阅读说明：本技术 衬底处理方法及衬底处理装置 (Substrate processing method and substrate processing apparatus ) 是由 奥谷学 吉田幸史 上田大 张松 安田周一 柴山宣之 金松泰范 于 2020-03-06 设计创作，主要内容包括：衬底处理方法包括下述工序：处理液供给工序,向衬底的表面供给含有溶质及溶剂的处理液；处理膜形成工序,使供给至所述衬底的表面的所述处理液固化或硬化,以在所述衬底的表面形成对存在于所述衬底的表面的除去对象物进行保持的处理膜；和除去工序,通过以液滴状态向所述衬底的表面供给除去液,以使所述除去液的液滴的物理力作用于所述处理膜及所述除去对象物,从而将所述处理膜及所述除去对象物从所述衬底的表面除去。(The substrate processing method includes the following steps: a treatment liquid supply step of supplying a treatment liquid containing a solute and a solvent to the surface of the substrate; a treatment film forming step of curing or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate, the treatment film holding an object to be removed existing on the surface of the substrate; and a removing step of supplying a removing liquid in a droplet state to the surface of the substrate so that a physical force of the droplet of the removing liquid acts on the processing film and the object to be removed, thereby removing the processing film and the object to be removed from the surface of the substrate.)

1. A substrate processing method comprising the steps of:

a treatment liquid supply step of supplying a treatment liquid containing a solute and a solvent to the surface of the substrate;

a treatment film forming step of curing or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate, the treatment film holding an object to be removed existing on the surface of the substrate; and

and a removing step of supplying a removing liquid in a droplet state to the surface of the substrate so that a physical force of the droplet of the removing liquid acts on the processing film and the object to be removed, thereby removing the processing film and the object to be removed from the surface of the substrate.

2. The substrate processing method according to claim 1, wherein said removing step comprises the steps of:

a treatment film removing step of peeling the treatment film holding the object to be removed from the surface of the substrate by applying physical force of the droplets of the removing liquid to the treatment film, and separating the treatment film from the surface of the substrate to remove the treatment film from the surface of the substrate; and

And a removal object removal step of removing the removal object from the surface of the substrate by causing physical force of the droplets of the removal liquid to act on the removal object.

3. The substrate processing method according to claim 1 or 2, wherein the process film forming step includes a step of forming the process film having a film thickness smaller than a radius of the removal target held by the process film.

4. The substrate processing method according to any one of claims 1 to 3, wherein the removing liquid is water or an alkaline liquid.

5. The substrate processing method according to any one of claims 1 to 4, further comprising:

and a protective liquid film forming step of forming a liquid film on the surface of the substrate by supplying a protective liquid in a continuous flow onto the surface of the substrate before the removing step is started, the liquid film covering the protective liquid supplied in a droplet state to the supply region of the removing liquid in the removing step.

6. The substrate processing method of any of claims 1 to 5, further comprising:

and a protective liquid parallel supply step of supplying a protective liquid in a continuous flow onto the surface of the substrate while the removal liquid is supplied in a droplet state onto the surface of the substrate in the removal step.

7. The substrate processing method according to claim 5 or 6, wherein the protective liquid has a property of partially dissolving the processing film.

8. The substrate processing method according to any one of claims 5 to 7, wherein the protective liquid is water or an alkaline liquid.

9. The substrate processing method according to any one of claims 1 to 8, further comprising:

and a residue removing step of supplying a solution for dissolving the treatment film to the surface of the substrate to remove the residue of the treatment film remaining on the surface of the substrate after the removing step.

10. The substrate processing method according to any one of claims 1 to 9, wherein the removing step comprises a step of supplying the removing liquid in a droplet state to the surface of the substrate to partially dissolve the processing film in the removing liquid.

11. The substrate processing method according to claim 10, wherein said solute has a high-solubility substance and a low-solubility substance having a lower solubility with respect to said removing liquid than said high-solubility substance,

the treatment film forming step includes a step of forming the treatment film having the high-solubility substance in a solid state and the low-solubility substance in a solid state,

The removing step includes a step of selectively dissolving the highly soluble substance in a solid state in the treatment film in the removing liquid.

12. The substrate processing method according to claim 10 or 11, wherein the solute has a solvency-enhancing substance,

the removing step includes a step of dissolving the treatment film partially in the removal liquid having the enhanced dissolving power by dissolving the treatment film in the removal liquid supplied to the surface of the substrate by eluting the dissolution-power-enhancing substance from the treatment film into the removal liquid supplied to the surface of the substrate.

13. A substrate processing apparatus, comprising:

a processing liquid supply unit which supplies a processing liquid containing a solute and a solvent to a surface of a substrate;

a solid forming unit that solidifies or hardens the treatment liquid;

a removing liquid supply unit that supplies a removing liquid in a droplet state to a surface of the substrate; and

a controller that controls the treatment liquid supply unit, the solid forming unit, and the removal liquid supply unit,

the controller is programmed to perform the following process: a processing liquid supply step of supplying the processing liquid from the processing liquid supply unit to the surface of the substrate; a treatment film forming step of forming a treatment film on the surface of the substrate, the treatment film holding an object to be removed existing on the surface of the substrate, by curing or hardening the treatment liquid supplied to the surface of the substrate by the solid forming means; and a removing step of supplying the removing liquid from the removing liquid supply unit to the surface of the substrate in a droplet state so that a physical force of the droplet of the removing liquid acts on the processing film and the object to be removed, thereby removing the processing film and the object to be removed from the surface of the substrate.

14. The substrate processing apparatus of claim 13, wherein the controller is programmed to perform the following in the removing process: a treatment film removing step of peeling the treatment film holding the object to be removed from the surface of the substrate by applying physical force of the droplets of the removing liquid to the treatment film, and separating the treatment film from the surface of the substrate to remove the treatment film from the surface of the substrate; and a removal object removal step of removing the removal object from the surface of the substrate by causing physical force of the droplets of the removal liquid to act on the removal object.

15. The substrate processing apparatus according to claim 13 or 14, wherein the controller is programmed to form the processing film having a film thickness smaller than a radius of the removal target held on the processing film in the processing film formation process.

16. The substrate processing apparatus according to any one of claims 13 to 15, further comprising a 1 st protective liquid supply unit that supplies a protective liquid in a continuous flow direction to a surface of the substrate,

the controller is programmed to perform a protective liquid film forming step of forming a liquid film on the surface of the substrate covering a supply region of the protective liquid supplied in a droplet state in the removing step by supplying the protective liquid from the 1 st protective liquid supply unit in a continuous flow onto the surface of the substrate before the removing step is started.

17. The substrate processing apparatus according to any one of claims 13 to 16, further comprising a 2 nd protective liquid supply unit that supplies a protective liquid in a continuous flow direction to a surface of the substrate,

the controller is programmed to perform a protective liquid parallel supply step of supplying a protective liquid from the 2 nd protective liquid supply unit in a continuous flow to the surface of the substrate while the removal liquid is supplied to the surface of the substrate in a droplet state in the removal step.

18. The substrate processing apparatus according to claim 16 or 17, wherein the protective liquid has a property of partially dissolving the processing film.

19. The substrate processing apparatus according to any one of claims 13 to 18, further comprising a dissolving solution supply unit that supplies a dissolving solution that dissolves the processing film to a surface of the substrate,

the controller is programmed to perform a residue removal process of supplying the solution from the solution supply unit to remove the residue of the processing film remaining on the surface of the substrate after the removal process.

20. The substrate processing apparatus according to any one of claims 13 to 19, wherein the controller performs a step of supplying the removal liquid in a droplet state to the surface of the substrate to partially dissolve the processing film in the removal liquid in the removal step.

Technical Field

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Examples of the substrate (substrate) to be processed include a semiconductor wafer, a substrate for a liquid crystal Display device, a substrate for an FPD (Flat Panel Display) such as an organic EL (Electroluminescence) Display device, a substrate for an optical disc, a substrate for a magnetic disc, a substrate for a magneto-optical disc, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and the like.

Background

In a manufacturing process of a semiconductor device, a cleaning process is performed to remove various contaminants adhering to a substrate, a processing liquid used in a previous process, residues such as a resist, various particles, and the like (hereinafter, collectively referred to as "objects to be removed").

In the cleaning step, generally, a cleaning liquid such as Deionized Water (DIW) is supplied to the substrate to remove the object to be removed by the physical action of the cleaning liquid, or a chemical liquid chemically reacting with the object to be removed is supplied to the substrate to chemically remove the object to be removed.

However, the uneven pattern formed on the substrate has become finer and more complicated. Therefore, it is becoming increasingly difficult to remove the object to be removed using a cleaning liquid or a chemical while suppressing damage to the uneven pattern.

Therefore, a method has been proposed in which a treatment liquid containing a volatile component is supplied to the upper surface of a substrate, a treatment film is formed by volatilization of the volatile component, and then the treatment film is removed (see patent document 1).

In this method, the treatment liquid is cured or hardened to form a treatment film, and the object to be removed is covered with the treatment film. Next, a stripping treatment liquid is supplied to the upper surface of the substrate. The peeling treatment liquid permeates the treatment film and enters between the substrate and the treatment film. The object to be removed is peeled from the upper surface of the substrate together with the processing film by allowing the peeling processing liquid to enter between the substrate and the processing film.

Documents of the prior art

Patent document

Patent document 1: U.S. patent application publication No. 2015/128994 specification

Disclosure of Invention

Problems to be solved by the invention

For example, when the size of the object to be removed on the substrate is large and the object to be removed cannot be held by the processing film with an appropriate holding force, the object to be removed may remain on the substrate when the processing film is peeled off from the upper surface of the substrate by the method of patent document 1. Thus, there is a possibility that the object to be removed cannot be sufficiently removed from the substrate.

Accordingly, an 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 existing on a surface of a substrate.

Means for solving the problems

One embodiment of the present invention provides a substrate processing method including the steps of: a treatment liquid supply step of supplying a treatment liquid containing a solute and a solvent to the surface of the substrate; a treatment film forming step of curing or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate, the treatment film holding an object to be removed existing on the surface of the substrate; and a removing step of supplying a droplet-state removing liquid to the surface of the substrate so that a physical force of the droplet-state removing liquid acts on the processing film and the object to be removed, thereby removing the processing film and the object to be removed from the surface of the substrate.

According to this method, the treatment liquid supplied to the surface of the substrate is cured or hardened, thereby forming a treatment film that holds the object to be removed. Then, the removing liquid is supplied to the surface of the substrate in a droplet state. Thus, the physical force of the droplets of the removal liquid acts on the processing film and the removal target.

Specifically, the physical force of the droplets of the removing liquid acts on the processing film, whereby the processing film holding the object to be removed is separated from the surface of the substrate and removed from the surface of the substrate. Then, the physical force of the droplets of the removing liquid acts on the object to be removed, and the object to be removed is removed from the surface of the substrate.

Therefore, the physical force of the droplets of the removal liquid can be applied to the processing film to remove most of the object to be removed from the surface of the substrate together with the processing film. Further, the physical force of the droplets of the removal liquid is applied to the object to be removed, whereby the object to be removed, which is not removed together with the treatment film, is removed from the surface of the substrate.

As a result, the object to be removed existing on the surface of the substrate can be efficiently removed.

In one embodiment of the present invention, the process film forming step includes a step of forming the process film having a film thickness smaller than a radius of the removal target held by the process film.

When the film thickness of the process film is smaller than the radius of the object to be removed, the process film hardly enters between the object to be removed and the substrate. Therefore, in this case, the object to be removed may not be held by the treatment film with a sufficient holding force. Therefore, in the method of peeling the treatment film holding the removal object from the surface of the substrate, the removal object cannot be taken away from the surface of the substrate by the treatment film, and therefore the removal object is likely to remain on the surface of the substrate.

Therefore, when the removal liquid is supplied in the form of droplets onto the surface of the substrate, the physical force of the droplets of the removal liquid acts not only on the processing film but also on the object to be removed. Thus, even when the film thickness of the processing film is smaller than the radius of the object to be removed, the object to be removed can be sufficiently removed from the surface of the substrate.

In one embodiment of the present invention, the removal liquid is water or an alkaline liquid. When the removal liquid is water or an alkaline liquid, the physical force of the liquid droplets can be applied not only to the treatment film but also to the object to be removed. In the case where the removing liquid is an alkaline liquid, the treatment film is more easily dissolved than in the case where the removing liquid is water. Therefore, the physical force can be applied to the processing film in a state where the strength of the processing film is reduced. On the other hand, when the removing liquid is water, the treatment film is less likely to be dissolved than when the removing liquid is an alkaline liquid. Therefore, the physical force can be applied to the processing film in a state where the number of objects to be removed held by the processing film is increased as much as possible.

In one embodiment of the present invention, the substrate processing method further includes a protective liquid film forming step of forming a liquid film of the protective liquid on the surface of the substrate so as to cover a supply region to which the removal liquid is supplied in a droplet state in the removal step by supplying the protective liquid to the surface of the substrate in a continuous flow before the removal step is started.

The physical force acting on the surface of the substrate from the droplets of the removing liquid is particularly large in the supply region. Therefore, when the supply region is covered with the liquid film of the protective liquid before the removal step is started, the physical force acting on the supply region from the droplets of the removal liquid can be appropriately reduced, and the physical force of the droplets of the removal liquid can be dispersed over the entire surface of the substrate. This protects the surface of the substrate and removes the processing film and the object to be removed from the surface of the substrate.

In particular, when the uneven pattern is formed on the surface of the substrate, the uneven pattern may collapse in the supply region due to a physical force acting on the surface of the substrate from the droplets of the removing liquid. When the supply region is covered with the liquid film of the protective liquid before the removal step is started, the physical force acting on the uneven pattern can be appropriately reduced in the supply region to protect the uneven pattern.

The physical force acting on the surface of the substrate when a continuous flow of liquid is supplied to the surface of the substrate is very small compared to the physical force acting on the surface of the substrate when a droplet is supplied to the surface of the substrate. Therefore, the surface damage of the substrate due to the supply of the protective liquid can be suppressed or prevented. In particular, when the uneven pattern is formed on the surface of the substrate, if the protective liquid is supplied in a continuous flow onto the surface of the substrate, collapse of the uneven pattern due to the supply of the protective liquid can be suppressed or prevented.

In one embodiment of the present invention, the substrate processing method further includes a protective liquid parallel supply step of supplying the protective liquid in a continuous flow onto the surface of the substrate while the removing liquid is supplied onto the surface of the substrate in a droplet state in the removing step.

According to this method, the protective liquid is supplied in a continuous flow onto the surface of the substrate while the removing liquid is supplied in a droplet state onto the surface of the substrate in the removing step. Therefore, the surface of the substrate can be maintained in a state of being covered with the protective solution in the removing step. This makes it possible to appropriately reduce the physical force acting on the region of the surface of the substrate to which the removal liquid is supplied in the form of droplets, and to disperse the physical force of the droplets of the removal liquid over the entire surface of the substrate. This makes it possible to remove the treatment film and the object to be removed from the surface of the substrate while protecting the surface of the substrate (particularly, the uneven pattern formed on the surface of the substrate).

In one embodiment of the present invention, the protective solution has a property of partially dissolving the treatment film.

According to this method, the treatment film is partially dissolved with the protective solution. Therefore, the strength of the treatment film can be reduced by the protective liquid, and the physical force of the droplets of the removal liquid can be applied to the treatment film. This makes it possible to efficiently split the processing film and efficiently peel the processing film from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

In one embodiment of the present invention, the protective solution is water or an alkaline liquid. In the case where the protective liquid is water or an alkaline liquid, the physical force of the droplets of the removal liquid acting on the surface of the substrate can be appropriately reduced, and the physical force of the droplets of the removal liquid can be dispersed over the entire surface of the substrate. When the protective liquid is an alkaline liquid, the treatment film is more easily dissolved than when the protective liquid is water. Therefore, the strength of the treated film is easily lowered. On the other hand, when the protective liquid is water, the treatment film is less likely to be dissolved than when the protective liquid is an alkaline liquid, and thus the treatment film is easily maintained in a state of being held on the removal target.

In one embodiment of the present invention, the substrate processing method further includes a residue removing step of supplying a solution for dissolving the processing film to the surface of the substrate to remove the residue of the processing film remaining on the surface of the substrate after the removing step.

After the treatment film is removed from the surface of the substrate in the removal step, a residue of the treatment film may remain on the surface of the substrate. Therefore, by supplying a solution for dissolving the treatment film to the surface of the substrate, the residue of the treatment film remaining on the surface of the substrate can be removed. This enables the surface of the substrate to be cleaned satisfactorily.

In one embodiment of the present invention, the removing step includes a step of supplying the removing liquid in a droplet state to the surface of the substrate to partially dissolve the treatment film in the removing liquid.

According to this method, the treatment film is partially dissolved by the removing liquid. Therefore, the physical force of the droplets of the removal liquid can be applied to the treatment film while the strength of the treatment film is reduced. This makes it possible to efficiently split the processing film and efficiently peel the processing film from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

In one embodiment of the present invention, the solute has a high-solubility substance and a low-solubility substance having a lower solubility than the high-solubility substance with respect to the removing solution. The treatment film forming step includes a step of forming the treatment film having the high-solubility substance in a solid state and the low-solubility substance in a solid state. The removing step includes a step of selectively dissolving the highly soluble substance in a solid state in the treatment film in the removing liquid to promote peeling of the treatment film from the surface of the substrate and splitting of the treatment film.

According to this method, the highly soluble substance in a solid state in the treatment film is selectively dissolved by the removing liquid. The phrase "the high-solubility substance in a solid state is selectively dissolved" does not mean that only the high-solubility substance in a solid state is dissolved, but that a small amount of the low-solubility substance in a solid state is dissolved and most of the high-solubility substance in a solid state is dissolved.

