JP7628636B2 - SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS - Google Patents

Description

This invention relates to a substrate processing method and a substrate processing apparatus for processing substrates. Substrates to be processed include, for example, semiconductor wafers, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, and substrates for FPDs (Flat Panel Displays) such as liquid crystal displays, plasma displays, and organic EL (Electroluminescence) displays.

In the manufacturing process of a semiconductor device, a process is carried out to remove various contaminants attached to a substrate, residues of processing liquids and resists used in previous processes, and various particles (hereinafter collectively referred to as "objects to be removed").
Specifically, it is common to supply deionized water (DIW) or the like to the substrate and remove the material to be removed by the physical action of the DIW, or to supply a chemical solution that chemically reacts with the material to be removed to the substrate and chemically remove the material.

However, as the unevenness patterns formed on the substrate become finer and more complicated, it is becoming more difficult to remove the target material using DIW or a chemical solution while preventing damage to the unevenness patterns.
Therefore, a method has been proposed in which a processing liquid is supplied to the surface of a substrate, the processing liquid on the substrate is solidified to form a retention layer that retains the object to be removed present on the substrate, and then a stripping liquid is supplied to the upper surface of the substrate, thereby peeling and removing the retention layer together with the object to be removed from the surface of the substrate (see Patent Document 1 below).

JP 2019-62171 A

In Patent Document 1, the stripping liquid forms an infiltration path by the stripping liquid, and the stripping liquid penetrates into the retention layer. However, depending on the surface condition of the substrate, the stripping liquid may not be able to penetrate sufficiently into the interface between the substrate and the retention layer, which may result in insufficient stripping of the retention layer from the surface of the substrate.
Therefore, there is a need for a method for effectively peeling off the retaining layer while retaining the object to be removed from the substrate. Therefore, one object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can effectively peel off the processing film while retaining the object to be removed from the surface of the substrate.

One embodiment of the present invention provides a substrate processing method including a hydrophilization step of hydrophilizing the surface of a substrate, a processing liquid supply step of supplying a processing liquid to the hydrophilized surface of the substrate, a processing film formation step of solidifying or curing the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate, and a peeling step of supplying a stripping liquid to the surface of the substrate to peel off the processing film that holds the object to be removed from the surface of the substrate. The peeling step includes a through hole formation step of partially dissolving the processing film in the stripping liquid to form a through hole in the processing film.

The inventors of the present application have discovered that the peeling action of the stripping solution to peel the treatment film from the substrate varies depending on the surface condition of the substrate. Specifically, the more hydrophilic the substrate surface is, the easier it is to peel the treatment film with the stripping solution. More specifically, the more hydrophilic the substrate surface is, the easier it is for the stripping solution to act on the interface between the treatment film and the substrate, and the treatment film can be effectively peeled off from the substrate surface.

Therefore, if a method is used in which a treatment film is formed on the hydrophilized surface of a substrate and a stripping liquid is supplied toward the surface of the substrate on which the treatment film is formed, the treatment film can be effectively stripped from the substrate.
Furthermore, since the through-holes are formed in the treatment film by the stripping solution supplied toward the surface of the substrate, the stripping solution can reach the interface between the treatment film and the substrate through the through-holes. This allows the stripping solution to act on the interface between the substrate and the portion of the treatment film surrounding the through-holes. Therefore, compared with a method in which the stripping solution is allowed to penetrate into the treatment film without forming through-holes in the treatment film and the stripping solution reaches the interface between the treatment film and the substrate, the stripping solution can act on the interface between the treatment film and the substrate more quickly. Although the treatment film is partially dissolved by the stripping solution to form the through-holes, the remaining portion remains in a solid state. Therefore, the treatment film holding the object to be removed can be effectively stripped from the surface of the substrate.

In this way, the stripping liquid can be rapidly applied to the interface between the treatment film and the substrate while maintaining most of the treatment film in a solid state, so that the treatment film, which still retains the material to be removed, can be effectively stripped from the substrate.
In one embodiment of the present invention, the stripping step includes a stripping liquid entry step of allowing a stripping liquid to enter between the surface of the substrate and the treatment film.

The inventors of the present application have found that the more hydrophilic the surface of the substrate, the higher the wettability (affinity) of the stripping liquid to the substrate, and the easier it is for the stripping liquid to penetrate between the substrate and the treatment film. Therefore, if a treatment film is formed on the hydrophilized surface of the substrate and the stripping liquid is supplied toward the surface of the substrate on which the treatment film is formed, the stripping liquid can be effectively inserted between the substrate and the treatment film. This allows the treatment film to be effectively stripped from the surface of the substrate.

In one embodiment of the invention, the hydrophilization step includes a step of hydrophilizing the surface of the substrate by supplying a liquid hydrophilization liquid to the surface of the substrate. By supplying the liquid hydrophilization liquid to the surface of the substrate, the hydrophilization liquid spreads on the surface of the substrate, and the hydrophilization liquid can be distributed over the entire surface of the substrate. Therefore, the entire surface of the substrate can be hydrophilized evenly. Since the entire surface of the substrate has been hydrophilized, in the subsequent peeling step, the peeling liquid can easily act on the interface between the treatment film and the substrate over the entire surface of the substrate. Therefore, uneven peeling of the treatment film on the surface of the substrate can be reduced.

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

On the other hand, when an oxidizing liquid is used as the hydrophilizing liquid, the portion near the surface of the substrate is oxidized, and since the portion near the surface of the substrate is oxidized, the hydrophilicity of the surface of the substrate is improved.
When an oxidizing liquid is used as the hydrophilizing liquid, the surface of the substrate can be hydrophilized regardless of the presence of organic matter. When an oxidizing liquid is used as the hydrophilizing liquid, the surface of the substrate can be hydrophilized regardless of the presence of organic matter. In other words, even if an organic matter that is difficult to dissolve in an organic solvent is present on the surface of the substrate, the surface of the substrate can be hydrophilized. Therefore, when an oxidizing liquid is used as the hydrophilizing liquid, the hydrophilicity of the surface of the substrate can be further increased.

