreatment liquid supply step of supplying a pretreatment liquid to the surface of the substrate;
A pretreatment film forming step of solidifying or hardening the pretreatment liquid supplied to the surface of the substrate to form a pretreatment film on the surface of the substrate, the pretreatment film holding the first removal object present on the surface of the substrate. and,
a pretreatment film stripping step of supplying a stripping solution to the surface of the substrate to strip the pretreatment film holding the first object to be removed from the surface of the substrate;
a processing liquid supply step of supplying a processing liquid to the surface of the substrate after the pretreatment film stripping step;
a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form on the surface of the substrate a treatment film holding the first object to be removed existing on the surface of the substrate;
a process film stripping step of supplying a stripping solution to the surface of the substrate to strip the process film holding the first object to be removed from the surface of the substrate;
The treatment film has a higher removal force for removing the first object to be removed existing in the second region than the pretreatment film removes the first object to be removed existing in the second region. ,
The removal power of the pretreatment film to remove the first object to be removed existing in the first region is higher than the removal force of the treatment film to remove the first object to be removed existing in the first region. , a substrate processing method. The removal force for removing the first object to be removed includes a holding force for holding the first object to be removed existing in the first region or the second region on the treatment film or the pretreatment film, and and a releasability representing the ease with which the treatment film or the pretreatment film holding the object to be removed is removed,
In the first region, the pretreatment film has higher releasability than the treatment film,
2. The substrate processing method according to claim 1, wherein said treatment film has higher holding power than said pretreatment film in said 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 treatment film has a higher removal force for removing the first object to be removed existing in the non-exposed region than the pretreatment film removes the first object to be removed existing in the non-exposed region. ,
The pretreatment film has a higher removal force for removing the first object to be removed existing in the exposed region than the removal force for removing the first object to be removed existing in the exposed region by the pretreatment film. Item 3. The substrate processing method according to Item 1 or 2. 4. The substrate according to claim 3, further comprising a process film residue removing step of supplying a removal liquid to the surface of the substrate to remove residues of the process film remaining on the surface of the substrate after the process film stripping step. Processing method. The step of removing the treatment film includes removing a portion of the treatment film covering the non-exposed region without removing a portion of the treatment film covering the exposed region,
5. The substrate processing method according to claim 4, wherein said processing film residue removing step includes a step of removing a portion of said processing film covering said exposed region by dissolving said portion of said processing film in said removing liquid. The treatment film forming step holds the first object to be removed existing in the non-exposed region of the surface of the substrate, and a separation target film that covers the non-exposed region, and a protective film that covers and protects the exposed region. forming on the surface of the substrate the treated film having a film;
4. The method according to claim 3, further comprising a cleaning step of supplying a cleaning liquid to the surface of the substrate after the process film stripping step, and dissolving and removing the second object to be removed present on the surface of the substrate with the cleaning liquid. The substrate processing method described. After the treatment film stripping step, a treatment film residue removal step of supplying a removal liquid to the surface of the substrate to remove the residue of the treatment film remaining on the surface of the substrate,
7. The substrate processing method according to claim 6, wherein said processing film residue removing step includes a step of removing said protective film as said residue. 8. The substrate processing method according to claim 7, wherein said first object to be removed and said second object to be removed are residues produced by a dry etching process. The first object to be removed is granular residue,
9. The substrate processing method according to claim 8, wherein said second object to be removed is a film-like residue covering at least part of said non-exposed region of said substrate surface. the treatment liquid comprises 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,
10. The substrate processing method according to claim 1, wherein said treatment film stripping step includes a step of selectively dissolving said first highly soluble component in a solid state in said stripping solution. 11. The process according to any one of claims 1 to 10, wherein said treatment film stripping step includes a first through hole forming step of partially dissolving said treatment film in said stripping solution to form first through holes in said treatment film. The substrate processing method according to the item. The pretreatment liquid has a second solute and a second solvent that dissolves the second solute,
The second solute has a second high-solubility component and a second low-solubility component that is less soluble in the stripping solution than the second high-solubility component,