Therefore, the strength of the treatment film is reduced, but the removal target is maintained in a state held by the treatment film. Therefore, in a state where the object to be removed is still held by the treatment film, the physical force of the droplets of the removal liquid can be applied to the treatment film in the removal step in a state where the strength of the treatment film is reduced. This makes it possible to efficiently separate the processing film and efficiently peel the processing film from the surface of the substrate.

In one embodiment of the present invention, the solute includes a dissolution-enhancing substance. The removing step includes a step of dissolving the treatment film in the removal liquid having the enhanced dissolving power by the removal liquid supplied to the surface of the substrate by eluting the dissolution-power-enhancing substance from the treatment film into the removal liquid supplied to the surface of the substrate, thereby enhancing the dissolving power with which the treatment film is dissolved by the removal liquid supplied to the surface of the substrate, and partially dissolving the treatment film in the removal liquid having the enhanced dissolving power.

According to this method, the dissolving force of the removing liquid for dissolving the treatment film is enhanced by dissolving the dissolving force enhancing substance from the treatment film into the removing liquid, and the treatment film is partially dissolved by the removing liquid. Therefore, even when a liquid having a low dissolving power is used as the removing liquid, the strength of the treatment film can be reduced and the physical force of the droplets of the removing liquid can be applied to the treatment film. This makes it possible to efficiently split the processing film and efficiently peel the processing film from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

Another embodiment of the present invention provides a substrate processing apparatus, including: a processing liquid supply unit which supplies a processing liquid containing a solute and a solvent to a surface of a substrate; a solid forming unit that solidifies or hardens the treatment liquid; a removing liquid supply unit that supplies a removing liquid in a droplet state to a surface of the substrate; and a controller that controls the treatment liquid supply unit, the solid forming unit, and the removal liquid supply unit.

And, the controller is programmed to perform the following process: a processing liquid supply step of supplying the processing liquid from the processing liquid supply unit to the surface of the substrate; a treatment film forming step of forming a treatment film on the surface of the substrate, the treatment film holding an object to be removed existing on the surface of the substrate, by curing or hardening the treatment liquid supplied to the surface of the substrate by the solid forming means; and a removing step of supplying the removing liquid in a droplet state from the removing liquid supply unit to the surface of the substrate so that a physical force of the droplet of the removing liquid acts on the processing film and the object to be removed, thereby removing the processing film and the object to be removed from the surface of the substrate.

According to this apparatus, the treatment liquid supplied to the surface of the substrate is cured or hardened, thereby forming a treatment film that holds the object to be removed. Then, the removing liquid is supplied to the surface of the substrate in a droplet state. Thus, the physical force of the droplets of the removal liquid acts on the processing film and the removal target.

In detail, the controller is programmed to perform the following process in the removing process: a treatment film removal step of peeling the treatment film holding the object to be removed from the surface of the substrate by applying physical force of the droplets of the removal liquid to the treatment film, and separating the treatment film to remove the treatment film from the surface of the substrate; and a removal object removal step of removing the removal object from the surface of the substrate by applying physical force of the droplets of the removal liquid to the removal object.

Therefore, the physical force of the droplets of the removal liquid can be applied to the processing film to remove most of the object to be removed from the surface of the substrate together with the processing film. Further, by applying physical force of the droplets of the removal liquid to the object to be removed, the object to be removed which is not removed together with the processing film can be removed from the surface of the substrate.

As a result, the object to be removed existing on the surface of the substrate can be efficiently removed.

In another embodiment of the present invention, the controller is programmed to form the process film having a film thickness smaller than a radius of the object to be removed held by the process film in the process film forming step.

When the film thickness of the process film is smaller than the radius of the object to be removed, the process film hardly enters between the object to be removed and the substrate. Therefore, in this case, the object to be removed may not be held by the treatment film with a sufficient holding force. Thus, in the method of peeling the processing film holding the object to be removed from the surface of the substrate, the object to be removed cannot be taken away from the surface of the substrate by the processing film, and therefore the object to be removed is likely to remain on the surface of the substrate.

Therefore, when the removal liquid is supplied to the surface of the substrate in a droplet state, the physical force of the droplet of the removal liquid acts not only on the processing film but also on the object to be removed. Thus, even when the film thickness of the processing film is smaller than the radius of the object to be removed, the object to be removed can be sufficiently removed from the surface of the substrate.

In another embodiment of the present invention, the substrate processing apparatus further comprises a 1 st protective liquid supply unit which supplies a protective liquid in a continuous flow onto the surface of the substrate. And the controller is programmed to perform a protective liquid film forming step of forming a liquid film on the surface of the substrate covering the protective liquid supplied in a droplet state to the supply region of the removal liquid in the removal step by supplying the protective liquid from the 1 st protective liquid supply unit in a continuous flow onto the surface of the substrate before the removal step is started.

The physical force acting on the surface of the substrate from the droplets of the removing liquid is particularly large in the supply region. Therefore, when the supply region is covered with the liquid film of the protective liquid before the removal step is started, the physical force acting on the supply region from the droplets of the removal liquid can be appropriately reduced, and the physical force of the droplets of the removal liquid can be dispersed over the entire surface of the substrate. This protects the surface of the substrate and removes the processing film and the object to be removed from the surface of the substrate.

In particular, when the uneven pattern is formed on the surface of the substrate, the uneven pattern may collapse in the supply region due to a physical force acting on the surface of the substrate from the droplets of the removing liquid. If the supply region is covered with the liquid film of the protective liquid before the removal step is started, the physical force acting on the uneven pattern in the supply region can be appropriately reduced to protect the uneven pattern.

The physical force acting on the surface of the substrate when a continuous flow of liquid is supplied to the surface of the substrate is very small compared to the physical force acting on the surface of the substrate when a droplet is supplied to the surface of the substrate. Therefore, the surface damage of the substrate due to the supply of the protective liquid can be suppressed or prevented. In particular, when the uneven pattern is formed on the surface of the substrate, if the protective liquid is supplied in a continuous flow onto the surface of the substrate, collapse of the uneven pattern due to the supply of the protective liquid can be suppressed or prevented.

In another embodiment of the present invention, the substrate processing apparatus further comprises a 2 nd protective liquid supply unit which supplies the protective liquid in a continuous flow to the surface of the substrate. And the controller is programmed to perform a protective liquid parallel supply step of supplying a protective liquid from the 2 nd protective liquid supply unit in a continuous flow to the surface of the substrate while the removal liquid is supplied to the surface of the substrate in a droplet state in the removal step.

According to this apparatus, while the removing liquid is supplied to the surface of the substrate in the form of droplets in the removing step, the protective liquid is supplied to the surface of the substrate in a continuous flow. Therefore, the surface of the substrate can be maintained in a state of being covered with the protective solution in the removing step. This makes it possible to appropriately reduce the physical force acting on the region of the surface of the substrate to which the removal liquid is supplied in the form of droplets, and to disperse the physical force of the droplets of the removal liquid over the entire surface of the substrate. This makes it possible to remove the treatment film and the object to be removed from the surface of the substrate while protecting the surface of the substrate (particularly, the uneven pattern formed on the surface of the substrate).

In another embodiment of the present invention, the protective solution has a property of partially dissolving the treatment film.

According to the apparatus, the treatment film is partially dissolved using the protective liquid. Therefore, the strength of the treatment film can be reduced by the protective liquid, and the physical force of the droplets of the removal liquid can be applied to the treatment film. This makes it possible to efficiently split the processing film and efficiently peel the processing film from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

In another embodiment of the present invention, the substrate processing apparatus further includes a dissolving solution supply unit that supplies a dissolving solution for dissolving the processing film to a surface of the substrate. And the controller is programmed to perform a residue removing step of supplying the solution from the solution supply unit to remove the residue of the processing film remaining on the surface of the substrate after the removing step.

After the treatment film is removed from the surface of the substrate in the removal step, a residue of the treatment film may remain on the surface of the substrate. Therefore, by supplying a solution for dissolving the treatment film to the surface of the substrate, the residue of the treatment film remaining on the surface of the substrate can be removed. This enables the surface of the substrate to be cleaned satisfactorily.

In another embodiment of the present invention, the controller performs a step of supplying the removal liquid in a droplet state to the surface of the substrate to partially dissolve the treatment film in the removal liquid in the removal step.

According to this apparatus, the treatment film is partially dissolved with the removing liquid. Therefore, the physical force of the droplets of the removal liquid can be applied to the treatment film while the strength of the treatment film is reduced. This makes it possible to efficiently split the processing film and efficiently peel the processing film from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

The above and other objects, features and effects of the present invention will be apparent from the following description of the embodiments with reference to the accompanying drawings.

Drawings

Fig. 1 is a schematic plan view showing the layout of a substrate processing apparatus according to embodiment 1 of the present invention.

Fig. 2 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit provided in the substrate processing apparatus.

Fig. 3A is a schematic side view of a removing liquid supply unit and a protective liquid supply unit provided in the substrate processing apparatus.

Fig. 3B is a schematic plan view of the removal liquid supply unit and the protective liquid supply unit.

Fig. 4 is a block diagram showing an electrical configuration of a main part of the substrate processing apparatus.

Fig. 5 is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus.

Fig. 6A is a schematic diagram for explaining the case of the processing liquid supply step (step S5) of the substrate processing.

Fig. 6B is a schematic diagram for explaining the case of the thinning process (step S6) of the substrate processing.

Fig. 6C is a schematic diagram for explaining the case of the thinning process (step S6) of the substrate processing.

Fig. 6D is a schematic diagram for explaining the case of the solid forming process (step S7) of the substrate processing.

Fig. 6E is a schematic diagram for explaining the case of the protective liquid film forming step (step S8) of the substrate processing.

Fig. 6F is a schematic diagram for explaining the case of the removal process (step S9) of the substrate processing.

Fig. 6G is a schematic diagram for explaining the case of the 2 nd rinsing process (step S10) of the substrate processing.

Fig. 6H is a schematic diagram for explaining the case of the 2 nd organic solvent supply process (step S11) of the substrate processing.

Fig. 6I is a schematic diagram for explaining the case of the spin drying process (step S12) of the substrate processing.

Fig. 7A is a schematic view for explaining a case where a processing film is removed from a substrate in the substrate processing.

Fig. 7B is a schematic view for explaining a case where a processing film is removed from a substrate in the substrate processing.

Fig. 7C is a schematic view for explaining a case where a processing film is removed from a substrate in the substrate processing.

Fig. 8 is a schematic view for explaining a case where the treatment film is removed from the substrate in the case where an alkaline aqueous solution is used as the protective solution.

Fig. 9A is a schematic view for explaining a case where a treatment film is removed from a substrate in substrate treatment by the substrate treatment apparatus according to embodiment 2 of the present invention.

Fig. 9B is a schematic view for explaining a case where a treatment film is removed from a substrate in substrate treatment by the substrate treatment apparatus of embodiment 2.

Fig. 9C is a schematic view for explaining a case where a treatment film is removed from a substrate in substrate treatment by the substrate treatment apparatus of embodiment 2.

Fig. 10A is a schematic view for explaining a case where a treatment film is removed from a substrate in substrate treatment by the substrate treatment apparatus according to embodiment 3 of the present invention.

Fig. 10B is a schematic view for explaining a case where a treatment film is removed from a substrate in substrate treatment by the substrate treatment apparatus of embodiment 3.

Fig. 10C is a schematic view for explaining a case where a treatment film is removed from a substrate in substrate treatment by the substrate treatment apparatus of embodiment 3.

Fig. 11 is a schematic view for explaining the case of the removing step (step S9) in the case where the protective liquid film forming step is omitted in the substrate processing.

Fig. 12 is a schematic diagram for explaining the case of the removal step (step S9) in the case where the supply of the protective liquid in the removal step is omitted in the substrate processing.

Fig. 13 is a schematic view for explaining the case of the removing step (step S9) in which the supply of the protective liquid and the protective liquid film forming step in the removing step are omitted in the substrate processing.

Fig. 14 is a schematic diagram showing a structure in which the protective liquid supply unit is held in the nozzle holder together with other protective liquid supply units.

Detailed Description

< embodiment 1 >

Fig. 1 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to embodiment 1 of the present invention.

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

The substrate processing apparatus 1 includes: a plurality of processing units 2 that process the substrate W using a fluid; a load port LP on which a carrier C accommodating a plurality of substrates W processed by the processing unit 2 is placed; transfer robots IR and CR that transfer the substrate W between the load port LP and the processing unit 2; and a controller 3 that controls the substrate processing apparatus 1.

The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing unit 2. The plurality of processing units 2 have, for example, the same configuration. As will be described in detail later, the processing fluid supplied to the substrate W in the processing unit 2 includes a chemical solution, a rinsing solution, a processing solution, a removing solution, a protective solution, a heat medium, a dissolving solution, an inert gas, and the like.

Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and processes on the substrate W are performed in the processing cup 7. The chamber 4 is provided with an entrance/exit (not shown) for carrying in/out the substrate W by the transfer robot CR. The chamber 4 includes a shutter unit (not shown) for opening and closing the entrance.

Fig. 2 is a schematic diagram for explaining a configuration example of the processing unit 2. The process unit 2 includes a spin chuck 5, an opposite member 6, a process cup 7, a1 st moving nozzle 8, a 2 nd moving nozzle 9, a 3 rd moving nozzle 10, a 4 th moving nozzle 11, a center nozzle 14, and a lower surface nozzle 15.

The spin chuck 5 rotates the substrate W about a vertical rotation axis a1 (vertical axis) passing through the center of the substrate W while holding the substrate W horizontally. The spin chuck 5 includes a plurality of chuck pins 20, a spin base 21, a spin shaft 22, and a spin motor 23.

The rotating base 21 has a circular plate shape along the horizontal direction. On the upper surface of the spin base 21, a plurality of chuck pins 20 for gripping the peripheral edge of the substrate W are arranged at intervals along 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 horizontally holds the substrate W. The substrate holding unit is also referred to as a substrate holder.

The rotary shaft 22 extends in the vertical direction along the rotation axis a 1. The upper end of the rotary shaft 22 is coupled to the center of the lower surface of the rotary base 21. The rotary motor 23 imparts a rotational force to the rotary shaft 22. The rotating base 21 is rotated by rotating the rotating shaft 22 by the rotating motor 23. Thereby, the substrate W is rotated about the rotation axis a 1. The spin motor 23 is an example of a substrate rotating unit that rotates the substrate W about the rotation axis a 1.

The opposed member 6 is opposed to the substrate W held by the spin chuck 5 from above. The opposing member 6 is formed in a disc shape having a diameter larger than or equal to the diameter of the substrate W. The opposed member 6 has an opposed surface 6a opposed to the upper surface (upper surface) of the substrate W. The facing surface 6a is arranged along a substantially horizontal plane above the spin chuck 5.

In the facing member 6, a hollow shaft 60 is fixed on the opposite side to the facing surface 6 a. In the opposed member 6, a communication hole 6b is formed in a portion overlapping with the rotation axis a1 in a plan view, and the communication hole 6b vertically penetrates the opposed member 6 and communicates with the internal space 60A of the hollow shaft 60.

The facing member 6 blocks an atmosphere in a space between the facing surface 6a and the upper surface of the substrate W from an atmosphere outside the space. Therefore, the opposing member 6 is also referred to as a partition plate.

The process unit 2 further includes an opposing member elevating unit 61 that drives the elevation of the opposing member 6. The opposing member lifting/lowering unit 61 can position the opposing member 6 at an arbitrary position (height) from the lower position to the upper position. The lower position is a position where the facing surface 6a is closest to the substrate W in the movable range of the facing member 6. The upper position is a position at which the facing surface 6a is farthest away from the substrate W within the movable range of the facing member 6.

The opposing member lifting unit 61 includes, for example: a ball screw mechanism (not shown) coupled to a support member (not shown) that supports the hollow shaft 60; and an electric motor (not shown) that applies a driving force to the ball screw mechanism. The opposing member elevating unit 61 is also referred to as an opposing member elevator (shielding plate elevator).

The processing cup 7 includes: a plurality of masks 71 that receive the liquid scattered outward from the substrate W held by the spin chuck 5; a plurality of cups 72 that receive the liquid guided downward by the plurality of hoods 71; and a cylindrical outer wall member 73 surrounding the plurality of hoods 71 and the plurality of cups 72.

In the present embodiment, an example in which 2 masks 71 (1 st mask 71A and 2 nd mask 71B) and 2 cups 72 (1 st cup 72A and 2 nd cup 72B) are provided is shown.

The 1 st cup 72A and the 2 nd cup 72B each have an annular groove that opens upward.

The 1 st mask 71A is disposed so as to surround the rotating base 21. The 2 nd mask 71B is disposed so as to surround the spin base 21 more outward in the rotation radial direction of the substrate W than the 1 st mask 71A.

The 1 st mask 71A and the 2 nd mask 71B each have a substantially cylindrical shape. The upper end of each hood 71 is inclined inward so as to face the rotating base 21.

The 1 st cup 72A receives the liquid guided downward by the 1 st hood 71A. The 2 nd cup 72B is formed integrally with the 1 st cup 71A, and receives the liquid guided downward by the 2 nd cup 71B.

The processing unit 2 includes a mask lifting unit 74 for independently lifting and lowering the 1 st mask 71A and the 2 nd mask 71B. The shield elevating unit 74 elevates the 1 st shield 71A between the lower position and the upper position. The shield elevating unit 74 elevates the 2 nd shield 71B between the lower position and the upper position.

When the 1 st shield 71A and the 2 nd shield 71B are both located at the upper positions, the 1 st shield 71A receives the liquid scattered from the substrate W. When the 1 st shield 71A is located at the lower position and the 2 nd shield 71B is located at the upper position, the liquid scattered from the substrate W is received by the 2 nd shield 71B.