In one embodiment of the present invention, at least one of Si, SiN, _SiO2 , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate. If these substances are exposed from the surface of the substrate, the surface of the substrate can be made hydrophilic by a hydrophilization step.
In one embodiment of the present invention, the surface layer of the substrate includes a TiN layer exposed from the surface of the substrate, and the hydrophilizing liquid is an oxidizing liquid. By supplying an oxidizing liquid such as hydrofluoric acid (HF, DHF) or an ammonia-hydrogen peroxide mixture (SC1) to the surface of the substrate as the hydrophilizing liquid, an oxide film can be formed on the surface of the TiN layer. By forming an oxide film on the surface of the TiN layer, the surface of the substrate can be made hydrophilic.

In one embodiment of the present invention, the hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water with respect to the surface of the substrate so that the contact angle is smaller than 41.7°. The contact angle of pure water with respect to the surface of the substrate becomes smaller as the hydrophilicity of the surface of the substrate increases. The inventors of the present application have found that if the contact angle of pure water with respect to the surface of the substrate is smaller than 41.7°, the stripping solution acts sufficiently on the interface between the substrate and the treatment film.

Therefore, if the surface of the substrate is made hydrophilic to reduce the contact angle of pure water to the surface of the substrate to less than 41.7°, the stripping solution can be allowed to act sufficiently on the interface between the substrate and the treatment film, thereby enabling the treatment film holding the object to be removed to be effectively stripped from the substrate.
In one embodiment of the present invention, the contact angle of pure water with the treatment film is greater than 52° and smaller than 61°. The present inventors have found that if the contact angle of pure water with the treatment film is greater than 52° and smaller than 61°, the stripping solution can act sufficiently on the interface between the substrate and the treatment film.

Therefore, if the contact angle of the treated film with pure water is greater than 52° and smaller than 61°, the stripping liquid can act sufficiently on the interface between the substrate and the treated film to effectively strip the treated film.
In one embodiment of the present invention, the processing liquid contains a solvent and a solute. The solute has a highly soluble component and a low solubility component that is less soluble in the stripping liquid than the highly soluble component. The processing film forming step includes a step of forming the processing film having a highly soluble solid formed by the highly soluble component and a low solubility solid formed by the low solubility component. The stripping step dissolves the highly soluble solid in the stripping liquid, and strips the processing film, which is holding the object to be removed, from the surface of the substrate.

According to this method, the solubility of the highly soluble component in the stripping solution is higher than the solubility of the less soluble component in the stripping solution, and therefore the highly soluble solid formed by the highly soluble component is more easily dissolved in the stripping solution than the less soluble solid formed by the less soluble component.
Therefore, by supplying a stripping solution to the surface of the substrate and dissolving the highly soluble solid in the stripping solution, gaps are formed in the treated film, while the less soluble solid remains in a solid state without being dissolved in the stripping solution.

Therefore, the highly soluble solid can be dissolved in the stripping liquid while the low soluble solid can be maintained in a solid state without being dissolved in the stripping liquid, and therefore the stripping liquid can reach the interface between the substrate and the low soluble solid through the gap (path) formed by the dissolution of the highly soluble solid.
Therefore, while the object to be removed is held by the low-solubility solid, the stripping liquid can be applied to the interface between the low-solubility solid and the substrate, so that the treatment film can be quickly stripped from the substrate, and the object to be removed can be efficiently removed from the substrate together with the treatment film.

One embodiment of the present invention provides a substrate processing method including a hydrophilization step of hydrophilizing a surface of a substrate, a processing liquid supply step of supplying a processing liquid to the hydrophilized surface of the substrate, a processing film formation step of solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that retains an object to be removed present on the surface of the substrate, and a peeling step of supplying a peeling liquid to the surface of the substrate to peel off the processing film that retains the object to be removed from the surface of the substrate.
The hydrophilization step preferably includes a contact angle reducing step of reducing the contact angle of pure water with respect to the surface of the substrate so that the contact angle is smaller than 41.7°.

According to this method, a treatment film is formed on the hydrophilized surface of the substrate, and a stripping liquid is supplied toward the surface of the substrate on which the treatment film is formed. As described above, the more hydrophilic the substrate surface is, the easier it is for the stripping liquid to act on the interface between the treatment film and the substrate, and the treatment film can be effectively stripped from the substrate surface. In this method, it is preferable that the substrate surface is hydrophilized so that the contact angle of pure water with the substrate surface is smaller than 41.7°. This allows the stripping liquid to act sufficiently on the interface between the substrate and the treatment film. This allows the treatment film, which is holding the object to be removed, to be effectively stripped from the substrate.

In one embodiment of the present invention, the contact angle of pure water with the treatment film is greater than 52° and smaller than 61°, so that the stripping solution can act sufficiently on the interface between the substrate and the treatment film to effectively strip the treatment film.
One embodiment of the present invention provides a substrate processing method including a hydrophilization step of hydrophilizing the surface of a substrate, a processing liquid supply step of supplying a processing liquid to the hydrophilized surface of the substrate, a processing film formation step of solidifying or curing the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate, and a stripping step of supplying a stripping liquid to the surface of the substrate to strip the processing film in a state in which the object to be removed is held from the surface of the substrate, the processing liquid containing a solvent and a solute, the solute having a highly soluble component and a low soluble component that is less soluble in the stripping liquid than the highly soluble component. In this substrate processing method, the processing film formation step includes a step of forming the processing film having a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component. Then, the stripping step dissolves the highly soluble solid in the stripping liquid to strip the processing film in a state in which the object to be removed is held from the surface of the substrate.