12. The substrate processing method according to claim 1, wherein said pretreatment film stripping step includes a step of selectively dissolving said second highly soluble component in a solid state in said stripping solution. The pretreatment film stripping step includes a second through hole forming step of partially dissolving the pretreatment film in the stripping solution to form second through holes in the pretreatment film, The substrate processing method according to any one of the items. A substrate processing apparatus for processing a substrate having a surface having a first region and a second region where different substances are exposed,
a processing liquid supply unit that supplies the processing liquid to the surface of the substrate;
a treatment film forming unit that solidifies or hardens the treatment liquid to form a treatment film on the surface of the substrate;
a pretreatment liquid supply unit that supplies a pretreatment liquid to the surface of the substrate;
a pretreatment film forming unit that solidifies or cures a pretreatment liquid to form a pretreatment film on the surface of the substrate;
a stripping liquid supply unit that supplies a stripping liquid to the surface of the substrate;
a controller that controls the pretreatment liquid supply unit, the pretreatment film formation unit, the treatment liquid supply unit, the treatment film formation unit, and the stripper supply unit;
the controller
supplying a pretreatment liquid from the pretreatment liquid supply unit toward the surface of the substrate;
solidifying or hardening the pretreatment liquid on the surface of the substrate by the pretreatment film forming unit to form a pretreatment film on the surface of the substrate that retains an object to be removed existing on the surface of the substrate;
supplying a stripping solution from the stripping solution supply unit to the surface of the substrate to strip the pretreatment film holding the object to be removed from the surface of the substrate;
after removing the pretreatment film, supplying a treatment liquid from the treatment liquid supply unit to the surface of the substrate;
Solidifying or hardening the processing liquid on the surface of the substrate by the processing film forming unit to form a processing film on the surface of the substrate that retains an object to be removed existing on the surface of the substrate;
programmed to supply a stripping solution from the stripping solution supply unit to the surface of the substrate to strip the treatment film holding the object to be removed from the surface of the substrate;
The removal force of the treatment film to remove the object to be removed existing in the second region is higher than the removal force of the pretreatment film to remove the object to be removed existing in the second region,
The substrate processing apparatus, wherein the removal force of the pretreatment film to remove the object to be removed existing in the first region is higher than the removal force of the treatment film to remove the object to be removed existing in the first region. . The removal 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 treatment film or the pretreatment film, and a holding force for holding the object to be removed. and a releasability that indicates the ease with which the treatment film or the pretreatment film in the state of being removed is composed,
In the first region, the pretreatment film has higher releasability than the treatment film,
15. The substrate processing apparatus according to claim 14, wherein said treatment film has higher holding power than said pretreatment film in said second region. A recipe selection method for selecting a recipe for performing a substrate processing method for processing a substrate to be processed, comprising:
an information acquisition step of acquiring information about the surface of the substrate to be processed;
The substrate to be processed has a surface on which both an exposed region where the specific substance is exposed and a non-exposed region where the specific substance is not exposed are present based on the information obtained by the information obtaining step; and a surface determination step of determining which of the substrates has a surface on which only the non-exposed area exists;
When the surface determination step determines that only the non-exposed region exists on the surface of the substrate to be processed, a first substrate processing method is performed to remove an object to be removed from the substrate to be processed using a processing liquid. When a first recipe is selected and the surface determination step determines that both the exposed region and the non-exposed region exist on the surface of the substrate to be processed, the removal of the object to be removed from the exposed region. A second substrate processing method comprising removing the object to be removed from the substrate to be processed using a pretreatment liquid having a higher force than the processing liquid, and then removing the object to be removed from the substrate to be processed using a processing liquid. and a recipe selection step of selecting a second recipe to run. The pretreatment liquid has a first component and a second component,
The second component has a higher removing power than the first component to remove the object to be removed from the exposed area,
When the surface determination step determines that both the exposed region and the non-exposed region exist on the surface of the substrate to be processed, the surface of the substrate to be processed is determined based on the information acquired by the information acquiring step. further comprising a type determination step of determining the type of the specific substance to be exposed;
In the recipe selection step, the concentration of the second component in the pretreatment liquid used in the second substrate processing method is set according to the type of the specific substance determined in the type determination step. 17. The recipe selection method of claim 16, comprising selecting two recipes.

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