The guard lifting and lowering unit 74 includes, for example, a1 st ball screw mechanism (not shown) coupled to the 1 st guard 71A, a1 st motor (not shown) that applies a driving force to the 1 st ball screw mechanism, a 2 nd ball screw mechanism (not shown) coupled to the 2 nd guard 71B, and a 2 nd motor (not shown) that applies a driving force to the 2 nd ball screw mechanism. The shield elevating unit 74 is also referred to as a shield elevator.

The 1 st moving nozzle 8 is an example of a chemical solution nozzle (chemical solution supply unit) that discharges a chemical solution onto the upper surface of the substrate W held by the spin chuck 5.

The 1 st moving nozzle 8 is moved in the horizontal direction and the vertical direction by the 1 st nozzle moving unit 36. The 1 st moving nozzle 8 is movable between a center position and a home position (retracted position) in the horizontal direction.

The 1 st moving nozzle 8 is opposed to the rotation center of the upper surface of the substrate W when located at the center position. The rotation center of the upper surface of the substrate W is the intersection position with the rotation axis a1 in the upper surface of the substrate W. The 1 st moving nozzle 8 is not opposed to the upper surface of the substrate W when it is located at the home position, and is located outside the processing cup 7 in a plan view.

The 1 st moving nozzle 8 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

The 1 st nozzle moving unit 36 includes, for example, a rotating shaft (not shown) extending in the vertical direction, an arm (not shown) coupled to the rotating shaft and extending horizontally, and a rotating shaft driving unit (not shown) for moving up and down or rotating the rotating shaft.

The pivot shaft driving unit pivots the arm by rotating the pivot shaft about a vertical pivot axis. The pivot shaft driving unit moves the arm up and down by moving the pivot shaft up and down in the vertical direction. The 1 st moving nozzle 8 is fixed to the arm. The 1 st moving nozzle 8 moves in the horizontal direction and the vertical direction in accordance with the swinging and lifting of the arm.

The 1 st moving nozzle 8 is connected to a chemical liquid pipe 40 for introducing a chemical liquid. When the chemical liquid valve 50 provided in the chemical liquid pipe 40 is opened, the chemical liquid is continuously discharged downward from the 1 st moving nozzle 8.

The chemical solution discharged from the first moving nozzle 8 is, for example, at least 1 solution containing sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, hydrogen peroxide, an organic acid (e.g., citric acid, oxalic acid, etc.), an organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), a surfactant, and an antiseptic. Examples of the chemical solution obtained by mixing the above components include SPM solution (sulfuric acid/hydrogen peroxide mixture solution: sulfuric acid hydrogen peroxide mixture solution), SC1 solution (ammonia-hydrogen peroxide mixture solution: ammonia hydrogen peroxide mixture solution), and the like.

The 2 nd moving nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (discharges) a processing liquid onto the upper surface of the substrate W held by the spin chuck 5.

The 2 nd moving nozzle 9 is moved in the horizontal direction and the vertical direction by the 2 nd nozzle moving unit 37. The 2 nd moving nozzle 9 is movable between a center position and a home position (retracted position) in the horizontal direction. The 2 nd moving nozzle 9 is opposed to the rotation center of the upper surface of the substrate W when located at the center position. The 2 nd moving nozzle 9 is not opposed to the upper surface of the substrate W when it is located at the home position, and is located outside the processing cup 7 in a plan view. The 2 nd moving nozzle 9 can be moved in the vertical direction to be close to the upper surface of the substrate W or retracted upward from the upper surface of the substrate W.

The 2 nd nozzle transfer unit 37 has the same configuration as the 1 st nozzle transfer unit 36. That is, the 2 nd nozzle moving means 37 includes, for example, a turning shaft (not shown) extending in the vertical direction, an arm (not shown) coupled to the turning shaft and the 2 nd moving nozzle 9 and extending horizontally, and turning shaft driving means (not shown) for raising and lowering or turning the turning shaft.

The 2 nd moving nozzle 9 is connected to a treatment liquid pipe 41 for guiding the treatment liquid. When the treatment liquid valve 51 attached to the treatment liquid pipe 41 is opened, the treatment liquid is continuously discharged downward from the 2 nd moving nozzle 9.

The processing liquid discharged from the 2 nd moving nozzle 9 contains a solute and a solvent. The treatment liquid is solidified or hardened by volatilization (evaporation) of at least a part of the solvent. The treatment liquid is cured or hardened on the substrate W, thereby forming a treatment film that holds the object to be removed, such as particles, present on the substrate W. The object to be removed is, for example, a foreign substance adhering to the surface of the substrate W after dry etching or ashing.

The solute contained in the treatment liquid discharged from the 2 nd moving nozzle 9 is, for example, novolac (novolac). The solvent contained in the processing liquid discharged from the 2 nd moving nozzle 9 may be a liquid that dissolves the solute, and may be an alcohol such as IPA, for example. The solvent contained in the treatment solution is preferably a liquid having compatibility (miscibility) with the removal solution.

As the solvent contained in the treatment liquid used in embodiment 1, those listed as the solvent contained in the treatment liquid used in embodiment 2 described later can be used. As the solute contained in the treatment liquid used in embodiment 1, those listed as low-solubility substances contained in the treatment liquid used in embodiment 2 described later can be used.

Here, "solidification" means that the solute becomes solid due to, for example, intermolecular or interatomic forces caused by volatilization of the solvent. "hardening" means that the solute becomes solid due to chemical changes such as polymerization, crosslinking, and the like. Thus, "set or harden" means that the solute "hardens" for a variety of reasons.

The 3 rd moving nozzle 10 is a spray nozzle that sprays a large amount of droplets of the removing liquid. An example of the removal liquid nozzle (removal liquid supply unit) is a nozzle that supplies (discharges) a removal liquid such as pure water in a droplet state onto the upper surface of the substrate W held by the spin chuck 5. The removal liquid is a liquid for removing a treatment film formed on the upper surface of the substrate W and an object to be removed existing on the upper surface of the substrate W from the upper surface of the substrate W.

The 3 rd moving nozzle 10 is moved in the horizontal direction and the vertical direction by the 3 rd nozzle moving unit 38. The 3 rd moving nozzle 10 is movable between a center position and a home position (retracted position) in the horizontal direction.

The 3 rd moving nozzle 10 is opposed to the rotation center of the upper surface of the substrate W when located at the center position. The 3 rd moving nozzle 10 is not opposed to the upper surface of the substrate W when it is located at the home position, and is located outside the processing cup 7 in a plan view. The 3 rd 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 3 rd nozzle moving unit 38 includes, for example: a rotation shaft 38C along the vertical direction; a nozzle arm 38A coupled to the rotation shaft and the 3 rd moving nozzle 10 and extending horizontally; and a turning shaft driving unit 38D that raises or rotates the turning shaft.

The pivot shaft driving unit 38D swings the nozzle arm 38A by pivoting the pivot shaft 38C about the vertical pivot axis a 2. The pivot shaft driving unit 38D moves the nozzle arm 38A up and down by moving the pivot shaft 38C up and down in the vertical direction. The 3 rd moving nozzle 10 is fixed to the front end of the nozzle arm 38A. The 3 rd moving nozzle 10 moves in the horizontal direction and the vertical direction in accordance with the swing and the lift of the nozzle arm 38A.

The 3 rd moving nozzle 10 is connected to a removal liquid supply source via a removal liquid pipe 42. The 3 rd moving nozzle 10 is connected to a discharge pipe 43 provided with a discharge valve 53. A removal liquid valve 52 and a pump 90 are disposed between the removal liquid supply source and the removal liquid pipe 42.

The removal liquid is supplied from the removal liquid supply source to the removal liquid pipe 42 by the pump 90. The removing liquid is supplied to the 3 rd moving nozzle 10 at a predetermined pressure (for example, 10MPa or less) at all times. The pump 90 can change the pressure of the removal liquid supplied to the 3 rd moving nozzle 10 to an arbitrary pressure.

The 3 rd moving nozzle 10 incorporates a piezoelectric element (piezo element) 91. The piezoelectric element 91 is connected to a voltage applying unit 93 via a wiring 92. The voltage applying unit 93 includes, for example, an inverter. The voltage application unit 93 applies an alternating voltage to the piezoelectric element 91. When an alternating voltage is applied to the piezoelectric element 91, the piezoelectric element 91 vibrates at a frequency corresponding to the frequency of the applied alternating voltage. The voltage applying unit 93 can change the frequency of the ac voltage applied to the piezoelectric element 91 to an arbitrary frequency (for example, several hundreds KHz to several MHz).

The removal liquid discharged from the 3 rd moving nozzle 10 is, for example, pure water (preferably DIW). The removing liquid is not limited to pure water, and may be an alkaline aqueous solution (alkaline liquid) or an aqueous solution (non-alkaline aqueous solution) of any of neutral and acidic properties. Specific examples of the alkaline aqueous solution include aqueous ammonia, SC1 solution, TMAH aqueous solution, choline aqueous solution, and a combination of any of the above.

The 4 th moving nozzle 11 is an example of a protective liquid nozzle (protective liquid supply unit) that supplies a protective liquid to the upper surface of the substrate W in a continuous flow. The protective liquid is a liquid for protecting the uneven pattern formed on the surface of the substrate W from the removal liquid in a droplet state.

The 4 th moving nozzle 11 is held by a nozzle holder 38B attached to the nozzle arm 38A. Therefore, the 4 th moving nozzle 11 is moved integrally with the 3 rd moving nozzle 10 by the 3 rd nozzle moving unit 38.

The 4 th moving nozzle 11 is connected to a protective liquid pipe 47. A protective liquid valve 57A and a protective liquid flow rate control valve 57B are attached to the protective liquid pipe 47.

The protective liquid discharged from the 4 th moving nozzle 11 is, for example, pure water (preferably DIW). The protective solution is not limited to pure water, and may be an alkaline aqueous solution (alkaline liquid) or an aqueous solution (non-alkaline aqueous solution) of any of neutral and acidic properties. Specific examples of the alkaline aqueous solution include aqueous ammonia, SC1 solution, TMAH aqueous solution, choline aqueous solution, and a combination of any of the above.

The center nozzle 14 is accommodated in the inner space 60a of the hollow shaft 60 of the opposite member 6. The discharge port 14a provided at the tip of the center nozzle 14 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 a region including the rotation center of the substrate W and its periphery in the upper surface of the substrate W.

The center nozzle 14 includes a plurality of tubes (1 st tube 31, 2 nd tube 32, and 3 rd tube 33) for discharging a fluid downward, and a cylindrical casing 30 surrounding the plurality of tubes. The plurality of pipes and the housing 30 extend in the vertical direction along the rotation axis a 1. The discharge port 14a of the center nozzle 14 is a discharge port of the 1 st pipe 31, a discharge port of the 2 nd pipe 32, and a discharge port of the 3 rd pipe 33 at the same time.

The 1 st pipe 31 (center nozzle 14) is an example of a rinse liquid supply unit that supplies a rinse liquid to the upper surface of the substrate W in a continuous flow. The 2 nd pipe 32 (center nozzle 14) is an example of gas supply means for supplying a gas between the upper surface of the substrate W and the facing surface 6a of the facing member 6. The 3 rd pipe 33 (central nozzle 14) is an example of an organic solvent supply means for supplying an organic solvent such as IPA to the upper surface of the substrate W in a continuous flow.

The 1 st pipe 31 is connected to an upper rinse liquid pipe 44 for guiding the rinse liquid to the 1 st pipe 31. When the upper rinse liquid valve 54 attached to the upper rinse liquid pipe 44 is opened, the rinse liquid is discharged from the 1 st pipe 31 (center nozzle 14) in a continuous flow toward the center region of the upper surface of the substrate W.

Examples of the rinsing liquid include DIW, carbonated water, electrolytic ionized water, hydrochloric acid water having a diluted concentration (for example, about 1 to 100 ppm), ammonia water having a diluted concentration (for example, about 1 to 100 ppm), and reduced water (hydrogen water).

The 2 nd pipe 32 is connected to a gas pipe 45 for guiding gas to the 2 nd pipe 32. When the gas valve 55 attached to the gas pipe 45 is opened, the gas is continuously discharged downward from the 2 nd pipe 32 (the center nozzle 14).

The gas discharged from the 2 nd pipe 32 is, for example, nitrogen (N)₂) And the like. The gas ejected from the 2 nd pipe 32 may be air. The inert gas is not limited to nitrogen gas, but is a gas that is inert to the pattern formed on the upper surface of the substrate W. Examples of the inert gas include a rare gas such as argon gas in addition to nitrogen gas.

The 3 rd pipe 33 is connected to an organic solvent pipe 46 for guiding the organic solvent to the 3 rd pipe 33. When the organic solvent valve 56 attached to the organic solvent pipe 46 is opened, the organic solvent is continuously discharged from the 3 rd pipe 33 (center nozzle 14) toward the center area of the upper surface of the substrate W.

The organic solvent discharged from the 3 rd pipe 33 is a residue removing liquid for removing the residue remaining on the upper surface of the substrate W after the treatment film is removed by the removing liquid. The organic solvent discharged from the 3 rd pipe 33 is preferably compatible with the treatment liquid and the rinse liquid.

Examples of the organic solvent discharged from the 3 rd pipe 33 include a solution containing at least 1 of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1, 2-dichloroethylene.

The organic solvent discharged from the 3 rd pipe 33 does not necessarily have to contain only a single component, and may be a liquid obtained by mixing with other components. For example, the liquid may be a mixture of IPA and DIW or a mixture of IPA and HFE.

The lower surface nozzle 15 is inserted into a through hole 21a opened in the center of the upper surface of the rotary base 21. The discharge port 15a of the lower surface nozzle 15 is exposed from the upper surface of the rotating base 21. The discharge port 15a of the lower surface nozzle 15 faces a central region of the lower surface (lower surface) of the substrate W from below. The central region of the lower surface of the substrate W is a region of the lower surface of the substrate W including the rotation center of the substrate W.

One end of a common pipe 80 that guides the rinse liquid, the removal liquid, and the heat medium to the lower surface nozzle 15 in common is connected to the lower surface nozzle 15. A lower rinse liquid pipe 81 for guiding the rinse liquid to the common pipe 80, a lower removal liquid pipe 82 for guiding the removal liquid to the common pipe 80, and a heat medium pipe 83 for guiding the heat medium to the common pipe 80 are connected to the other end of the common pipe 80.

When the lower rinse liquid valve 86 attached to the lower rinse liquid pipe 81 is opened, the rinse liquid is continuously discharged from the lower surface nozzle 15 toward the central region of the lower surface of the substrate W. When the lower removing liquid valve 87 attached to the lower removing liquid pipe 82 is opened, the removing liquid is discharged from the lower surface nozzle 15 so as to flow continuously toward the central region of the lower surface of the substrate W. When the heat medium valve 88 attached to the heat medium pipe 83 is opened, the heat medium is discharged from the lower surface nozzle 15 in a continuous flow toward the central region of the lower surface of the substrate W.

The lower surface nozzle 15 is an example of a lower rinse liquid supply unit that continuously supplies the rinse liquid to the lower surface of the substrate W. The lower surface nozzle 15 is an example of a lower removing liquid supply unit that continuously supplies the removing liquid to the lower surface of the substrate W. The lower surface nozzle 15 is an example of a heat medium supply unit that supplies a heat medium for heating the substrate W to the substrate W in a continuous flow. The lower surface nozzle 15 is also a substrate heating unit that heats the substrate W.

The heat medium discharged from the lower surface nozzle 15 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 to 80 ℃ is used as the heat medium, for example. The heat medium discharged from the lower surface nozzle 15 is not limited to the high temperature DIW, and may be a high temperature inert gas having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid, or a high temperature gas such as high temperature air.

Fig. 3A is a schematic side view of the 3 rd moving nozzle 10 and the 4 th moving nozzle 11. Fig. 3B is a schematic plan view of the 3 rd moving nozzle 10 and the 4 th moving nozzle 11.

As shown in fig. 3A, the 3 rd moving nozzle 10 includes a main body 94 that ejects droplets of the removal liquid, a cover 95 that covers the main body 94, a piezoelectric element 91 covered by the cover 95, and a seal portion 96 interposed between the main body 94 and the cover 95.

The body 94 and the cover 95 are formed of a material having chemical resistance. The body 94 is formed of quartz, for example. The cap 95 is made of, for example, a fluorine resin.

The seal portion 96 is formed of an elastic material such as EPDM (ethylene-propylene-diene rubber). The main body 94 has pressure resistance. A part of the body 94 and the piezoelectric element 91 are housed inside the cover 95. One end of the wiring 92 is connected to the voltage applying unit 93. The other end of the wiring 92 is connected to the piezoelectric element 91 by soldering, for example, inside the cover 95. The interior of the cover 95 is sealed by a sealing portion 96.

The main body 94 includes a supply port 94a for supplying the removal liquid, a discharge port 94b for discharging the removal liquid supplied to the supply port 94a, a removal flow path 94c for connecting the supply port 94a and the discharge port 94b, and a plurality of ejection ports 94d (ejection ports) connected to the removal flow path 94 c.

The removal flow path 94c is provided inside the main body 94. The supply port 94a, the discharge port 94b, and the ejection port 94d are open on the surface of the body 94. The supply port 94a and the discharge port 94b are located above the ejection port 94 d. The lower surface of the main body 94 is, for example, a horizontal flat surface, and the ejection port 94d opens at the lower surface of the main body 94. The ejection opening 94d is a fine hole having a diameter of, for example, several μm to several tens μm. The removal liquid pipe 42 and the discharge pipe 43 are connected to the supply port 94a and the discharge port 94b, respectively.