According to this method, a treatment film is formed on the hydrophilized surface of a substrate, and a stripping liquid is supplied toward the surface of the substrate on which the treatment film is formed. As described above, the more hydrophilic the substrate surface is, the easier it is for the stripping liquid to act on the interface between the treatment film and the substrate, and the treatment film can be effectively stripped from the substrate surface. Therefore, the treatment film can be effectively stripped from the substrate.
According to this method, the solubility of the highly soluble component in the stripping solution is further higher than the solubility of the less soluble component in the stripping solution, so that the highly soluble solid formed by the highly soluble component is more easily dissolved in the stripping solution than the less soluble solid formed by the less soluble component.

Therefore, by supplying a stripping solution to the surface of the substrate and dissolving the highly soluble solid in the stripping solution, gaps are formed in the treated film, while the less soluble solid remains in a solid state without being dissolved in the stripping solution.
Therefore, the highly soluble solid can be dissolved in the stripping liquid while the low soluble solid can be maintained in a solid state without being dissolved in the stripping liquid, and therefore the stripping liquid can reach the interface between the substrate and the low soluble solid through the gap (path) formed by the dissolution of the highly soluble solid.

Therefore, while the object to be removed is held by the low-solubility solid, the stripping liquid can be applied to the interface between the low-solubility solid and the substrate, thereby making it possible to effectively strip the treated film, which is holding the object to be removed, from the substrate.
As a result, the treatment film can be quickly peeled off from the substrate, while the object to be removed can be efficiently removed from the substrate together with the treatment film.

In this substrate processing method, at least one of Si, SiN, _SiO2 , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate. If these substances are exposed from the surface of the substrate, the surface of the substrate can be made hydrophilic by a hydrophilization step.
In this substrate processing method, the hydrophilization step includes a contact angle reduction step of reducing the contact angle of pure water with respect to the surface of the substrate so that the contact angle is smaller than 41.7°. This allows the stripping solution to act sufficiently on the interface between the substrate and the processing film. This allows the processing film, which is holding the object to be removed, to be effectively stripped from the substrate.
In the above substrate processing method, it is preferable that a contact angle of the treatment film with pure water is greater than 52° and smaller than 61°.

One embodiment of the present invention provides a substrate processing apparatus including a hydrophilization liquid supply unit that supplies a hydrophilization liquid to the surface of the substrate to hydrophilize the surface of the substrate, a processing liquid supply unit that supplies a processing liquid to the surface of the substrate, a processing film forming unit that solidifies or hardens the processing liquid in contact with the surface of the substrate to form a processing film, a stripping liquid supply unit that supplies a stripping liquid to the surface of the substrate to strip the processing film formed on the surface of the substrate, and a controller that controls the hydrophilization liquid supply unit, the processing liquid supply unit, the processing film forming unit, and the stripping liquid supply unit.

The controller included in this substrate processing apparatus is programmed to supply a hydrophilizing liquid from the hydrophilizing liquid supply unit to the surface of the substrate to hydrophilize the surface of the substrate, supply a processing liquid from the processing liquid supply unit to the substrate whose surface has been hydrophilized, solidify or harden the processing liquid supplied to the surface of the substrate by the processing film forming unit to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate, supply a stripping liquid from the stripping liquid supply unit to the surface of the substrate to strip the processing film that holds the object to be removed from the surface of the substrate, and partially dissolve the processing film with the stripping liquid to form a through hole in the processing film.

According to this configuration, the same effects as those of the above-mentioned substrate processing method are achieved.
One embodiment of the present invention provides a substrate processing apparatus including a hydrophilization liquid supply unit that supplies a hydrophilization liquid to a surface of a substrate to hydrophilize the surface of the substrate, a processing liquid supply unit that supplies a processing liquid to the surface of the substrate, a processing film forming unit that solidifies or hardens the processing liquid in contact with the surface of the substrate to form a processing film, a stripping liquid supply unit that supplies a stripping liquid to the surface of the substrate to strip the processing film formed on the surface of the substrate, and a controller that controls the hydrophilization liquid supply unit, the processing liquid supply unit, the processing film forming unit, and the stripping liquid supply unit, wherein the processing liquid contains a solvent and a solute, the solute has a highly soluble component and a low solubility component that is less soluble in the stripping liquid than the highly soluble component, and the processing film has a highly soluble solid formed by the highly soluble component and a low solubility solid formed by the low solubility component.

The controller included in this substrate processing apparatus is programmed to hydrophilize the surface of the substrate by supplying a hydrophilizing liquid from the hydrophilizing liquid supply unit to the surface of the substrate, supply a processing liquid from the processing liquid supply unit to the hydrophilized surface of the substrate, solidify or harden the processing liquid supplied to the surface of the substrate by the processing film forming unit to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate, supply a stripping liquid from the stripping liquid supply unit to the surface of the substrate, dissolve the highly soluble solid in the stripping liquid, and strip the processing film that holds the object to be removed from the surface of the substrate.

According to this configuration, the same effects as those of the above-mentioned substrate processing method are achieved.
The hydrophilization preferably involves reducing the contact angle of pure water with respect to the surface of the substrate so that the contact angle is smaller than 41.7°.
It is also preferable that the contact angle of pure water with the treatment film is greater than 52° and smaller than 61°.