As shown in fig. 3B, the plurality of ejection openings 94d constitute a plurality of (e.g., 4) rows L. Each row L is constituted by a large number (for example, 10 or more) of ejection openings 94d arranged at equal intervals. Each column L extends linearly along the horizontal longitudinal direction D1. Each row L is not limited to a straight line, and may be curved. The 4 columns L are parallel. 2 columns L of the 4 columns L are adjacent to each other in a horizontal direction orthogonal to the longitudinal direction D1. Similarly, the remaining 2 columns L are also adjacent in the horizontal direction orthogonal to the longitudinal direction D1.

The adjacent 2 columns L are paired. In the pair of 2 rows L, the plurality of ejection openings 94D constituting one row L are shifted from the plurality of ejection openings 94D constituting the other row L in the longitudinal direction D1. The 3 rd moving nozzle 10 is held by the nozzle arm 38A so that, for example, 4 rows L intersect with the moving trajectory of the 3 rd moving nozzle 10 when viewed from the vertical direction.

The removing liquid is supplied to the 3 rd moving nozzle 10 at a high pressure at all times. The removal liquid supplied to the supply port 94a is supplied to the removal liquid flow path 94 c. In a state where the discharge valve 53 is closed, the pressure (hydraulic pressure) of the removal liquid in the removal flow path 94c is high. Therefore, the removal liquid is ejected from each ejection port 94d by the hydraulic pressure in a state where the discharge valve 53 is closed. When an ac voltage is applied to the piezoelectric element 91 in a state where the discharge valve 53 is closed, vibration of the piezoelectric element 91 is applied to the removal liquid flowing through the removal flow path 94c, and the removal liquid ejected from each ejection port 94d is divided by the vibration. Therefore, when an ac voltage is applied to the piezoelectric element 91 in a state where the discharge valve 53 is closed, the removal liquid in a droplet state is ejected from each ejection port 94 d. Thereby, a large number of droplets of the removing liquid having a uniform particle diameter are simultaneously ejected at a uniform speed.

On the other hand, in a state where the discharge valve 53 is opened, the removal liquid supplied to the removal liquid flow path 94c is discharged from the discharge port 94b to the discharge pipe 43. That is, in a state where the discharge valve 53 is opened, the hydraulic pressure in the removal flow path 94c does not sufficiently rise, and therefore the removal liquid supplied to the removal flow path 94c is not ejected from the injection port 94d, which is a fine hole, but is discharged from the discharge port 94b to the discharge pipe 43. Therefore, the ejection of the removal liquid from the ejection port 94d is controlled by opening and closing the discharge valve 53.

A region of the upper surface of the substrate W to which the removal liquid in a droplet state is supplied (a region to which droplets of the removal liquid are blown) is referred to as a supply region S. The 4 th moving nozzle 11 ejects the protective liquid toward the target position P1 on the substrate W. The target position P1 is a position on the upstream side of the supply region S in the rotation direction Dr of the substrate W.

Fig. 4 is a block diagram showing an electrical configuration of a main part of the substrate processing apparatus 1. The controller 3 includes a microcomputer and controls a control target provided in the substrate processing apparatus 1 according to a predetermined control program.

Specifically, the controller 3 includes a processor (CPU)3A and a memory 3B in which a control program is stored. The controller 3 is configured to execute various controls for performing substrate processing by executing a control program by the processor 3A.

In particular, the controller 3 is programmed to control the transfer robot arms IR and CR, the rotation motor 23, the 1 st nozzle transfer unit 36, the 2 nd nozzle transfer unit 37, the 3 rd nozzle transfer unit 38, the counter member elevating unit 61, the mask elevating unit 74, the pump 90, the voltage applying unit 93, the chemical liquid valve 50, the treatment liquid valve 51, the removal liquid valve 52, the discharge valve 53, the upper rinsing liquid valve 54, the gas valve 55, the organic solvent valve 56, the protective liquid valve 57A, the protective liquid flow rate adjusting valve 57B, the lower rinsing liquid valve 86, the lower removal liquid valve 87, and the heat medium valve 88. By performing valve control by the controller 3, whether or not the treatment fluid is discharged from the corresponding nozzle and the discharge flow rate of the treatment fluid from the corresponding nozzle are controlled.

Fig. 5 is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1. Fig. 5 mainly shows processing realized by executing a program by the controller 3. Fig. 6A to 6I are schematic views for explaining the respective steps of the substrate processing.

In the substrate processing performed by the substrate processing apparatus 1, for example, as shown in fig. 5, a substrate carrying-in process (step S1), a chemical liquid supply process (step S2), a 1 st rinsing process (step S3), a 1 st organic solvent supply process (step S4), a processing liquid supply process (step S5), a thin film forming process (step S6), a solid forming process (step S7), a protective liquid film forming process (step S8), a removing process (step S9), a 2 nd rinsing process (step S10), a 2 nd organic solvent supply process (step S11), a spin drying process (step S12), and a substrate carrying-out process (step S13) are sequentially performed.

First, unprocessed substrates W are carried from the carrier C into the processing unit 2 by the transfer robot IR, CR (see fig. 1) and delivered to the spin chuck 5 (step S1). Thereby, the substrate W is horizontally held by the spin chuck 5 (substrate holding step). The spin chuck 5 holds the substrate W until the spin drying process (step S12) is completed. When the substrate W is carried in, the opposing member 6 is retracted to the upper position.

Next, after the transport robot CR is retracted out of the processing unit 2, the chemical liquid supply step (step S2) is started. Specifically, the rotation motor 23 rotates the rotating base 21. Thereby, the substrate W held horizontally rotates (substrate rotating step). The mask lifting and lowering unit 74 moves the 1 st mask 71A and the 2 nd mask 71B to the upper position.

The 1 st nozzle moving unit 36 moves the 1 st moving nozzle 8 to the processing position. The processing position of the 1 st moving nozzle 8 is, for example, a center position. Then, the liquid medicine valve 50 is opened. Thereby, the chemical solution is supplied (discharged) from the 1 st moving nozzle 8 toward the central region of the upper surface of the substrate W in the rotating state. The chemical solution supplied to the upper surface of the substrate W is subjected to a centrifugal force to be diffused radially over the entire upper surface of the substrate W. Thereby, the upper surface of the substrate W is treated with the chemical solution. The discharge of the chemical liquid from the 1 st moving nozzle 8 continues for a predetermined time, for example, 30 seconds. In the chemical solution supplying step, the substrate W is rotated at a predetermined chemical solution rotation speed, for example, 800 rpm.

Next, the 1 st rinsing process (step S3) is started. In the first rinsing step 1, the chemical solution on the substrate W is washed with the rinsing solution.

Specifically, the chemical liquid valve 50 is closed. Thereby, the chemical solution supply to the substrate W is stopped. Then, the 1 st nozzle moving unit 36 moves the 1 st moving nozzle 8 to the home position. Then, the opposing member elevating unit 61 moves the opposing member 6 to the processing position between the upper position and the lower position. When the opposing member 6 is positioned at the processing position, the distance between the upper surface of the substrate W and the opposing surface 6a is, for example, 30 mm. In the 1 st rinsing step, the 1 st and 2 nd masks 71A and 71B are maintained at the upper positions.

In a state where the opposing member 6 is located at the treatment position, the upper rinse liquid valve 54 is opened. Thereby, the rinse liquid is supplied (discharged) from the center nozzle 14 to the center region of the upper surface of the rotating substrate W. The rinse liquid supplied from the central nozzle 14 to the upper surface of the substrate W is dispersed radially over the entire upper surface of the substrate W by centrifugal force. Thereby, the chemical solution on the upper surface of the substrate W is flushed out of the substrate W. In the 1 st rinsing step, the substrate W is rotated at a predetermined 1 st rinsing rotation speed, for example, 800 rpm.

Substantially simultaneously with the opening of the upper rinse liquid valve 54, the lower rinse liquid valve 86 is opened. Thereby, the rinse liquid is supplied (discharged) from the lower surface nozzle 15 to the central region of the lower surface of the rotating substrate W. The rinse liquid supplied from the lower surface nozzle 15 to the lower surface of the substrate W is dispersed radially over the entire lower surface of the substrate W by centrifugal force. Even when the chemical solution scattered from the substrate W in the chemical solution supply step adheres to the lower surface, the chemical solution adhering to the lower surface is flushed by the rinse solution supplied from the lower surface nozzle 15.

The rinsing liquid is continuously discharged from the center nozzle 14 and the lower surface nozzle 15 for a predetermined time, for example, 30 seconds.

Next, the 1 st organic solvent supply process (step S4) is started. In the 1 st organic solvent supply step, the rinsing liquid on the substrate W is replaced with an organic solvent.

Specifically, the upper rinse liquid valve 54 and the lower rinse liquid valve 86 are closed. This stops the supply of the rinse liquid to the upper and lower surfaces of the substrate W. The mask lifting and lowering unit 74 moves the 1 st mask 71A to the lower position while maintaining the 2 nd mask 71B at the upper position. The opposing member 6 is maintained at the processing position.

In a state where the opposing member 6 is maintained at the processing position, the organic solvent valve 56 is opened. Thereby, the organic solvent is supplied (discharged) from the center nozzle 14 to the center region of the upper surface of the substrate W in the rotating state.

The organic solvent supplied from the central nozzle 14 to the upper surface of the substrate W is subjected to a centrifugal force to be diffused radially over the entire upper surface of the substrate W. Thereby, the rinsing liquid on the substrate W is replaced with the organic solvent. The ejection of the organic solvent from the center nozzle 14 is continued for a predetermined time, for example, 10 seconds.

In the 1 st organic solvent supply step, the substrate W is rotated at a predetermined 1 st organic solvent rotation speed, for example, 300 to 1500 rpm. The substrate W does not need to be rotated at a constant rotation speed in the 1 st organic solvent supply step. For example, the spin motor 23 may rotate the substrate W at 300rpm when the supply of the organic solvent is started, and accelerate the rotation of the substrate W to 1500rpm while supplying the organic solvent to the substrate W.

Next, the processing liquid supplying step (step S5) is started. In the treatment liquid supply step, the organic solvent on the substrate W is replaced with the treatment liquid.

Specifically, the organic solvent valve 56 is closed. Thereby, the supply of the organic solvent to the substrate W is stopped. Then, the opposing member elevating unit 61 moves the opposing member 6 to the upper position. Then, the shield elevating unit 74 moves the 1 st shield 71A to the upper position. In the process of supplying the processing liquid, the substrate W is rotated at a predetermined processing liquid rotation speed, for example, 1500 rpm.

In a state where the opposing member 6 is retracted to the upper position, as shown in fig. 6A, the 2 nd nozzle moving unit 37 moves the 2 nd moving nozzle 9 to the processing position. The processing position of the 2 nd moving nozzle 9 is, for example, a center position.

In a state where the 2 nd moving nozzle 9 is located at the treatment position, the treatment liquid valve 51 is opened. Thereby, the processing liquid is supplied (discharged) from the 2 nd moving nozzle 9 to the central region of the upper surface of the substrate W in the rotating state (processing liquid supply step, processing liquid discharge step). Thereby, the organic solvent on the substrate W is replaced with the treatment liquid, and a liquid film 101 of the treatment liquid is formed in the central region of the upper surface of the substrate W (treatment liquid film forming step, treatment liquid nucleus forming step). A liquid film 101 of the processing liquid formed in the central region of the upper surface of the substrate W is referred to as a processing liquid core 102. The supply of the processing liquid from the 2 nd moving nozzle 9 is continued for a predetermined time, for example, 2 seconds to 4 seconds.

The treatment liquid valve 51 may be opened after most of the organic solvent on the substrate W is removed by centrifugal force. In this case, the processing liquid supplied to the central region of the upper surface of the substrate W is less likely to diffuse on the upper surface of the substrate W than in a state where the liquid film of the organic solvent remains on the substrate W, and thus the processing liquid nuclei 102 are more likely to be formed in the central region of the upper surface of the substrate W.

Next, a treatment film forming process is performed (step S6 and step S7). In the process film forming step, the process liquid on the substrate W is cured or hardened to form a process film 100 on the upper surface of the substrate W, the process film holding the object to be removed existing on the substrate W (see fig. 6D).

In the treatment film forming process, first, a thinning process is performed (step S6). In the thin film forming process, the processing liquid on the substrate W is removed by a centrifugal force to thin the liquid film 101 of the processing liquid formed on the upper surface of the substrate W.

Specifically, in the thin film forming process, the treatment liquid valve 51 is first closed. Thereby, the supply of the processing liquid to the substrate W is stopped. And, the 2 nd moving nozzle 9 is moved to the home position by the 2 nd nozzle moving unit 37. In the film-forming step, the opposing member 6, the 1 st mask 71A, and the 2 nd mask 71B are maintained at the upper positions.

As shown in fig. 6B, in the thinning step, the substrate W is rotated at a predetermined increasing speed. The increase rate is, for example, 1500rpm, and is a high rate as in the case of the rotational speed of the treatment liquid. Therefore, the liquid film 101 (treatment liquid nuclei 102) rapidly spreads to the periphery of the substrate W and becomes thin (an expansion and thinning step). When the liquid film 101 spreads to the peripheral edge of the substrate W, as shown in fig. 6C, the processing liquid starts to be removed from the upper surface of the substrate W to the outside of the substrate W.

By increasing the rotation speed (increase speed) of the substrate W in the thin film formation expansion step (for example, 1500rpm), the processing liquid is easily and uniformly spread on the upper surface of the substrate W. This can suppress the occurrence of a phenomenon (Spike phenomenon) in which the upper surface of the substrate W is partially exposed in the processing film 100.

When the process liquid starts to be removed from the upper surface of the substrate W to the outside of the substrate W, the spin motor 23 changes the rotation speed of the substrate W to a predetermined film thickness adjustment speed. Thereby, the liquid film 101 of the processing liquid is adjusted to a desired thickness (film thickness adjusting step). The film thickness adjusting speed is, for example, 300rpm or 1500 rpm.

The amount of the liquid film 101 (the thickness of the liquid film 101) remaining on the upper surface of the substrate W after the completion of the thin-film forming process is determined based on the value of the film thickness adjustment rate, and the thickness (film thickness) of the process film 100 after the completion of the process film forming process is determined. The higher the film thickness adjustment speed, the thinner the film thickness of the process film 100. Therefore, when the film thickness adjustment speed is 1500rpm, the film thickness of the process film 100 formed in the process film formation step is smaller than that in the case where the film thickness adjustment speed is 300 rpm.

In this manner, the film thickness of the treatment film 100 is adjusted by changing the substrate rotation speed by the rotation motor 23 to thin the liquid film 101 of the treatment liquid. That is, the rotary motor 23 functions as a thin film forming means for forming a thin film of the liquid film 101 of the processing liquid, and functions as a processing film thickness adjusting means for adjusting the thickness of the processing film 100.

In the treatment film forming step, after the thin film forming step (step S6), a solid forming step of curing or hardening the liquid film 101 of the treatment liquid is performed (step S7). In the solid forming step, the liquid film 101 on the substrate W is heated in order to volatilize (evaporate) a part of the solvent of the processing liquid on the substrate W.

Specifically, in the solid forming step, as shown in fig. 6D, the opposing member lifting and lowering unit 61 moves the opposing member 6 to the close position between the upper position and the lower position. The approach position may also be a 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. In the heating step, the 1 st mask 71A and the 2 nd mask 71B are held at the upper positions.

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).

Evaporation (volatilization) of the solvent in the liquid film 101 is promoted by blowing a gas onto the liquid film 101 on the substrate W (solvent evaporation step, solvent evaporation promotion step). Therefore, the time required for forming the processing film 100 can be shortened. The central nozzle 14 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the processing liquid.

In addition, the heating medium valve 88 is opened. Thereby, the heat medium is supplied (discharged) from the lower surface nozzle 15 (heat medium supply step, heat medium discharge step). The heat medium supplied from the lower surface nozzle 15 to the lower surface of the substrate W is subjected to a centrifugal force to be diffused radially over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W is continued for a predetermined time, for example, 60 seconds. In the solid forming step, the substrate W is rotated at a predetermined solid forming rotation speed, for example, 1000 rpm.

The liquid film 101 on the substrate W is heated through the substrate W by supplying a heat medium to the lower surface of the substrate W (heating step). Thereby, evaporation (volatilization) of the solvent in the liquid film 101 is promoted (solvent evaporation step, solvent evaporation promotion step). Therefore, the time required for forming the processing film 100 can be shortened. The lower surface nozzle 15 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

By performing the thinning step and the solid forming step, the processing liquid is cured or hardened, and as shown in fig. 6D, a processing film 100 is formed on the substrate W. In this manner, the substrate rotating unit (the rotary motor 23), the center nozzle 14, and the lower surface nozzle 15 constitute a solid forming unit that solidifies or hardens the processing liquid to form a solid (the processing film 100).

In the solid forming step, the substrate W is preferably heated so that the temperature of the processing liquid on the substrate W is lower than the boiling point of the solvent. By heating the treatment liquid to a temperature lower than the boiling point of the solvent, the solvent can be appropriately left in the treatment film 100. Thus, the solvent remaining in the processing film 100 interacts with the removing solution in the subsequent removing step, so that the removing solution is more likely to penetrate into the processing film 100, as compared with the case where no solvent remains in the processing film 100. Therefore, the treatment film 100 can be easily removed by the removing liquid.

The heat medium scattered to the outside of the substrate W by the centrifugal force is received by the 1 st mask 71A. There is a case where the heat medium received by the 1 st shield 71A bounces back from the 1 st shield 71A. However, since the opposing member 6 is close to the upper surface of the substrate W, the upper surface of the substrate W can be protected against the heat medium rebounded from the 1 st mask 71A. Therefore, the adhesion of the heat medium to the upper surface of the treatment film 100 can be suppressed, and the generation of particles caused by the rebound of the heat medium from the 1 st mask 71A can be suppressed.

Further, as shown in fig. 6D, by supplying the gas from the central nozzle 14, a gas flow F moving from the central region of the upper surface of the substrate W toward the peripheral edge of the upper surface of the substrate W is formed in the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W. By forming the air flow F moving from the central area of the upper surface of the substrate W toward the peripheral edge of the upper surface of the substrate W, the heat medium rebounded from the 1 st mask 71A can be pushed back toward the 1 st mask 71A. Therefore, the adhesion of the heat medium to the upper surface of the treatment film 100 can be further suppressed.

In the substrate processing, the processing liquid supplied to the upper surface of the substrate W in the processing liquid supply step (step S5) shown in fig. 6A may run along the peripheral edge of the substrate W to the lower surface of the substrate W. The processing liquid scattered from the substrate W may bounce off the 1 st mask 71A and adhere to the lower surface of the substrate W. In this case as well, as shown in fig. 6D, since the heat medium is supplied to the lower surface of the substrate W in the solid forming step (step S7), the processing liquid can be removed from the lower surface of the substrate W by the flow of the heat medium.

Next, a protective liquid film forming process is performed (step S8). In the protective liquid film forming step, a liquid film of the protective liquid (protective liquid film 105) is formed on the upper surface of the substrate W.

Specifically, the heating medium valve 88 is closed. This stops the supply of the heat medium to the lower surface of the substrate W. In addition, the gas valve 55 is closed. Thereby, the supply of the gas from the center nozzle 14 to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is stopped.

The opposing member elevating unit 61 moves the opposing member 6 to the upper position in a state where the supply of the gas from the center nozzle 14 is stopped. Then, as shown in fig. 6E, the 3 rd nozzle moving unit 38 moves the 3 rd moving nozzle 10 to the processing position.

The processing position of the 3 rd moving nozzle 10 is, for example, a center position. At this time, the 4 th moving nozzle 11 is disposed laterally of the center position. Referring to fig. 3B, in order to set the target position P1 on the substrate W at which the 4 th moving nozzle 11 discharges the protective liquid to a position on the upstream side of the supply region S in the rotation direction Dr of the substrate W, the 3 rd moving nozzle 10 may be arranged at a position slightly shifted from the center position toward the peripheral edge of the substrate W.

Then, the protection liquid valve 57A is opened. Thereby, as shown in fig. 6E, the protective liquid is supplied (discharged) from the 4 th moving nozzle 11 in a continuous flow to the central region of the upper surface of the substrate W in the rotating state. The protective liquid supplied to the upper surface of the substrate W is radially diffused by the centrifugal force and spreads over the entire upper surface of the substrate W. Thereby, the protective liquid film 105 is formed on the upper surface of the substrate W. In this manner, the 4 th movable nozzle 11 functions as the 1 st protective liquid supply unit.

The ejection of the protective liquid from the 4 th moving nozzle 11 is continued for a predetermined time, for example, 30 seconds. In the protective liquid supplying step, the substrate W is rotated at a predetermined protective liquid rotation speed, for example, 800 rpm.

Next, a removal process is performed (step S9). In the removal step, the processing film 100 is removed from the upper surface of the substrate W.

Specifically, the removal liquid valve 52 is opened, and the discharge valve 53 is closed. The voltage application unit 93 applies an alternating voltage to the piezoelectric element 91. As a result, as shown in fig. 6F, the removal liquid is supplied (discharged) from the 3 rd moving nozzle 10 in a droplet state to the central region of the upper surface of the substrate W in the rotating state (upper removal liquid supply step, upper removal liquid discharge step, droplet supply step).

The supply of the removing liquid to the upper surface of the substrate W is continued for a predetermined time, for example, 60 seconds. In the removal step, the substrate W is rotated at a predetermined removal rotation speed, for example, 800 rpm.

While the removal liquid is supplied in a droplet state to the upper surface of the substrate W, as shown in fig. 6F, the supply of the protective liquid from the 4 th moving nozzle 11 is continued (protective liquid parallel supply step). In this manner, the 4 th movable nozzle 11 functions as the 2 nd protective liquid supply unit. The supply of the protective liquid from the 4 th moving nozzle 11 to the upper surface of the substrate W is continued from the protective liquid film forming step.

Further, the lower-side liquid removal valve 87 is opened. Thereby, the removal liquid is supplied (discharged) from the lower surface nozzle 15 in a continuous flow to the central region of the lower surface of the substrate W in the rotating state (lower removal liquid supply step, lower removal liquid discharge step). The removal liquid supplied to the lower surface of the substrate W is diffused to the entire lower surface of the substrate W by the centrifugal force.

By supplying the removal liquid in a droplet state to the upper surface of the substrate W, a physical force of the droplet 106 acts on the processing film 100. The physical force of the droplets 106 of the removal liquid is an impact (kinetic energy) when the droplets 106 of the removal liquid collide with the protective liquid film 105.

The physical force of the liquid droplet 106 can be adjusted by changing the frequency of the alternating voltage applied to the piezoelectric element 91. Specifically, the larger the frequency of the alternating voltage applied to the piezoelectric element 91, the smaller the size of the liquid droplets 106, and the larger the number of liquid droplets 106 ejected per unit time by the 3 rd moving nozzle 10. Therefore, the physical force of the droplet 106 acting on the upper surface of the substrate W increases.

The physical force of the droplets 106 can also be adjusted by altering the pressure of the pump 90. Specifically, the larger the pressure of the pump 90, the larger the flow rate of the removal liquid ejected from the ejection port 94d of the 3 rd moving nozzle 10 and the larger the amount of the droplets 106. Therefore, the physical force of the droplet 106 acting on the upper surface of the substrate W increases.

The physical force of the liquid droplets 106 is transmitted to the treatment film 100 and the object to be removed via the protective liquid film 105. Thereby, the processing film 100 and the object to be removed are peeled off from the upper surface of the substrate W (peeling step, processing film peeling step, object to be removed peeling step). The processing film 100 is split into films when peeled off from the upper surface of the substrate W (splitting step).

When the droplets 106 of the removal liquid are supplied onto the upper surface of the substrate W, the 3 rd nozzle transfer unit 38 may reciprocate the 3 rd transfer nozzle 10 between the peripheral edge positions where the center position faces the peripheral edge region of the upper surface of the substrate W. This allows the droplet 106 to collide with the entire upper surface of the substrate W without fail, and hence the portion of the droplet 106 on which the physical force acts can be dispersed over the entire process film 100.

When the supply region S is the central region of the upper surface of the substrate W, the physical force of the liquid droplets 106 always acts on the same portion on the upper surface of the substrate W regardless of the rotation angle of the substrate W. On the other hand, if the supply region S is a region (for example, a peripheral region) other than the central region on the upper surface of the substrate W, a portion of the upper surface of the substrate W that receives the physical force of the droplet 106 changes in association with the rotation of the substrate W. Therefore, when the supply region S is fixed to the central region of the upper surface of the substrate W, the uneven pattern on the upper surface of the substrate W is easily damaged. Therefore, by reciprocating the 3 rd moving nozzle 10 between the center position and the peripheral position, it is possible to avoid concentration of physical force particularly to the center area of the upper surface of the substrate W.

After the treatment film 100 is peeled and split, the removal liquid is continuously supplied to the upper surface of the substrate W, whereby the film pieces of the treatment film 100 formed by the split are removed from the substrate W together with the removal liquid. Thereby, the object to be removed and the diaphragm of the processing film 100 are removed from the upper surface of the substrate W (removing step).

The 2 nd rinsing process (step S10) is performed after the removing process (step S9). Specifically, the protection liquid valve 57A and the lower removal liquid valve 87 are closed, and the discharge valve 53 is opened. Thus, the supply of the protective liquid to the upper surface of the substrate W and the supply of the removal liquid to the upper surface and the lower surface of the substrate W are stopped. The purge valve 52 may be always open. Then, the voltage application unit 93 stops the application of the alternating voltage to the piezoelectric element 91. Then, the 3 rd nozzle moving unit 38 moves the 3 rd moving nozzle 10 and the 4 th moving nozzle 11 to the home positions.

In a state where the 3 rd moving nozzle 10 and the 4 th moving nozzle 11 are moved to the home positions, as shown in fig. 6G, the opposing member elevating unit 61 moves the opposing member 6 to the processing position. In the 2 nd rinsing step, the substrate W is rotated at a predetermined 2 nd rinsing rotation speed, for example, 800 rpm. The 1 st and 2 nd masks 71A and 71B are maintained at the upper position.

Then, the upper rinse liquid valve 54 is opened. Thereby, the rinse liquid is supplied (discharged) from the center nozzle 14 to the central region of the upper surface of the rotating substrate W (the 2 nd upper rinse liquid supply step, the 2 nd upper rinse liquid discharge step). The rinse liquid supplied to the upper surface of the substrate W is diffused to the entire upper surface of the substrate W due to the centrifugal force. Thereby, the removal liquid adhering to the upper surface of the substrate W is washed by the rinse liquid.

In addition, the lower rinse liquid valve 86 is opened. Thereby, the rinse liquid is supplied (discharged) from the lower surface nozzle 15 to the central region of the lower surface of the rotating substrate W (the 2 nd lower rinse liquid supply step, the 2 nd lower rinse liquid discharge step). Thereby, the removal liquid adhering to the lower surface of the substrate W is washed with the rinse liquid. The supply of the rinse liquid to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, 35 seconds.

Next, the 2 nd organic solvent supply process is performed (step S11). In the 2 nd organic solvent supply step, the organic solvent is supplied to the upper surface of the substrate W, whereby the residue of the processing film 100 remaining on the upper surface of the substrate W is dissolved in the organic solvent and removed.

Specifically, the upper rinse liquid valve 54 and the lower rinse liquid valve 86 are closed. This stops the supply of the rinse liquid to the upper and lower surfaces of the substrate W. Then, as shown in fig. 6H, the shield elevating unit 74 moves the 1 st shield 71A to the lower position. The opposing member 6 is maintained at the processing position. In the 2 nd organic solvent supply step, the substrate W is rotated at a predetermined 2 nd organic solvent rotation speed of, for example, 300 rpm.

In a state where the opposing member 6 is maintained at the processing position, the organic solvent valve 56 is opened. Thereby, the organic solvent is supplied (discharged) from the center nozzle 14 to the center region of the upper surface of the substrate W in the rotating state (the 2 nd organic solvent supply step, the 2 nd organic solvent discharge step, and the residue removing liquid supply step). The supply of the organic solvent to the upper surface of the substrate W is continued for a predetermined time, for example, 30 seconds.

The organic solvent supplied to the upper surface of the substrate W is subjected to a centrifugal force to be diffused in a radial shape and to be diffused to the entire upper surface of the substrate W. Thereby, the rinsing liquid on the upper surface of the substrate W is replaced with the organic solvent. The organic solvent supplied to the upper surface of the substrate W dissolves the residue of the process film 100 remaining on the upper surface of the substrate W, and is then discharged from the periphery of the upper surface of the substrate W (residue removal step). This removes the residue of the processing film 100 from the upper surface of the substrate W, and thus the upper surface of the substrate W can be cleaned satisfactorily.

In this manner, in the 2 nd organic solvent supply step, the organic solvent functions as a dissolving solution for dissolving the residue of the processing film 100 on the upper surface of the substrate W. The central nozzle 14 also functions as a solution supply unit for supplying a solution to the upper surface of the substrate W.

Next, a spin drying process is performed (step S12). By performing the spin drying process, the upper and lower surfaces of the substrate W are dried.

Specifically, the organic solvent valve 56 is closed. Thereby, the supply of the organic solvent to the upper surface of the substrate W is stopped. Then, as shown in fig. 6I, the opposing member elevating unit 61 moves the opposing member 6 to the drying position below the processing position. When the opposed member 6 is located at the drying position, the distance between the opposed surface 6a of the opposed member 6 and the upper surface of the substrate W is, for example, 1.5 mm. 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 6a of the facing member 6.

Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed. The substrate W in the spin drying process is rotated at a drying speed of, for example, 1500 rpm. The spin-drying process is continuously performed for a predetermined time, for example, 30 seconds. Thereby, a large centrifugal force acts on the organic solvent on the substrate W, and the organic solvent on the substrate W is spun out to the periphery of the substrate W. In the spin drying step, the evaporation of the organic solvent is promoted by supplying a gas into the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

Then, the rotation motor 23 stops the rotation of the substrate W. The mask lifting and lowering unit 74 moves the 1 st mask 71A and the 2 nd mask 71B to the lower position. The gas valve 55 is closed. Then, the opposing member elevating unit 61 moves the opposing member 6 to the upper position.

The transfer robot CR enters the processing unit 2, lifts up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries the substrate W out of the processing unit 2 (step S13). The substrate W is transferred from the transfer robot CR to the transfer robot IR, and is stored in the carrier C by the transfer robot IR.

Next, a change in the vicinity of the upper surface of the substrate W when the processing film 100 is removed from the substrate W in the case where the protective liquid and the removing liquid are both pure water will be described with reference to fig. 7A to 7C.

Fig. 7A shows the vicinity of the upper surface of the substrate W immediately after the solid-state forming process (step S7) is completed. Fig. 7B shows the upper surface of the substrate W immediately after the protective liquid film formation step (step S8) is completed. Fig. 7C shows the vicinity of the upper surface of the substrate W in the execution of the removal process (step S9).

In the solid forming step (step S7) performed in the treatment film forming step, as described above, the liquid film 101 on the upper surface of the substrate W is heated with the heat medium through the substrate W. At least a part of the solvent evaporates, and as shown in fig. 7A, a processing film 100 holding a removal object 103 such as particles is formed.

The thickness T of the processing film 100 is about several tens nm (e.g., 30 nm). The film thickness T of the process film 100 is the thickness of the process film 100 at a portion where the object to be removed 103 is not present. Objects to be removed 103 of various sizes are attached to the upper surface of the substrate W. Fig. 7A shows objects to be removed 103 of 3 sizes.

On the substrate W, there may be a 1 st object to be removed 103A having a radius R larger than the film thickness T of the process film 100 and a 2 nd object to be removed 103B having a radius smaller than the film thickness T of the process film 100.

In the processing liquid supply step described above, the processing liquid enters between the 2 nd object to be removed 103B and the upper surface of the substrate W. Therefore, the solid solute enters between the 2 nd removal object 103B and the upper surface of the substrate W. The 2 nd object to be removed 103B is firmly held by the processing film 100.

On the other hand, in the processing liquid supply step, the processing liquid may not smoothly enter a space below the height position of the center of the 1 st removal object 103A between the 1 st removal object 103A and the upper surface of the substrate W.

The height of the center of the 1 st object to be removed 103A corresponds to the radius of the 1 st object to be removed 103A. The space below the height position of the center of the 1 st removal object 103A is also a space below the horizontal cross section passing through the center of the 1 st removal object 103A.

In this case, a cavity 104 may be formed between the 1 st object to be removed 103A and the upper surface of the substrate W. Alternatively, even if the processing liquid enters a space below the height position of the center of the 1 st object to be removed 103A between the 1 st object to be removed 103A and the upper surface of the substrate W, the processing liquid may form the cavity 104 during solidification. In any of the above cases, the holding force of the processing film 100 for holding the 1 st removal object 103A is smaller than the holding force of the processing film 100 for holding the 2 nd removal object 103B.

Then, by supplying the protective liquid to the upper surface of the substrate W in the protective liquid film forming step, a protective liquid film 105 covering the processing film 100 is formed on the upper surface of the substrate W as shown in fig. 7B.

Thereafter, in a state where the protective liquid film 105 is formed on the upper surface of the substrate W, as shown in fig. 7C, the physical force of the droplet 106 acts on the processing film 100 and the object to be removed 103 by supplying the droplet 106 of the removing liquid in the removing step. When the physical force of the liquid droplets 106 acts on the processing film 100, the processing film 100 is split and becomes the diaphragm 107, and the diaphragm 107 is peeled from the upper surface of the substrate W (processing film splitting step, processing film peeling step).

The 2 nd object to be removed 103B is firmly held by the membrane 107 of the processing film 100. Therefore, when the processing film 100 is peeled, the 2 nd removal object 103B is pulled by the diaphragm 107 of the processing film 100 and peeled from the substrate W.

The 1 st object to be removed 103A may not be held by the treatment film 100 with a sufficient holding force, and thus may have a higher adhesive force with the substrate W than the holding force of the treatment film 100. In this case, the processing film 100 cannot carry the 1 st object to be removed 103A away from the upper surface of the substrate W. However, the physical force of the droplets 106 of the removal liquid directly acts on the object to be removed 103. Therefore, the 1 st object to be removed 103A can be peeled off from the upper surface of the substrate W (object to be removed peeling step).

When the processing film 100 is split, a plurality of cracks (cracks) are formed in the processing film 100. The cracks are elongated grooves, and serve as base points for splitting the processed film 100. Depending on the position of the crack, the 2 nd object to be removed 103B having a radius smaller than the film thickness T of the process film 100 may be detached from the process film 100. In this case, the 2 nd object to be removed 103B is also peeled off from the upper surface of the substrate W by the physical force of the droplets 106 of the removal liquid acting on the 2 nd object to be removed 103B.

In this manner, the removal object 103 can be peeled off from the upper surface of the substrate W regardless of the holding force of the processing film 100 to the removal object 103.

Then, by continuing the supply of the removal liquid, the processing film 100 that becomes the membrane sheet 107 is washed away (pushed out of the substrate W) while holding the 2 nd removal object 103B, and removed from the upper surface of the substrate W (removal step).

The 1 st object to be removed 103A that is not sufficiently held by the processing film 100 and the 2 nd object to be removed 103B detached from the processing film 100 are also washed away (pushed out of the substrate W) by continuing to supply the removal liquid, and removed from the upper surface of the substrate W (removal step).