FIG. 1 is a schematic plan view showing a layout of a substrate processing apparatus according to an embodiment 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. 3 is a schematic diagram of a droplet of pure water on a substrate and its surroundings. FIG. 4A is a schematic diagram for explaining how the surface of the substrate is made hydrophilic by an organic solvent. FIG. 4B is a schematic diagram for explaining how the surface of the substrate is made hydrophilic by the oxidizing liquid. FIG. 5 is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus. FIG. 6 shows an example of the configuration of the surface layer of a substrate to be processed. FIG. 7 shows another example of the configuration of the surface layer of the substrate to be processed. FIG. 8 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus. FIG. 9A is a schematic diagram for explaining the hydrophilization step (step S2) of the substrate processing. FIG. 9B is a schematic diagram for explaining the first rinsing step (step S3) of the substrate processing. FIG. 9C is a schematic diagram for explaining the replacement step (step S4) of the substrate processing. FIG. 9D is a schematic diagram for explaining the processing liquid supplying step (step S5) of the substrate processing. FIG. 9E is a schematic diagram for explaining the processing film forming step (step S6) of the substrate processing. FIG. 9F is a schematic diagram for explaining the processing film forming step (step S6) of the substrate processing. FIG. 9G is a schematic diagram for explaining the peeling step (step S7) of the substrate processing. FIG. 9H is a schematic diagram for explaining the second rinsing step (step S8) of the substrate processing. FIG. 9I is a schematic diagram for explaining the residue removing step (step S9) of the substrate processing. FIG. 10A is a schematic diagram for explaining how a treatment film is peeled off from a surface of a substrate. FIG. 10B is a schematic diagram for explaining how the treatment film is peeled off from the surface of the substrate. FIG. 10C is a schematic diagram for explaining how the treatment film is peeled off from the surface of the substrate. FIG. 11 is a flow chart for explaining another example of substrate processing by the substrate processing apparatus. FIG. 12A is a schematic diagram for explaining a procedure for measuring the contact angle of pure water with respect to the surface of an experimental substrate. FIG. 12B is a schematic diagram for explaining the procedure for peeling off the treatment film from the experimental substrate. FIG. 13 is a table showing the contact angle of pure water with respect to the surface of the experimental substrate and the suitability of the treatment film with the stripping liquid. FIG. 14 is a schematic diagram for explaining the procedure for measuring the contact angle of pure water with respect to the surface of the treatment film. FIG. 15 is a table showing the contact angle of pure water with respect to the surface of the treatment film.

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

The substrate W may be a substrate having at least one of Si (silicon), SiN (silicon nitride), SiO ₂ (silicon oxide), SiGe (silicon germanium), Ge (germanium), SiCN (silicon carbonitride), W (tungsten), TiN (titanium nitride), Co (cobalt), Cu (copper), Ru (ruthenium) and a-C (amorphous carbon) exposed on its surface. That is, only one of the above-mentioned substances may be exposed on the surface of the substrate W, or a plurality of the above-mentioned substances may be exposed on the surface of the substrate W.

The substrate processing apparatus 1 includes a plurality of processing units 2 that process substrates W with a fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W to be processed in the processing units 2 is placed, transport robots IR and CR that transport the substrates W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.
The transport robot IR transports the substrate W between the carrier C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing units 2. The processing units 2 have, for example, the same configuration. Although described in detail below, the processing fluids supplied to the substrate W in the processing units 2 include a hydrophilization liquid, a rinsing liquid, a replacement liquid, a processing liquid, a stripping liquid, a residue removal liquid, a heat medium, an inert gas (gas), etc.

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

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

The spin base 21 has a disk shape that extends horizontally. On the upper surface of the spin base 21, a number of chuck pins 20 that grip the periphery of the substrate W are arranged at intervals in the circumferential direction of the spin base 21. The spin base 21 and the number of chuck pins 20 form a substrate holding unit that holds the substrate W horizontally. The substrate holding unit is also called a substrate holder.

The rotating shaft 22 extends vertically along the rotation axis A1. The upper end of the rotating shaft 22 is connected to the center of the lower surface of the spin base 21. The spin motor 23 applies a rotational force to the rotating shaft 22. The spin motor 23 rotates the rotating shaft 22, thereby rotating the spin base 21. This causes the substrate W to rotate around the rotation axis A1. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

The spin chuck 5 is not limited to a clamping type chuck that brings multiple chuck pins 20 into contact with the peripheral edge surface of the substrate W, but may also be a vacuum type chuck that holds the substrate W horizontally by adsorbing the lower surface of the substrate W to the upper surface of the spin base 21.
The facing member 6 faces the substrate W held by the spin chuck 5 from above. The facing member 6 is formed in a disk shape having a diameter substantially equal to or greater than that of the substrate W. The facing member 6 has a facing surface 6a facing the top surface (upper surface) of the substrate W. The facing surface 6a is disposed above the spin chuck 5 and along a substantially horizontal plane.

A hollow shaft 60 is fixed to the opposing member 6 on the side opposite to the opposing surface 6a. A communication hole 6b that passes vertically through the opposing member 6 is formed in a portion of the opposing member 6 that overlaps with the rotation axis A1 in a plan view. The communication hole 6b communicates with an internal space 60a of the hollow shaft 60.
The facing member 6 isolates the atmosphere in the space between the facing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. For this reason, the facing member 6 is also called a blocking plate.

The processing unit 2 further includes a counter member lifting unit 61 that drives the lifting and lowering of the counter member 6, and a counter member rotating unit 62 that rotates the counter member 6 about the rotation axis A1.
The opposing member lifting unit 61 can position the opposing member 6 in the vertical direction at any position (height) between the lower position and the upper position. The lower position is a position where the opposing surface 6a is closest to the substrate W within the movable range of the opposing member 6. The upper position is a position where the opposing surface 6a is farthest from the substrate W within the movable range of the opposing member 6. When the opposing member 6 is located at the upper position, the transport robot CR can access the spin chuck 5 to load and unload the substrate W.