According to embodiment 1, the treatment liquid supplied to the upper surface of the substrate W is cured or hardened, thereby forming the treatment film 100 holding the object to be removed 103 on the upper surface of the substrate (treatment film forming step). Then, the removal liquid is supplied in a droplet state to the upper surface of the substrate W. Thereby, the physical force of the droplets 106 of the removal liquid acts on the processing film 100 and the object to be removed 103.

Specifically, by applying a physical force of the droplets 106 of the removing liquid to the processing film 100, the processing film 100 holding the object to be removed 103 is separated from the upper surface of the substrate W and removed from the upper surface of the substrate W (processing film removing step). Then, the physical force of the droplets 106 of the removing liquid is applied to the object to be removed 103, whereby the object to be removed 103 is removed from the upper surface of the substrate W (an object-to-be-removed removing step).

Therefore, the physical force of the droplets 106 of the removal liquid is applied to the processing film 100, so that most of the objects to be removed 103 (the 2 nd objects to be removed 103B) can be removed from the upper surface of the substrate W together with the processing film 100.

Further, by applying physical force of the droplets 106 of the removal liquid to the object to be removed, the 1 st object to be removed 103A which is not held on the processing film 100 with sufficient holding force and the 2 nd object to be removed 103B which is detached from the processing film 100 can also be removed from the upper surface of the substrate W. That is, even when the film thickness T of the process film 100 is smaller than the radius R of the 1 st object to be removed 103A, the 1 st object to be removed 103A can be sufficiently removed from the upper surface of the substrate W.

As a result, the object 103 can be efficiently removed from the upper surface of the substrate W.

The physical force acting on the upper surface of the substrate W from the droplet 106 of the removal liquid is particularly large in the supply region S. Therefore, the concave-convex pattern formed in the supply region S may collapse due to the physical force acting on the upper surface of the substrate W from the droplets 106 of the removal liquid.

In embodiment 1, the supply region S is covered with the protective liquid film 105 before the removal step is started. By appropriately reducing the physical force acting on the supply region S from the droplets 106 of the removal liquid, the physical force of the droplets 106 of the removal liquid can be dispersed over the entire upper surface of the substrate W. This makes it possible to remove the processing film 100 and the object to be removed 103 from the upper surface of the substrate W while protecting the uneven pattern formed on the upper surface of the substrate W.

The physical force acting on the upper surface of the substrate W when a continuous flow of liquid is supplied to the upper surface of the substrate W is very small compared to the physical force acting on the upper surface of the substrate W when liquid droplets are supplied to the upper surface of the substrate W. Therefore, if the protective liquid is supplied in a continuous flow onto the upper surface of the substrate W, collapse of the uneven pattern formed on the upper surface of the substrate W due to the supply of the protective liquid can be suppressed or prevented.

In embodiment 1, while the removal liquid is supplied in the form of droplets onto the upper surface of the substrate W in the removal step, the protective liquid is supplied in a continuous flow onto the upper surface of the substrate W (protective liquid parallel supply step). Therefore, the protective liquid film 105 can be maintained even during the removal step. This can reduce the physical force acting on the supply region S from the droplets 106 of the removal liquid appropriately, and can disperse the physical force of the droplets 106 of the removal liquid over the entire upper surface of the substrate W. This makes it possible to remove the processing film 100 and the object to be removed 103 from the upper surface of the substrate W while protecting the uneven pattern formed on the upper surface of the substrate W.

Pure water has a higher surface tension than an alkaline aqueous solution such as SC 1. Therefore, when pure water is used as the removal liquid, the physical force applied to the treatment film 100 can be increased as compared with when an alkaline aqueous solution such as SC1 is used as the removal liquid.

When the removal liquid is water, the treatment film 100 is less likely to be dissolved than when the removal liquid is an alkaline liquid. Therefore, the physical force can be applied to the processing film 100 in a state where the number of the objects to be removed 103 held in the processing film 100 is as large as possible. When the protective liquid is water, the treatment film 100 is less likely to be dissolved than when the protective liquid is an alkaline liquid, and thus the treatment film 100 is likely to maintain the state in which the object 103 to be removed is held.

Unlike the case where both the protective solution and the removal solution are pure water (see fig. 7A to 7C), in the case where pure water is used as the removal solution and an alkaline aqueous solution such as SC1 solution is used as the protective solution, the treatment film 100 is partially dissolved by the protective solution supplied to the upper surface of the substrate W in the protective solution film formation step (step S8), so that the strength of the treatment film 100 is reduced. The treatment film 100 is partially dissolved means that the treatment film 100 is dissolved to the extent that the treatment film 100 is formed with cracks.

Specifically, as shown in fig. 8, the treatment film 100 is partially dissolved by the protective liquid supplied to the upper surface of the substrate W in the protective liquid film forming step, whereby the crack 108 is formed in the treatment film 100. Thereby, the treatment film 100 becomes easily cracked. By forming the crack 108, the protective liquid easily reaches the vicinity of the upper surface of the substrate W. Therefore, the protective liquid enters the gap G1 between the processing film 100 and the substrate W, and dissolves the surface of the processing film 100. This makes it easier for the process film 100 to be peeled off from the upper surface of the substrate W.

Therefore, in the removal step, the physical force of the droplets 106 of the removal liquid can be applied to the treatment film 100 while the strength of the treatment film is reduced by the protective liquid. This makes it possible to efficiently split the processing film 100 and to efficiently peel the processing film 100 from the upper surface of the substrate W. As a result, the processing film 100 can be efficiently removed from the upper surface of the substrate W.

In fig. 8, the crack 108 penetrates the processed film 100, but the crack 108 may not penetrate the processed film 100 and may locally thin the processed film 100.

Unlike the case where both the protective solution and the removal solution are pure water (see fig. 7A to 7C), when an alkaline aqueous solution such as SC1 solution is used as the removal solution and pure water is used as the protective solution, the treatment film 100 is partially dissolved by the removal solution supplied in the form of droplets to the upper surface of the substrate W, and the strength of the treatment film 100 is lowered.

Therefore, in the removal step, the strength of the treatment film 100 can be reduced by the removal liquid, and the physical force of the droplets 106 of the removal liquid can be applied to the treatment film 100. This makes it possible to efficiently split the processing film 100 and efficiently peel the processing film 100 from the upper surface of the substrate W. As a result, the processing film 100 can be efficiently removed from the upper surface of the substrate W. Further, the physical force of the droplet 106 of the removal liquid can be alleviated by the protective liquid.

Unlike the case where both the protective solution and the removal solution are pure water (see fig. 7A to 7C), when both the removal solution and the protective solution are an alkaline aqueous solution such as SC1 solution, the treatment film 100 is partially dissolved in the protective solution film formation step and the removal step, and the strength of the treatment film 100 is lowered.

Therefore, in the removal step, the strength of the treatment film 100 can be reduced by the protective solution and the removal solution, and the physical force of the droplets 106 of the removal solution can be applied to the treatment film 100. This makes it possible to efficiently split the processing film 100 and efficiently peel the processing film 100 from the upper surface of the substrate W. As a result, the processing film 100 can be efficiently removed from the upper surface of the substrate W. Further, the physical force of the droplet 106 of the removal liquid can be alleviated by the protective liquid.

< embodiment 2 >

In embodiment 2, a substrate processing apparatus having the same configuration as the substrate processing apparatus 1 of embodiment 1 can be used to perform the same substrate processing as that described in embodiment 1. The main difference between embodiment 2 and embodiment 1 is that the solute in the processing liquid discharged from the 2 nd moving nozzle 9 contains a low-solubility substance and a high-solubility substance.

The low-solubility substance and the high-solubility substance may have different solubilities with respect to the removing solution and the protecting solution.

The low-solubility substance contained in the treatment liquid discharged from the 2 nd moving nozzle 9 is, for example, novolac. The highly soluble substance contained in the treatment liquid discharged from the 2 nd moving nozzle 9 is, for example, 2-bis (4-hydroxyphenyl) propane.

The solvent contained in the treatment liquid discharged from the 2 nd moving nozzle 9 may be a liquid in which a low-solubility substance and a high-solubility substance are dissolved. The solvent contained in the treatment solution is preferably a liquid having compatibility (miscibility) with the removal solution.

Details of the solvent, the low-solubility substance, and the high-solubility substance contained in the treatment liquid discharged from the 2 nd moving nozzle 9 will be described later.

The substrate processing of embodiment 2 is different from the substrate processing of embodiment 1 in the vicinity of the upper surface of the substrate W. With reference to fig. 9A to 9C, a case where the processing film is removed from the substrate W in the substrate processing of embodiment 2 will be described. In fig. 9A to 9C, a case where both the removing solution and the protecting solution are alkaline aqueous solutions will be described as an example.

Fig. 9A shows the vicinity of the upper surface of the substrate W immediately after the solid-state forming process (step S7) is completed. Fig. 9B shows the upper surface of the substrate W when the treatment film 200 is partially dissolved in the protective solution film forming step (step S8) and the removing step (step S9). Fig. 9C shows the vicinity of the upper surface of the substrate W when the physical force acts on the processing film 200 in the removal step (step S9).

In the solid forming step, as described above, the liquid film 101 of the processing liquid on the substrate W is heated by the heat medium through the substrate W. As a result, as shown in fig. 9A, the processing film 200 holding the objects to be removed 103 such as particles is formed.

In detail, at least a part of the solvent is evaporated, and thus the highly soluble substance contained in the solute of the treatment liquid forms the highly soluble solid 210 (highly soluble substance in a solid state). In addition, at least a part of the solvent evaporates, whereby a low-solubility substance contained in the solute of the treatment liquid forms a low-solubility solid 211 (a low-solubility substance in a solid state). The low-solubility substance and the high-solubility substance are formed into a film together.

"filmed" is not the case where the low-solubility material and the high-solubility material form separate layers. One way of "filming" is "curing", "hardening".

A high-solubility solid 210 and a low-solubility solid 211 are mixed in the treatment film 200. The high-solubility solid 210 and the low-solubility solid 211 are not uniformly distributed throughout the entire processing film 200, but there are a portion in which the high-solubility solid 210 is localized and a portion in which the low-solubility solid 211 is localized. In the processing film 200, a cavity 104 may be formed between the 1 st object to be removed 103A and the upper surface of the substrate W.

As shown in fig. 9B, the highly soluble solid 210 is selectively dissolved by the protective liquid supplied to the upper surface of the substrate W in the protective liquid film forming step (step S8) and the removing liquid supplied to the upper surface of the substrate W in the removing step (step S9). That is, the processing film 200 is partially dissolved. The highly soluble solid 210 is dissolved, and thereby the through-hole 202 is formed in the processed film 200 at a portion where the highly soluble solid 210 is located (through-hole forming step). The through-hole 202 is particularly easily formed in a portion of the highly soluble solid 210 extending in the thickness direction D of the substrate W (also in the thickness direction of the handle film 200). The through hole 202 has a diameter of, for example, several nm in a plan view.

The protective solution and the removing solution reach the vicinity of the upper surface of the substrate W through the through hole 202. The low-solubility solid 211 is dissolved in a small amount in an alkaline aqueous solution. Therefore, in the low-solubility solid 211, a portion in the vicinity of the upper surface of the substrate W is dissolved by a small amount. Thus, as shown in the enlarged view of fig. 9B, the protective solution and the removing solution gradually dissolve the low-solubility solid 211 near the upper surface of the substrate W and enter the gap G2 between the processing film 200 and the upper surface of the substrate W (removing solution entering step, protective solution entering step).

Finally, the treatment film 200 is split into the membrane 207 starting from the periphery of the through hole 202 by the physical force of the droplets 106 of the removal liquid. Then, as shown in fig. 9C, the membrane sheet 207 of the processing film 200 is peeled off from the substrate W in a state where the removal object 103 is held (a splitting step, a processing film peeling step). At the same time, the object to be removed 103 is peeled off from the upper surface of the substrate W by the physical force of the droplets 106 of the removing liquid (object-to-be-removed peeling step). Therefore, even when the 1 st object to be removed 103A having the radius R larger than the film thickness T of the process film 200 is present on the upper surface of the substrate W, the 1 st object to be removed 103A is peeled off from the upper surface of the substrate W.

When the treatment film 200 is partially dissolved, the 2 nd removal object 103B held by a portion of the treatment film 200 in which the highly soluble solid 210 is localized may be detached from the treatment film 200. Even in such a case, the 2 nd object to be removed 103B is peeled off from the upper surface of the substrate W by the physical force of the droplets 106 of the removal liquid acting on the 2 nd object to be removed 103B.

Then, by continuing the supply of the removal liquid, the processing film 200 serving as the membrane 207 is washed (pushed out of the substrate W) in a state where the 2 nd removal object 103B is held, and removed from the upper surface of the substrate W (removal step).

The 1 st object to be removed 103A that is not sufficiently held by the processing film 200 and the 2 nd object to be removed 103B detached from the processing film 200 are also washed away (pushed out of the substrate W) by continuing to supply the removal liquid, and are removed from the upper surface of the substrate W (removal step).

When one of the protective solution and the removing solution is pure water, the case of removing the processing film 200 from the substrate W is slightly different from the case where both the protective solution and the removing solution are alkaline aqueous solutions (see fig. 9A to 9C).

Specifically, when the protective solution is an alkaline aqueous solution and the removal solution is pure water, the highly soluble solid 210 is dissolved in the protective solution, and the treatment film 200 is hardly dissolved in the removal solution. In the case where the protective solution is pure water and the removal solution is an alkaline aqueous solution, the highly soluble solid 210 is dissolved in the removal solution, and the treatment film 200 is hardly dissolved in the protective solution.

Embodiment 2 has the same effects as embodiment 1.

Further, according to embodiment 2, the highly soluble solid 210 in a solid state in the processing film 200 is selectively dissolved by at least one of the protective liquid and the removing liquid. Therefore, the strength of the treatment film 200 is reduced. On the other hand, the low-solubility solid 211 in the processing film 200 is maintained in a solid state in which the object to be removed 103 is held. Therefore, the physical force of the droplets 106 of the removal liquid can be applied to the processing film 200 in the removal step while the removal object 103 is still held on the processing film 200 and the strength of the processing film 200 is reduced. Thereby, the processing film 200 is efficiently split, and the processing film 200 is efficiently peeled from the surface of the substrate.

The removing solution and the protecting solution may be pure water. However, in this case, since the treatment film 200 is hardly dissolved in the protective solution and the removing solution, it is basically broken by only the physical force of the droplets 106 of the removing solution and is peeled off from the upper surface of the substrate W.

< details of the treating liquid used in embodiment 2 >

Hereinafter, each component in the treatment liquid used in embodiment 2 will be described.

Hereinafter, "C_x～y”、“C_x～C_y"and" C_x"etc. indicates the number of carbons in a molecule or substituent. E.g. C_1～6The alkyl group represents an alkyl chain having 1 to 6 carbons (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.).

In the case of polymers having a plurality of repeating units, these repeating units are copolymerized. The copolymerization may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or the like, as long as it is not particularly limited. When the polymer or resin is represented by a structural formula, n, m, etc. indicated in parentheses represent the number of repetitions.

The same applies to the components in the treatment liquid, the removing liquid, and the protective liquid in embodiment 3 described later.

< Low-solubility substance >

(A) The low-solubility material comprises at least 1 of a copolymer of novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and combinations thereof. Preferably, (a) the low-solubility substance may also contain at least 1 of a copolymer of novolac, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and combinations thereof. Further preferably, (a) the low-solubility substance may also contain at least 1 of a copolymer of novolac, polyhydroxystyrene, polycarbonate, and a combination thereof. The novolac may also be a novolac (phenolic novolac).

The treatment liquid may contain 1 or a combination of 2 or more of the above-described preferred examples as the low-solubility substance (a). For example, (a) the low-solubility material may also comprise both novolac and polyhydroxystyrene.

(A) The low-solubility substance is dried to form a film, and most of the film is not dissolved by the removing solution and is peeled off in a state of holding the object to be removed. The method (a) allows a very small portion of the low-soluble substance to be dissolved in the removing solution.

Preferably (a) the low-solubility substance does not contain fluorine and/or silicon, and more preferably does not contain both.

The copolymerization is preferably a random copolymerization or a block copolymerization.

Specific examples of the low-solubility substance (a) include, but are not limited to, compounds represented by the following chemical formulae 1 to 7.

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

(asterisks indicate bonding to adjacent building blocks.)

[ chemical formula 4]

(RIs represented by C_1～4Alkyl groups, and the like. Asterisks indicate bonding to adjacent building blocks. )

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

(Me represents a methyl group.)

The weight average molecular weight (Mw) of the low-solubility substance (A) is preferably 150 to 500000, more preferably 300 to 300000, still more preferably 500 to 100000, and still more preferably 1000 to 50000.

(A) Low solubility materials can be obtained by synthesis. In addition, it can be purchased. In the case of purchase, for example, the suppliers are as follows. The (A) polymer may also be synthesized by a supplier.

Phenolic aldehyde varnish: shoghe chemical industry (strain), xu organic material (strain), qurong chemical industry (strain), sumitomo bakelite (strain)

Polyhydroxystyrene: nippon Caoda, Wanshan petrochemical, Toho chemical industry

Polyacrylic acid derivatives: japanese catalyst

Polycarbonate (C): Sigma-Aldrich

Polymethacrylic acid derivatives: Sigma-Aldrich

A) The ratio of the low-solubility substance to the total mass of the treatment liquid is 0.1 to 50 mass%, preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, and still more preferably 1 to 10 mass%. That is, the low-solubility substance (A) is 0.1 to 50% by mass based on 100% by mass of the total mass of the treatment liquid. That is, "compare with … …" can be replaced with "based on … …". Unless otherwise specified, the same applies hereinafter.

The solubility can be evaluated by a known method. For example, whether or not (A) or (B) has been dissolved can be determined by adding 100ppm of the above (A) or (B) to 5.0 mass% ammonia water in a flask under conditions of 20 to 35 ℃ (more preferably 25. + -.2 ℃), closing the flask, and shaking with a shaker for 3 hours. The vibration may be stirring. Dissolution can also be visually determined. If not dissolved, the solubility is less than 100ppm, and if dissolved, the solubility is 100ppm or more. The solubility is less than 100ppm and is insoluble or poorly soluble, and the solubility is 100ppm or more and is soluble. Broadly, soluble comprises slightly soluble. The solubility is reduced in the order of insolubility, insolubility and solubility. In a narrow sense, slightly soluble is less soluble than soluble and more insoluble.

< highly soluble substance >

(B) The highly soluble substance is (B') a crack-accelerating component. (B') the crack promoting component comprises a hydrocarbon, and further comprises a hydroxyl group (-OH) and/or a carbonyl group (-C (═ O) -). In the case where the crack-promoting component (B') is a polymer, one of the structural units contains a hydrocarbon per 1 unit, and further has a hydroxyl group and/or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and ketene, and a carboxylic acid is preferable.

Without intending to limit the scope of claims, it is theoretically assumed that (B) the highly soluble substance forms a portion which becomes a starting point of peeling of the process film when the process liquid is dried to form the process film on the substrate and the process film is peeled by the removing liquid. Therefore, it is preferable that the solubility of the highly soluble substance (B) in the removing solution is higher than that of the low soluble substance (a). The (B') crack-accelerating component may be a cyclic hydrocarbon in which the carbonyl group includes a ketone. Specific examples thereof include 1, 2-cyclohexanedione and 1, 3-cyclohexanedione.

More specifically, the highly soluble substance (B) is represented by at least one of the following (B-1), (B-2) and (B-3).

(B-1) contains 1 to 6 (preferably 1 to E) structural units4) each structural unit of the following chemical formula 8 and a linking group (linker L) ₁) A bonded compound. Here, L₁Is selected from a single bond and C_1～6At least 1 of alkylene groups. C above_1～6The alkylene group serves as a linker (linker) to link the structural units, and is not limited to the 2-valent group. Preferably 2 to 4. C above_1～6The alkylene group may be either a straight chain or a branched chain.

[ chemical formula 8]

Cy₁Is C_5～30The hydrocarbon ring of (2) is preferably a phenyl group, a cyclohexane group or a naphthyl group, and more preferably a phenyl group. Preferably, the linker L₁A plurality of Cys₁And (7) connecting.

R₁Each independently is C_1～5Alkyl, preferably methyl, ethyl, propyl or butyl. C above_1～5The alkyl group may be either a straight chain or a branched chain.

n_b1Is 1, 2 or 3, preferably 1 or 2, more preferably 1. n is_b1’Is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

The structural unit shown in chemical formula 8 is represented by chemical formula 9 using linker L₉The chemical formula shown. Preference is given to the linker L₉Is a single bond, methylene, ethylene or propylene.

[ chemical formula 9]

Without intending to limit the scope of the claims, preferred examples of (B-1) include 2, 2-bis (4-hydroxyphenyl) propane, 2, 2 '-methylenebis (4-methylphenol), 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenol, 1, 3-cyclohexanediol, 4' -dihydroxybiphenyl, 2, 6-naphthalenediol, 2, 5-di-tert-butylhydroquinone, and 1, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane. The above-mentioned substances can also be obtained by polymerization or condensation.

As an example, 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl group) shown in the following chemical formula 10 is given]4-methylphenol. The compound has 3 structural units of chemical formula 8 in (B-1), wherein L represents a structural unit₁(methylene) bonding. n is_b1＝n_b1’＝1，R₁Is methyl.

[ chemical formula 10]

(B-2) is represented by the following chemical formula 11.

[ chemical formula 11]

R₂₁、R₂₂、R₂₃And R₂₄Each independently is hydrogen or C_1～5The alkyl group of (b) is preferably hydrogen, methyl, ethyl, tert-butyl or isopropyl, more preferably hydrogen, methyl or ethyl, and still more preferably methyl or ethyl.

L₂₁And L₂₂Each independently is C_1～20Alkylene of (C)_1～20Cycloalkylene radical of (2)_2～4Alkenylene of (A), C_2～4Alkynylene of (a) or C_6～20An arylene group of (a). These radicals may also be substituted by C_1～5Alkyl or hydroxy. Here, alkenylene represents 1 or more divalent hydrocarbon groups having a double bond, and alkynylene represents 1 or more divalent hydrocarbon groups having a triple bond. Preferably L₂₁And L₂₂Is C_2～4Alkylene group, ethynylene group (C)₂Alkynylene of (a) or phenylene, more preferably C_2～4The alkylene group or the ethynylene group of (a), is more preferably an ethynylene group.

n_b2Is 0, 1 or 2, preferably 0 or 1, more preferably 0.

Without intending to limit the scope of the claims, preferable examples of (B-2) include 3, 6-dimethyl-4-octyne-3, 6-diol and 2, 5-dimethyl-3-hexyne-2, 5-diol. As another embodiment, 3-hexyne-2, 5-diol, 1, 4-butynediol, 2, 4-hexadiyne-1, 6-diol, 1, 4-butanediol, cis-1, 4-dihydroxy-2-butene, 1, 4-benzenedimethanol can also be cited as preferable examples of (B-2).

(B-3) a polymer having a weight average molecular weight (Mw) of 500 to 10000, which contains a structural unit represented by the following chemical formula 12. The Mw is preferably 600 to 5000, and more preferably 700 to 3000.

[ chemical formula 12]

Herein, R is₂₅is-H, -CH₃or-COOH, preferably-H or-COOH. It is also permissible that 1 (B-3) polymer contains 2 or more kinds of structural units each represented by chemical formula 12.

Without intending to limit the scope of claims, preferable examples of the (B-3) polymer include polymers of acrylic acid, maleic acid, acrylic acid, or a combination thereof. Polyacrylic acid and maleic acrylic acid copolymer are further preferable examples.

In the case of copolymerization, random copolymerization or block copolymerization is preferable, and random copolymerization is more preferable.

An example of the copolymer is a maleic acid-acrylic copolymer represented by the following chemical formula 13. The copolymer is contained in (B-3), has 2 kinds of structural units represented by chemical formula 12, and R is contained in 1 structural unit₂₅is-H, in another structural unit, R₂₅is-COOH.

[ chemical formula 13]

It is needless to say that the highly soluble substance (B) and the treatment solution may contain 1 or a combination of 2 or more of the above-mentioned preferred examples. For example, (B) the high-solubility material may also comprise both 2, 2-bis (4-hydroxyphenyl) propane and 3, 6-dimethyl-4-octyne-3, 6-diol.

(B) The molecular weight of the highly soluble substance may be 80 to 10000. The molecular weight of the highly soluble substance is preferably 90 to 5000, and more preferably 100 to 3000. In the case where the (B) high-solubility substance is a resin, a polymer (Japanese: a doublet) or a polymer (Japanese: ポリマー), the molecular weight is represented by a weight-average molecular weight (Mw).

(B) Highly soluble materials can be either synthetic or commercially available. The suppliers include Sigma-Aldrich, Tokyo chemical industry and Japanese catalyst.

In the treatment liquid, the amount of the high-solubility substance (B) is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, relative to the amount of the low-solubility substance (A). In the treatment liquid, the amount of the highly soluble substance (B) is more preferably 1 to 30% by mass, compared with the amount of the lowly soluble substance (A).

< solvent >

Preferably, the (C) solvent comprises an organic solvent. (C) The solvent may also be volatile. Having volatility means that the volatility is high compared to water. For example, the boiling point of the solvent (C) is preferably 50 to 250 ℃ at 1 atm. The boiling point of the solvent at 1 atmosphere is more preferably 50 to 200 ℃, and still more preferably 60 to 170 ℃. More preferably, the boiling point of the solvent at 1 atmosphere is 70 to 150 ℃. (C) The solvent is also allowed to contain a small amount of pure water. The pure water contained in the solvent (C) is preferably 30 mass% or less of the entire solvent (C). The pure water contained in the solvent is more preferably 20% by mass or less, and still more preferably 10% by mass or less. Further preferably, the pure water contained in the solvent is 5% by mass or less. It is also a preferable embodiment that the solvent does not contain pure water (0 mass%). Preferably, the pure water is DIW.

Examples of the organic solvent include alcohols such as isopropyl alcohol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as Propylene Glycol Monomethyl Ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as Propylene Glycol Monomethyl Ether Acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and Ethyl Lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N, N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ -butyrolactone. These organic solvents can be used alone or in combination of 2 or more.

In a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. In the case where the organic solvent is a combination of 2 kinds, it is preferable that the volume ratio thereof is 20: 80-80: 20, more preferably 30: 70-70: 30.

(C) the ratio of the total mass of the solvent to the total mass of the treatment solution is 0.1 to 99.9 mass%. The ratio of the total mass of the solvent (C) to the total mass of the treatment liquid is preferably 50 to 99.9 mass%, and more preferably 75 to 99.5 mass%. The ratio of the total mass of the solvent (C) to the total mass of the treatment solution is preferably 80 to 99 mass%, and more preferably 85 to 99 mass%.

< other additives >

The treatment solution of the present invention may further contain (D) other additives. In one embodiment of the present invention, (D) the other additive includes a surfactant, an acid, an alkali, an antibacterial agent, a bactericide, an antiseptic agent, or an antifungal agent (preferably, a surfactant), and may include any combination of the above.

In one embodiment of the present invention, the mass ratio of the (D) other additives (the sum in the case of plural types) to the (a) low-solubility substance in the treatment liquid is 0 to 100 mass% (preferably 0 to 10 mass%, more preferably 0 to 5 mass%, further preferably 0 to 3 mass%, further preferably 0 to 1 mass%). The treatment liquid (D) does not contain other additives (0 mass%) and is one embodiment of the present invention.

< embodiment 3 >

In embodiment 3, a substrate processing apparatus having the same configuration as the substrate processing apparatus 1 of embodiment 1 can be used to perform the same substrate processing as that described in embodiment 1. The main difference between embodiment 3 and embodiment 1 is that the solute in the processing liquid discharged from the 2 nd moving nozzle 9 contains a low-solubility substance, a high-solubility substance, and a dissolution-force enhancing substance.

As will be described in detail later, in embodiment 3, the removing liquid and the protecting liquid are, for example, pure water.

The dissolving power enhancing substance is a substance that increases the dissolving power of the removing solution to dissolve the treatment film by dissolving in the removing solution. By dissolving the solubilizing-force enhancing substance in the protective solution, the solubilizing force of the protective solution for solubilizing the treatment film is also increased. The dissolving power enhancing substance is, for example, a salt (alkali component) which dissolves in the removing solution to exhibit alkalinity (alkalinity).

As will be described in detail later, examples of the solubility enhancing substance include primary amines, secondary amines, tertiary amines, quaternary ammonium salts, and the like. When the removal liquid is pure water, the dissolution-enhancing substance is eluted from the treatment film into the removal liquid, whereby the removal liquid becomes an aqueous solution of a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium salt, or the like, that is, an alkaline aqueous solution (alkaline liquid). When the removing solution is an alkaline aqueous solution, the solubilizing-force-enhancing substance is eluted from the treatment film into the removing solution, thereby enhancing the alkalinity of the removing solution.

The low-solubility substance and the high-solubility substance can be substances having different solubilities with respect to the removing solution. The low-solubility substance contained in the treatment liquid discharged from the 2 nd moving nozzle 9 is, for example, novolac, and the high-solubility substance contained in the treatment liquid discharged from the 2 nd moving nozzle 9 is, for example, 2-bis (4-hydroxyphenyl) propane.

The solvent contained in the treatment liquid discharged from the 2 nd moving nozzle 9 may be a liquid that dissolves the low-solubility substance, the high-solubility substance, and the dissolution-strength-enhancing substance. The solvent contained in the treatment solution is preferably a liquid having compatibility (miscibility) with the removal solution.

Details of the solvent, the low-solubility substance, the high-solubility substance, and the dissolution force enhancing substance contained in the treatment liquid discharged from the 2 nd moving nozzle 9 will be described later together with details of the removal liquid discharged from the 3 rd moving nozzle 10.

The substrate processing of embodiment 3 is different from the substrate processing of embodiment 1 in the vicinity of the upper surface of the substrate W. Referring to fig. 10A to 10C, a case where the treatment film 300 is removed from the substrate W in the substrate treatment of embodiment 3 when the removing liquid and the protective liquid are both pure water will be described.

Fig. 10A shows the vicinity of the upper surface of the substrate W immediately after the solid-state forming process (step S7) is completed. Fig. 10B shows the upper surface of the substrate W when the treatment film 300 is partially dissolved in the protective liquid film forming step (step S8) and the removing step (step S9). Fig. 10C shows the vicinity of the upper surface of the substrate W when the physical force acts on the handle film 300 in the removal process (step S9).

In the solid forming step performed in the treatment film forming step, as described above, the liquid film 101 on the substrate W is heated with the heat medium through the substrate W. As a result, as shown in fig. 10A, a processing film 300 holding the objects to be removed 103 such as particles is formed.

In detail, at least a part of the solvent is evaporated, and thus the high-solubility substance contained in the solute of the treatment liquid forms the high-solubility solid 310 (high-solubility substance in a solid state), and the low-solubility substance contained in the solute of the treatment liquid forms the low-solubility solid 311 (low-solubility substance in a solid state). At least a part of the solvent evaporates, and the solvency-enhancing substance contained in the solute of the treatment liquid forms a solvency-enhancing solid 312 (a solid state solvency-enhancing substance). The low-solubility substance, the high-solubility substance and the dissolution-enhancing substance are formed into a film together.

In the treatment film 300, the high-solubility solid 310, the low-solubility solid 311, and the dissolving-force enhancing solid 313 are present in a mixture. The high-solubility solid 310, the low-solubility solid 311, and the dissolution-strength enhancing solid 313 are not uniformly distributed throughout the entire processing film 300, and there are portions of the processing film 300 where the high-solubility solid 310 is localized and portions of the processing film 300 where the low-solubility solid 311 is localized. The dissolving-force enhancing solid 312 is formed on the entire processing film 300 without leakage. In the processing film 300, a cavity 104 may be formed between the 1 st object to be removed 103A and the upper surface of the substrate W.

As shown in fig. 10B, the dissolution-force-reinforcing solid 312 in the processing film 300 dissolves out the protective solution supplied to the upper surface of the substrate W in the protective solution film forming step and the removing solution supplied to the upper surface of the substrate W in the removing step. The dissolving power-enhancing solid 312 is dissolved in the protective solution and the removing solution to form an alkaline aqueous solution. When the protective solution and the removing solution are aqueous alkaline solutions, the dissolving power of the protective solution and the removing solution for dissolving the treatment film 300 is strengthened, and the treatment film 300 is partially dissolved.

Specifically, the highly soluble solid 310 is dissolved by the alkaline aqueous solution, which is the protective solution and the removing solution having enhanced dissolving power, to form the through-holes 302 in the treated film 300 at the portions where the highly soluble solid 310 is located (through-hole forming step). The through-hole 302 is easily formed in the thickness direction D of the substrate W (also in the thickness direction of the handle film 300), particularly in a portion where the highly soluble solid 310 extends. The through hole 302 has a diameter of several nm in plan view, for example.

The alkaline aqueous solution reaches the vicinity of the upper surface of the substrate W through the through-hole 302. The low-solubility solid 311 is dissolved in a small amount in an aqueous alkaline solution. Therefore, in the low-solubility solid 311, a portion in the vicinity of the upper surface of the substrate W is dissolved by a small amount. Thus, as shown in the enlarged view of fig. 10B, the alkaline aqueous solution gradually dissolves the low-solubility solid 311 near the upper surface of the substrate W and enters the gap G3 between the processing film 300 and the upper surface of the substrate W (the removing solution introducing step and the protective solution introducing step).

In the treatment film 300, when the high-solubility solid 310 is partially dissolved, the dissolution-strength enhancing solid 312 present in the portion and the dissolution-strength enhancing solid 312 present in the portion of the treatment film 100 surrounding the through-hole 302 are dissolved in the alkaline aqueous solution. Similarly, the protective solution and the removal solution enter the gap G3, whereby the dissolution-force-intensifying solid 312 existing in the processing film 300 in the vicinity of the upper surface of the substrate W is dissolved by the protective solution. This further increases the concentration of the alkali component in the aqueous alkali solution. Therefore, the peeling of the low-solubility solid 311 of the processing film 300 is further promoted.

Finally, the processing film 300 is split into the membrane 307 starting from the periphery of the through hole 302 by the physical force of the droplet 106 of the removing liquid. Then, as shown in fig. 10C, the film 307 of the processing film 300 is peeled off from the substrate W in a state where the removal object 103 is held (a splitting step, a processing film peeling step). At the same time, the object to be removed 103 is peeled off from the upper surface of the substrate W by the physical force of the droplets 106 of the removing liquid (object-to-be-removed peeling step). Therefore, even when the 1 st object to be removed 103A having the radius R larger than the film thickness T of the process film 300 is present on the upper surface of the substrate W, the 1 st object to be removed 103A is peeled off from the upper surface of the substrate W.

When the treatment film 300 is partially dissolved, the 2 nd removal object 103B held by the portion of the treatment film 300 biased by the highly soluble solid 310 may be detached from the treatment film 300. Even in such a case, the 2 nd object to be removed 103B is peeled off from the upper surface of the substrate W by the physical force of the droplets 106 of the removal liquid acting on the 2 nd object to be removed 103B.

Then, by continuing the supply of the removal liquid, the processing film 300 which becomes the membrane 307 is washed away (pushed out of the substrate W) while holding the 2 nd removal object 103B, and removed from the upper surface of the substrate W (removal step).