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 provides a driving force to the ball screw mechanism. The opposing member lifting unit 61 is also called an opposing member lifter (shield lifter). The opposing member rotation unit 62 includes, for example, a motor (not shown) that rotates the hollow shaft 60.

The processing cup 7 includes a plurality of guards 71 for receiving liquid that splashes outward from the substrate W held on the spin chuck 5, a plurality of cups 72 for receiving liquid guided downward by the multiple guards 71, and a cylindrical outer wall member 73 that surrounds the multiple guards 71 and the multiple cups 72.
In this embodiment, an example is shown in which two guards 71 (a first guard 71A and a second guard 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided.

Each of the first cup 72A and the second cup 72B has the form of an upwardly opening annular groove.
The first guard 71A is disposed so as to surround the spin base 21. The second guard 71B is disposed so as to surround the spin base 21 on the outer side of the first guard 71A.

The first guard 71A and the second guard 71B each have a substantially cylindrical shape. The upper end of each guard 71 is inclined inward toward the spin base 21.
The first cup 72A receives the liquid guided downward by the first guard 71 A. The second cup 72B is formed integrally with the first guard 71 A, and receives the liquid guided downward by the second guard 71B.

The processing unit 2 includes a guard lifting unit 74 that vertically raises and lowers the first guard 71A and the second guard 71B separately. The guard lifting unit 74 raises and lowers the first guard 71A between a lower position and an upper position. The guard lifting unit 74 raises and lowers the second guard 71B between a lower position and an upper position.
When the first guard 71A and the second guard 71B are both located in the upper position, liquid splashed from the substrate W is received by the first guard 71A. When the first guard 71A is located in the lower position and the second guard 71B is located in the upper position, liquid splashed from the substrate W is received by the second guard 71B. When the first guard 71A and the second guard 71B are both located in the lower position, the transport robot CR can access the spin chuck 5 to load and unload the substrate W.

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

The first movable nozzle 9 is an example of a hydrophilization liquid nozzle (hydrophilization liquid supply unit) that supplies (discharges) a hydrophilization liquid toward the upper surface of the substrate W held by the spin chuck 5 .
The first movable nozzle 9 is moved in the horizontal and vertical directions by the first nozzle movement unit 35. The first movable nozzle 9 can move in the horizontal direction between a central position and a home position (retracted position). When the first movable nozzle 9 is located at the central position, it faces a central region of the upper surface of the substrate W. The central region of the upper surface of the substrate W refers to a region on the upper surface of the substrate W that includes the center of rotation of the substrate W and its surroundings.

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

The pivot drive unit rotates the pivot about a vertical axis to swing the arm. The pivot drive unit raises and lowers the pivot in the vertical direction to raise and lower the arm. The first moving nozzle 9 moves in the horizontal and vertical directions in response to the swing and raising and lowering of the arm.
The first movable nozzle 9 is connected to a hydrophilization liquid pipe 40 that guides the hydrophilization liquid. When a hydrophilization liquid valve 50 interposed in the hydrophilization liquid pipe 40 is opened, the hydrophilization liquid is discharged in a continuous flow downward from the first movable nozzle 9. When the first movable nozzle 9 is located at the central position and the hydrophilization liquid valve 50 is opened, the hydrophilization liquid is supplied to the central region of the upper surface of the substrate W.

Examples of the hydrophilizing liquid include hydrofluoric acid (HF, DHF), an oxidizing liquid such as an ammonia-hydrogen peroxide mixture (SC1), and a sulfuric acid-hydrogen peroxide mixture (SPM), an organic solvent such as isopropyl alcohol (IPA), and hydrochloric acid (HCl), etc. The hydrophilizing liquid is a liquid for hydrophilizing the surface of the substrate W (enhancing its hydrophilicity).
The oxidizing liquid is a liquid that contains a substance (oxidizing agent) that has oxidizing power. For example, SC1 contains hydrogen peroxide as an oxidizing agent, hydrofluoric acid contains hydrogen fluoride as an oxidizing agent, and SPM contains persulfuric acid as an oxidizing agent.

Hydrophilicity refers to affinity for water. Hydrophilicity is also called wettability. Contact angle is an index of hydrophilicity. Contact angle is a numerical representation of the degree of swelling of a droplet (height of liquid) that occurs when a liquid is dropped onto a solid. Specifically, contact angle is the angle between the liquid surface and the surface of a solid when the liquid adhering to the surface of the solid is viewed from the side. The larger the contact angle, the lower the wettability of the surface of the solid, and the smaller the contact angle, the higher the wettability of the surface of the solid.

Figure 3 is a schematic diagram of a droplet of pure water on a substrate W and its surroundings. As shown in Figure 3, it is preferable that the contact angle θ of the pure water with respect to the surface of the substrate W is greater than 0° and smaller than 41.7°. In this embodiment, DIW is used as the pure water. If the contact angle of the pure water with respect to the surface of the substrate W is greater than 0° and smaller than 41.7°, the treatment film (described later) is easily peeled off from the surface of the substrate W by the stripping liquid (described later). It is more preferable that the contact angle θ of the pure water with respect to the surface of the substrate W is greater than 0° and 36.0° or less. It is even more preferable that the contact angle θ of the pure water with respect to the surface of the substrate W is greater than 0° and 32.7° or less.

Next, a description will be given of how the surface of the substrate W is rendered hydrophilic. Figures 4A and 4B are schematic diagrams for explaining how the surface of the substrate W is rendered hydrophilic by the hydrophilizing liquid.
When an organic solvent such as IPA is used as the hydrophilizing liquid, the hydrophobic organic matter 170 adhering to the surface of the substrate W is removed, thereby making the surface of the substrate W hydrophilic. Specifically, as shown in Fig. 4A, the hydrophobic organic matter 170 present on the surface of the substrate W is dissolved in the organic solvent, making the surface of the substrate W hydrophilic. Therefore, organic matter 170A that is difficult to dissolve in the hydrophilizing liquid may remain on the surface of the substrate W. Therefore, hydrophilization by the organic solvent is affected by the type of organic matter 170 present on the surface of the substrate W.