The 1 st object to be removed 103A not sufficiently held by the processing film 300 and the 2 nd object to be removed 103B detached from the processing film 300 are also washed away (pushed out of the substrate W) by continuing to supply the removing liquid, and are removed from the upper surface of the substrate W (removing step).

Embodiment 3 achieves the same effects as embodiment 1.

Further, according to embodiment 3, the high-solubility solid 310 in a solid state in the processing membrane 300 is selectively dissolved by the removing liquid. Therefore, the strength of the processing film 300 is reduced. On the other hand, the low-solubility solid 311 in the processing film 300 is maintained in a solid state in which the object to be removed 103 is held. Therefore, the physical force of the droplets 106 of the removal liquid can be applied to the processing film 300 in the removal step while the removal object 103 is still held on the processing film 300 and the strength of the processing film 200 is reduced. Thereby, the processing film 300 is efficiently split, and the processing film 300 is efficiently peeled from the surface of the substrate.

Further, according to embodiment 3, the dissolving power of the treatment film 300 by the protective solution and the removing solution is enhanced by the dissolving power enhancing substance being eluted from the treatment film 300 into the protective solution and the removing solution. Therefore, the treatment film 300 is partially dissolved by the protective solution and the removing solution. Therefore, even when a liquid having a low dissolving power such as pure water is used as the removing liquid, the strength of the treatment film 300 can be reduced and the physical force of the droplets of the removing liquid can be applied to the treatment film 300. This makes it possible to efficiently split the processing film 300 and efficiently peel the processing film 300 off the upper surface of the substrate W. As a result, the processing film 300 can be efficiently removed from the upper surface of the substrate W.

In the case of using an alkaline aqueous solution as the removing solution, even if the dissolution-strength-enhancing substance is eluted into the removing solution, the degree of enhancement of the dissolution force of the removing solution is lower than in the case of using a non-alkaline aqueous solution as the removing solution. The same applies to the case where an alkaline aqueous solution is used as the protective solution. That is, even if the dissolution-strength enhancing substance is eluted into the protective solution, the dissolution strength of the protective solution is enhanced to a lesser extent than in the case where the protective solution is a non-alkaline aqueous solution.

< details of the treating solution, the removing solution and the protecting solution used in embodiment 3 >

Hereinafter, each component of the treatment liquid used in embodiment 3, the removing liquid, and the protective liquid will be described.

< Low-solubility substance >

As the low-solubility substance (a), the same substance as the low-solubility substance contained in the treatment liquid used in embodiment 2 can be used. The weight average molecular weight (Mw) of the low-solubility substance (A) used in embodiment 3 is preferably 150 to 500000. The ratio of the low-solubility substance (a) used in embodiment 3 to the total mass of the treatment solution is 0.1 to 50 mass%. In other words, the low-solubility substance (a) used in embodiment 3 is 0.1 to 50% by mass based on 100% by mass of the total mass of the treatment liquid.

< substance having enhanced dissolving power >

(B) The solubility enhancing substance contains at least 1 of a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt (preferably a primary amine, a secondary amine, and a tertiary amine), and (B) the solubility enhancing substance contains a hydrocarbon. In a preferred embodiment, (B) the dissolution force enhancing substance remains in the treatment film 100 formed from the treatment solution, and when the treatment film is peeled off by the removing solution, (B) the dissolution force enhancing substance is eluted into (F) the removing solution. Therefore, the boiling point of the alkali component (B) is preferably 20 to 400 ℃ at 1 atm.

Without intending to limit the kind of the solubilizing-force enhancing substance, preferable examples of (B) include N-benzylethanolamine, diethanolamine, monoethanolamine, 2- (2-aminoethylamino) ethanol, 4' -diaminodiphenylmethane, 2- (butylamino) ethanol, 2-anilinoethanol, triethanolamine, ethylenediamine, diethylenetriamine, tris (2-aminoethyl) amine, and tris [2- (dimethylamino) ethyl ] amine.

The kind of the solubilizing-strength-enhancing substance is not limited, and preferable examples of (B) include N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine and N, N, N ', N' -tetraethylethylenediamine.

The kind of the solubilizing-strength-enhancing substance is not intended to be limited, and specific examples of (B) having a cage-type three-dimensional structure include 1, 4-diazabicyclo [2.2.2] octane and hexamethylenetetramine. Without intending to limit the present invention, preferable examples of (B) having a planar ring structure include 1, 4, 7, 10-tetraazacyclododecane and 1, 4, 7, 10, 13, 16-hexaazacyclooctadecane.

It goes without saying that the treatment liquid of the present invention may contain 1 or a combination of 2 or more of the above-described preferred examples as the solubilizing power enhancing substance (B). For example, the (B) solvency-enhancing substance may also contain both N-benzylethanolamine and diethanolamine. In addition, the (B) solvency-enhancing substance may contain both N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine and 1, 4-diazabicyclo [2.2.2] octane.

The molecular weight of the (B) dissolution-enhancing substance is preferably 50 to 500.

(B) The solvency enhancing material can be either synthetic or commercially available. As the supplier, Sigma-Aldrich and Tokyo chemical industry can be cited.

In one embodiment of the present invention, the mass ratio of the dissolution-strength enhancing substance (B) to the low-solubility substance (a) in the treatment liquid is preferably 1 to 100% by mass.

< solvent >

Preferably, the (C) solvent comprises an organic solvent. (C) The solvent is volatile. Having volatility means that the volatility is high compared to water. The boiling point of the solvent (C) is preferably 50 to 200 ℃ at 1 atm. It is also permissible that the (C) solvent contains a small amount of pure water. The pure water contained in the solvent (C) is preferably 30 mass% or less of the entire solvent (C). Pure water (0 mass%) is also a preferred embodiment. Preferably, the pure water is DIW.

In a preferred embodiment of the present invention, the component (including the additive) included in the treatment liquid is dissolved in the solvent (C). The treatment solution of this type is considered to have good embeddability and good film uniformity.

Examples of the organic solvent contained in (C) include alcohols such as isopropyl alcohol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as Propylene Glycol Monomethyl Ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as Propylene Glycol Monomethyl Ether Acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid esters such as methyl lactate and Ethyl Lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N, N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ -butyrolactone. These organic solvents can be used alone or in combination of 2 or more.

In a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. In the case where the organic solvent is a combination of 2 kinds, it is preferable that the volume ratio thereof is 20: 80-80: 20.

(C) the ratio of the total mass of the solvent to the total mass of the treatment solution is 0.1 to 99.9 mass%.

< highly soluble substance >

(D) The highly soluble substance contains a hydrocarbon, and further contains a hydroxyl group (-OH) and/or a carbonyl group (-C (═ O) -). In the case where (D) the high-solubility substance is a polymer, one of the structural units contains a hydrocarbon per 1 unit, and further contains a hydroxyl group and/or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and ketene, and a carboxylic acid is preferable.

As described above, the processing liquid is dried, and (D) the highly soluble substance remains in the processing film formed on the substrate. When (F) the removing solution peels off the treatment film, and (D) the highly soluble substance forms a portion that becomes a peeling start of the treatment film. Therefore, as the (D) highly soluble substance, a substance having a higher solubility in the (F) removing solution than the (a) low soluble substance is preferably used.

As the mode of (D) the high-solubility substance containing a ketone as a carbonyl group, a cyclic hydrocarbon can be mentioned. Specific examples thereof include 1, 2-cyclohexanedione and 1, 3-cyclohexanedione.

Without intending to limit the scope of the claims, preferred examples of (D) include 2, 2-bis (4-hydroxyphenyl) propane, 2, 2 '-methylenebis (4-methylphenol), 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenol, 1, 3-cyclohexanediol, 4' -dihydroxybiphenyl, 2, 6-naphthalenediol, 2, 5-di-tert-butylhydroquinone, and 1, 1, 2, 2-tetrakis (4-hydroxyphenyl) ethane. These substances can also be obtained by polymerization or condensation.

Without intending to limit the scope of the claims, preferable examples of (D) include 3, 6-dimethyl-4-octyne-3, 6-diol and 2, 5-dimethyl-3-hexyne-2, 5-diol. In another embodiment, 3-hexyne-2, 5-diol, 1, 4-butynediol, 2, 4-hexadiyne-1, 6-diol, 1, 4-butanediol, cis-1, 4-dihydroxy-2-butene, and 1, 4-benzenedimethanol can also be cited as preferable examples of (D).

Without intending to limit the scope of the claims, preferable examples of the polymer (D) include polymers of acrylic acid, maleic acid, or a combination thereof. Polyacrylic acid and maleic acrylic acid copolymer are further preferable examples.

In the case of copolymerization, random copolymerization or block copolymerization is preferable, and random copolymerization is more preferable.

It is needless to say that the treatment liquid may contain 1 or a combination of 2 or more of the above-mentioned preferable examples as the highly soluble substance (D). For example, (D) the high-solubility material may also comprise both 2, 2-bis (4-hydroxyphenyl) propane and 3, 6-dimethyl-4-octyne-3, 6-diol.

(D) The high-solubility substance has a molecular weight of, for example, 80 to 10000. In the case where (D) the high-solubility substance is a resin, a polymer or a polymer, the molecular weight is expressed as a weight average molecular weight (Mw).

(D) Highly soluble materials can be both synthetic and commercially available. The suppliers include Sigma-Aldrich, Tokyo chemical industry and Japanese catalyst.

In one embodiment of the present invention, the mass ratio of the highly soluble substance (D) to the low soluble substance (a) in the treatment liquid is preferably 1 to 100% by mass.

< other additives >

The treatment solution of the present invention may further contain (E) other additives. (E) Other additives may also include surfactants, antimicrobials, bactericides, preservatives, antifungals, or bases (preferably surfactants), and may also include any combination of the above.

The mass ratio of the other additives (E) (the sum of the additives in a plurality of cases) to the low-solubility substance (a) in the treatment liquid is preferably 0 to 10% by mass. The treatment solution may contain (E) no other additive (0 mass%).

< removing solution, protecting solution >

The removing solution and the protecting solution (F) are preferably neutral or weakly acidic. The pH of the removing solution and the protecting solution (F) is preferably 4 to 7, more preferably 5 to 7, and still more preferably 6 to 7. In order to avoid the influence of the dissolution of carbon dioxide in the air, it is preferable that the measurement of pH is performed in a degassed manner.

Preferably, the removing solution and the protecting solution (F) contain pure water. As described above, since the treatment solution of the present invention contains (B) the dissolution-enhancing substance, the dissolution force of the removal solution and the protective solution is enhanced by dissolving the substances into the removal solution and the protective solution (F) and increasing the pH of the removal solution and the protective solution (F). Therefore, the removing solution and the protecting solution (F) may be mostly pure water.

The ratio of the pure water contained in (F) to the total mass of the removed liquid of (F) is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and even more preferably 99 to 100 mass%. The (F) removing liquid is preferably composed of pure water alone (100 mass%).

The total mass ratio of pure water and the protective solution contained in the protective solution is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, even more preferably 95 to 100 mass%, and even more preferably 99 to 100 mass%. The protective solution is preferably composed of pure water alone (100 mass%).

< other embodiments >

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

For example, the protective liquid film forming step (step S8) may be omitted, unlike the substrate processing in the above embodiment. In this case, in the removing step (step S9), as shown in fig. 11, the removing liquid is supplied from the 3 rd moving nozzle 10 to the processing film 100 whose surface is not protected, and the protective liquid is supplied from the 4 th moving nozzle 11. In this case, since the protective liquid film 105 is not formed before the removal liquid in a droplet state is supplied, the substrate processing time can be shortened.

In the removing step (step S9), the protective liquid parallel supply step may be omitted. In this case, in the removing step (step S9), as shown in fig. 12, the removing liquid is supplied from the 3 rd moving nozzle 10 to the treatment film 100 whose surface is protected by the protective liquid film 105, and the protective liquid is not supplied from the 4 th moving nozzle 11.

At the start of the removal process, the protective liquid film 105 is sufficiently held on the upper surface of the substrate W. Therefore, at the start of the removal process, the action of the physical force on the supply region S is particularly alleviated by the protective liquid film 105. In particular, when the 3 rd moving nozzle 10 starts moving from the center position in the removal step, the action of the physical force on the center region of the upper surface of the substrate W can be alleviated.

The protective liquid film forming step (step S8) and the protective liquid parallel supply step in the removing step (step S9) may be omitted. In this case, as shown in fig. 13, the removing liquid is supplied from the 3 rd moving nozzle 10 to the processing film 100 whose surface is not protected, and the protective liquid is not supplied from the 4 th moving nozzle 11.

In this case, since the droplets 106 of the removal liquid are supplied to the processing film 100 in a state where the surface of the processing film 100 is not protected by the protective liquid, a strong physical force acts on the processing film 100. The strong physical force can efficiently remove the object to be removed 103 from the upper surface of the substrate W, and is therefore particularly useful when a substrate W on which an uneven pattern is not formed is used. Even in this case, if the 3 rd moving nozzle 10 supplies the removal liquid to the processing film 100 while moving between the center position and the peripheral position, it is possible to apply a strong physical force to the entire processing film 100 without leakage.

In addition, unlike the substrate processing in the above embodiment, the kind of the liquid supplied as the protective liquid to the upper surface of the substrate W in the protective liquid film forming step (step S8) may be different from the kind of the liquid supplied as the protective liquid to the upper surface of the substrate W in the protective liquid parallel supply step in the removing step (step S9). For example, pure water may be used as the protective liquid in the protective liquid film forming step, and an alkaline aqueous solution may be used as the protective liquid in the protective liquid parallel supply step.

For this purpose, for example, as shown in fig. 14, the substrate processing apparatus 1 may include the 5 th moving nozzle 12 which is held by the nozzle holder 38B together with the 4 th moving nozzle 11 and discharges the protective liquid.

Since the 5 th moving nozzle 12 is held by the nozzle holder 38B, the 3 rd moving nozzle 10 and the 4 th moving nozzle 11 are integrally moved by the 3 rd nozzle moving unit 38. The 5 th moving nozzle 12 is connected to the 2 nd protective liquid pipe 49. A 2 nd protective liquid valve 59A and a 2 nd protective liquid flow rate adjusting valve 59B are attached to the 2 nd protective liquid pipe 49. The 2 nd protection liquid valve 59A and the 2 nd protection liquid flow rate adjustment valve 59B are controlled by the controller 3 (see fig. 4).

Unlike the substrate processing in the above embodiment, the chemical liquid supply step (step S2), the 1 st rinsing step (step S3), and the 1 st organic solvent supply step (step S4) may be omitted.

In the substrate processing (see fig. 5) in the above embodiment, in the process film formation step (steps S6 and S7), the solvent of the processing liquid is evaporated by heating the substrate W with the heat medium. However, the substrate W is not limited to the supply of the heat medium, and may be heated by a heater or the like (not shown) built in the spin base 21 or the counter member 6, for example. In this case, the heater functions as a substrate heating unit and an evaporation unit (evaporation promotion unit).

In the thin film forming process (step S6), the solvent may evaporate to form the treatment film 100 when the liquid film 101 of the treatment liquid is formed into a thin film. In this case, the thin-film forming process (step S6) is executed in parallel with the solid-state forming process (step S7). In this case, the solid forming unit does not include the center nozzle 14 and the lower surface nozzle 15, and the solid forming unit is constituted by the substrate rotating unit (the rotating motor 23) and the center nozzle 14. In the solid forming step (step S7), only the heating step or only the gas supply step may be omitted.

In the substrate processing, the 2 nd rinsing step (step S10) is performed after the removing step (step S9). However, the 2 nd rinsing step may be omitted. Specifically, when the removal solution supplied to the substrate W in the removal step is compatible with the organic solvent (residue removal solution) supplied to the substrate W in the 2 nd organic solvent supply step (step S10) performed after the 2 nd rinsing step, the 2 nd rinsing step need not be performed.

In the above embodiment, a nozzle for ejecting the removing liquid in a droplet state by applying a voltage is used. However, unlike the above-described embodiment, a two-fluid nozzle may be used in which an inert gas such as nitrogen gas is caused to collide (mix) with the removal liquid in the vicinity of the ejection port to form droplets of the removal liquid, and the droplets of the removal liquid are supplied onto the upper surface of the substrate W. In the two-fluid nozzle, the physical force of removing the liquid droplets can be adjusted by adjusting the flow rate of the liquid toward the ejection port and the flow rate of the gas toward the ejection port.

The embodiments of the present invention have been described in detail, but these embodiments are merely specific examples used for clearly understanding the technical contents of the present invention, and the present invention should not be construed as being limited to these specific examples, and the scope of the present invention is defined only by the claims.

The present application corresponds to the application No. 2019-056285, filed by the patent office on 3/25/2019, the entire disclosure of which is incorporated by reference.

Description of the reference numerals

1: substrate processing apparatus

1P: substrate processing apparatus

3: controller

9: no. 2 moving nozzle (treatment liquid supply unit)

10: no. 3 moving nozzle (removing liquid supply unit)

11: the 4 th movable nozzle (1 st protective liquid supply unit, 2 nd protective liquid supply unit)

12: the 5 th moving nozzle (1 st protective liquid supply unit, 2 nd protective liquid supply unit)

14: central nozzle (solid forming unit, solution supply unit)

15: lower surface nozzle (solid forming unit)

23: rotary motor (solid forming unit)

100: treatment film

102: through hole

103: removing objects

200: treatment film

210: highly soluble solid (highly soluble substance in solid state)

211: low-solubility solid (low-solubility substance in solid state)

300: treatment film

310: highly soluble solid (highly soluble substance in solid state)

311: low-solubility solid (low-solubility substance in solid state)

312: solvency-reinforcing solid (solid state solvency-reinforcing material)

R: radius of

S: supply area

T: film thickness

W: substrate