The organic matter is a part of the object to be removed that is present on the surface of the substrate W, and even if the organic matter is removed with an organic solvent, it cannot be said that the object to be removed is sufficiently removed. Therefore, even if the surface of the substrate W is made hydrophilic by an organic solvent, it is necessary to remove the object to be removed by peeling off the processing film, as described below.
On the other hand, when an oxidizing liquid such as hydrofluoric acid or SC1 is used as the hydrophilizing liquid, as shown in Fig. 4B, the surface of the substrate W is oxidized to form an oxide film 171 on the surface of the substrate W. By oxidizing the surface of the substrate W, oxygen atoms are bonded to the material exposed from the surface of the substrate W. Since oxygen atoms are bonded to the material exposed from the surface of the substrate W, the hydrophilicity of the surface of the substrate W is improved.

When an oxidizing liquid is used as the hydrophilizing liquid, the surface of the substrate W can be made hydrophilic regardless of the presence of organic matter 170. In other words, even if organic matter 170A that is not easily dissolved in an organic solvent is present on the surface of the substrate W, the surface of the substrate W can be made hydrophilic. Therefore, when an oxidizing liquid is used as the hydrophilizing liquid, the hydrophilicity of the surface of the substrate W can be increased more efficiently than when an organic solvent is used as the hydrophilizing liquid.

A substrate W having a surface on which at least one of Si, SiN, SiO ₂ , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C is exposed can be hydrophilized by the hydrophilization liquid. In particular, a substrate W having a surface on which at least one of Si, SiN, SiO ₂ , W, TiN, Co, Cu, Ru, and a-C is exposed is easily hydrophilized by the hydrophilization liquid, and a substrate W having a surface on which at least one of Si, SiN, SiO ₂ , W, TiN, Co, and Cu is even more easily hydrophilized by the hydrophilization liquid.

Referring again to FIG. 2, the second movable nozzle 10 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (discharges) a processing liquid toward the upper surface of the substrate W held by the spin chuck 5 .
The second moving nozzle 10 is moved in the horizontal and vertical directions by the second nozzle moving unit 36. The second moving nozzle 10 can move in the horizontal direction between a central position and a home position (retracted position). When the second moving nozzle 10 is located at the central position, it faces a central region of the upper surface of the substrate W.

When the second moving nozzle 10 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The second moving nozzle 10 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.
The second nozzle moving unit 36 has a configuration similar to that of the first nozzle moving unit 35. That is, the second nozzle moving unit 36 may include an arm (not shown) connected to the second moving nozzle 10 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending along the vertical direction, and a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

The second moving nozzle 10 is connected to a processing liquid pipe 44 that guides the processing liquid. When a processing liquid valve 54 disposed in the processing liquid pipe 44 is opened, the processing liquid is discharged in a continuous flow downward from the second moving nozzle 10. When the processing liquid valve 54 is opened while the second moving nozzle 10 is located at the central position, the processing liquid is supplied to a central region of the upper surface of the substrate W.
The processing liquid contains a solute and a solvent. The processing liquid is solidified or hardened by volatilization (evaporation) of at least a portion of the solvent contained in the processing liquid. The processing liquid is solidified or hardened on the substrate W to form a solid processing film that holds objects to be removed, such as particles, present on the substrate W.

Here, "solidification" refers to the solidification of a solute due to forces acting between molecules or atoms as a solvent evaporates, for example. "Hardening" refers to the solidification of a solute due to chemical changes such as polymerization or crosslinking, for example. Therefore, "solidification or hardening" refers to the "solidification" of a solute due to various factors.
The treatment liquid contains, as solutes, a low solubility component and a high solubility component.

A corrosion prevention component may be contained in the treatment liquid discharged from the second moving nozzle 10. Although the details will be described later, the corrosion prevention component is, for example, BTA (benzotriazole).
The low solubility component and the high solubility component may be substances having different solubilities in the stripping solution described below. The low solubility component may be, for example, novolak. The high solubility component may be, for example, 2,2-bis(4-hydroxyphenyl)propane.

The solvent contained in the treatment liquid may be any liquid that dissolves the low solubility component and the high solubility component. The solvent contained in the treatment liquid is preferably a liquid that is compatible (miscible) with the stripping liquid. Compatibility refers to the property of two types of liquids dissolving and mixing with each other.
The treatment film is mainly composed of a low solubility component in a solid state and a high solubility component in a solid state. The solvent may remain in the treatment film. Details of each component (solvent, low solubility component, high solubility component, and corrosion prevention component) contained in the treatment liquid will be described later.

If the contact angle of the treatment film with pure water is greater than 52° and smaller than 61°, a stripping liquid described below can be sufficiently applied to the interface between the treatment film and the substrate W. If a treatment liquid described below is used, a treatment film can be formed in which the contact angle of pure water is greater than 52° and smaller than 61°.
The third moving nozzle 11 is an example of a stripping liquid nozzle (stripping liquid supply unit) that supplies (discharges) a continuous flow of a stripping liquid such as ammonia water toward the upper surface of the substrate W held by the spin chuck 5. The stripping liquid is a liquid for stripping the processing film, which is holding the object to be removed, from the upper surface of the substrate W.

The third movable nozzle 11 is moved in the horizontal and vertical directions by the third nozzle movement unit 37. The third movable nozzle 11 can move in the horizontal direction between a central position and a home position (retracted position).
When the third moving nozzle 11 is located at the central position, it faces a central region of the upper surface of the substrate W. When the third moving nozzle 11 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The third moving nozzle 11 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

The third nozzle moving unit 37 has a similar configuration to the first nozzle moving unit 35. That is, the third nozzle moving unit 37 may include an arm (not shown) connected to the third moving nozzle 11 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending vertically, and a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

The third moving nozzle 11 is connected to an upper stripping liquid pipe 45 that guides the stripping liquid to the third moving nozzle 11. When an upper stripping liquid valve 55 interposed in the upper stripping liquid pipe 45 is opened, the stripping liquid is ejected downward in a continuous flow from the ejection port of the third moving nozzle 11. When the upper stripping liquid valve 55 is opened while the third moving nozzle 11 is located at the central position, the stripping liquid is supplied to the central region of the upper surface of the substrate W.

The stripping liquid is a liquid that dissolves the highly soluble components contained in the processing liquid more easily than the less soluble components contained in the processing liquid. The stripping liquid is, for example, ammonia water, and the mass percent concentration of ammonia in the stripping liquid is 0.4%.
The stripping solution may be, for example, an alkaline aqueous solution (alkaline liquid) other than ammonia water. Specific examples of alkaline aqueous solutions other than ammonia water include a TMAH (tetramethylammonium hydroxide) aqueous solution, a choline aqueous solution, and any combination thereof. The stripping solution may be pure water (preferably DIW) or a neutral or acidic aqueous solution (non-alkaline aqueous solution).

The stripping solution is preferably alkaline. The pH of the stripping solution is preferably 7 to 13. More specifically, the pH of the stripping solution is preferably 8 to 13, more preferably 10 to 13, and even more preferably 11 to 12.5. The pH is preferably measured after degassing to avoid the effects of dissolution of carbon dioxide gas in the air.

The majority of the solvent in the stripper solution is pure water. The ratio of pure water to the solvent in the stripper solution is 50 to 100% by mass (preferably 70 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and even more preferably 99 to 100% by mass). "% by mass" refers to the ratio of the mass of a certain component to the total mass of the liquid. The mass percent concentration of the solute in the stripper solution is 0.1 to 10% (preferably 0.2 to 8%, and even more preferably 0.3 to 6%).

The central nozzle 12 is housed in an internal space 60a of a hollow shaft 60 of the facing member 6. A discharge port 12a provided at the tip of the central nozzle 12 is exposed from the communication hole 6b, and faces the central region of the top surface of the substrate W from above.
The central nozzle 12 includes a plurality of tubes (a first tube 31, a second tube 32, and a third tube 33) that discharge fluid downward, and a cylindrical casing 30 that surrounds the plurality of tubes. The plurality of tubes and the casing 30 extend in the vertical direction along the rotation axis A1. The outlet 12a of the central nozzle 12 is also the outlet of the first tube 31, the outlet of the second tube 32, and the outlet of the third tube 33.

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

The first tube 31 is connected to an upper rinsing liquid piping 41 that guides the rinsing liquid to the first tube 31. When an upper rinsing liquid valve 51 provided in the upper rinsing liquid piping 41 is opened, the rinsing liquid is discharged in a continuous flow from the first tube 31 (the central nozzle 12) toward the central region of the upper surface of the substrate W.
The rinse liquid is a liquid that washes away liquid adhering to the surface of the substrate W. Examples of the rinse liquid include DIW, carbonated water, electrolytic ion water, hydrochloric acid water with a diluted concentration (for example, about 1 ppm to 100 ppm), ammonia water with a diluted concentration (for example, about 1 ppm to 100 ppm), reduced water (hydrogen water), and the like.

The second tube 32 is connected to an organic solvent pipe 42 that guides an organic solvent such as IPA to the second tube 32. When an organic solvent valve 52 provided in the organic solvent pipe 42 is opened, the organic solvent is discharged in a continuous flow from the second tube 32 (central nozzle 12) toward the central region of the upper surface of the substrate W.
The organic solvent discharged from the second tube 32 is preferably compatible with the rinsing liquid and the processing liquid. The organic solvent discharged from the second tube 32 functions as a residue removing liquid for dissolving and removing the residue of the processing film remaining on the upper surface of the substrate W after it is peeled off and removed from the upper surface of the substrate W by the stripping liquid. For this reason, the residue removing liquid is also called a residue dissolving liquid.

In the substrate processing described later, the organic solvent discharged from the second tube 32 is supplied to the upper surface of the substrate W covered with a liquid film of the rinsing liquid, and the processing liquid is supplied to the upper surface of the substrate W covered with the liquid film of the organic solvent. When the organic solvent is supplied to the upper surface of the substrate W covered with the liquid film of the rinsing liquid, most of the rinsing liquid on the substrate W is swept away by the organic solvent and discharged from the substrate W. The remaining trace amount of the rinsing liquid dissolves in the organic solvent and diffuses into the organic solvent. The diffused rinsing liquid is discharged from the substrate W together with the organic solvent. Therefore, the rinsing liquid on the substrate W can be efficiently replaced with the organic solvent. For the same reason, the organic solvent on the substrate W can be efficiently replaced with the processing liquid. This allows the amount of rinsing liquid contained in the processing liquid on the substrate W to be reduced. The organic solvent discharged from the second tube 32 functions as a replacement liquid that replaces the rinsing liquid.

The organic solvent discharged from the second tube 32 is preferably a low surface tension liquid having a surface tension lower than that of the rinsing liquid. In the substrate processing described below, the upper surface of the substrate W is not dried by shaking off the rinsing liquid on the substrate W, but rather, the rinsing liquid on the substrate W is replaced by the organic solvent, and then the organic solvent on the substrate W is shaken off to dry the upper surface of the substrate W. Therefore, if the organic solvent is a low surface tension liquid, the surface tension acting on the upper surface of the substrate W can be reduced when the upper surface of the substrate W is dried.

Examples of organic solvents that function as residue removal liquids, low surface tension liquids, and replacement liquids include liquids containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.
The organic solvent that functions as the residue removal liquid, the low surface tension liquid, and the replacement liquid does not need to be composed of a single component, but may be a liquid mixed with other components, for example, a mixture of IPA and DIW, or a mixture of IPA and HFE.

The third tube 33 is connected to a gas pipe 43 that guides gas to the third tube 33. When a gas valve 53 installed in the gas pipe 43 is opened, gas is discharged downward from the third tube 33 (central nozzle 12) in a continuous flow.
The gas discharged from the third tube 33 is, for example, an inert gas such as nitrogen gas. The gas discharged from the third tube 33 may be air. The inert gas is not limited to nitrogen gas, but is a gas that is inert to the upper surface of the substrate W. Examples of the inert gas include nitrogen gas and rare gases such as argon.

The lower nozzle 13 is inserted into a through hole 21a that opens in the center of the upper surface of the spin base 21. The outlet 13a of the lower nozzle 13 is exposed from the upper surface of the spin base 21. The outlet 13a of the lower nozzle 13 faces the central region of the lower surface (lower surface) of the substrate W from below. The central region of the lower surface of the substrate W refers to the region of the lower surface of the substrate W that includes the center of rotation of the substrate W.

One end of a common pipe 80 that commonly guides the rinsing liquid, the stripping liquid, and the heat medium to the lower nozzle 13 is connected to the lower nozzle 13. The other end of the common pipe 80 is connected to a lower rinsing liquid pipe 81 that guides the rinsing liquid to the common pipe 80, a lower stripping liquid pipe 82 that guides the stripping liquid to the common pipe 80, and a heat medium pipe 83 that guides the heat medium to the common pipe 80.
When a lower rinse liquid valve 86 provided in the lower rinse liquid piping 81 is opened, the rinse liquid is discharged in a continuous flow from the lower nozzle 13 toward the central region of the lower surface of the substrate W. When a lower remover liquid valve 87 provided in the lower remover liquid piping 82 is opened, the remover liquid is discharged in a continuous flow from the lower nozzle 13 toward the central region of the lower surface of the substrate W. When a heat medium valve 88 provided in the heat medium piping 83 is opened, the heat medium is discharged in a continuous flow from the lower nozzle 13 toward the central region of the lower surface of the substrate W.

The lower surface nozzle 13 is an example of a lower rinse liquid supply unit that supplies rinse liquid to the lower surface of the substrate W. The lower surface nozzle 13 is also an example of a lower stripping liquid supply unit that supplies stripping liquid to the lower surface of the substrate W. The lower surface nozzle 13 is also an example of a heat medium supply unit that supplies a heat medium to the substrate W for heating the substrate W. The lower surface nozzle 13 is also an example of a substrate heating unit that heats the substrate W.

The rinsing liquid discharged from the lower nozzle 13 is similar to the rinsing liquid discharged from the central nozzle 12, and therefore a description thereof will be omitted. The stripping liquid discharged from the lower nozzle 13 is similar to the stripping liquid discharged from the third moving nozzle 11, and therefore a description thereof will be omitted.
The heat medium discharged from the lower nozzle 13 is, for example, high-temperature DIW having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid. When the solvent contained in the processing liquid is IPA, for example, DIW at 60° C. to 80° C. is used as the heat medium. The heat medium discharged from the lower nozzle 13 is not limited to high-temperature DIW, and may be a high-temperature gas such as a high-temperature inert gas or high-temperature air having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid.

5 is a block diagram showing an electrical configuration of the main parts of the substrate processing apparatus 1. The controller 3 includes a microcomputer, and controls the controlled objects 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 perform various controls for substrate processing by the processor 3A executing the control program.

In particular, the controller 3 is programmed to control the transport robots IR and CR, the spin motor 23, the first nozzle moving unit 35, the second nozzle moving unit 36, the third nozzle moving unit 37, the opposing member lifting unit 61, the opposing member rotating unit 62, the guard lifting unit 74, the hydrophilization liquid valve 50, the upper rinsing liquid valve 51, the organic solvent valve 52, the gas valve 53, the processing liquid valve 54, the upper stripping liquid valve 55, the lower rinsing liquid valve 86, the lower stripping liquid valve 87, and the heat medium valve 88. By controlling the valves with the controller 3, it is possible to control whether or not processing fluid is discharged from the corresponding nozzle, and the discharge flow rate of the processing fluid from the corresponding nozzle.

<Configuration of substrate to be processed>
6 shows an example of details of a surface layer of a substrate W to be processed by the substrate processing apparatus 1. A semiconductor layer 151, an insulating layer 152, and a barrier layer 153 are provided on a surface layer 150 of the substrate W. The semiconductor layer 151 is made of, for example, Si (silicon). An impurity region 154 is formed in a surface portion of the semiconductor layer 151.

The insulating layer 152 is formed of, for example, SiO 2 (silicon oxide). Above the impurity region 154, a contact hole 155 penetrating the insulating layer 152 is provided.
The barrier layer 153 is formed on the upper surface of the insulating layer 152 and on the inner surface of the contact hole 155. The barrier layer 153 is a TiN layer made of TiN (titanium nitride), and is formed by an ALD (atomic layer deposition) method or the like. Therefore, TiN is exposed on the surface of the substrate W.

Contact holes 155 may be provided at equal intervals in the insulating layer 152, and a fine uneven pattern may be formed by the insulating layer 152 and the contact holes 155. In this case, the barrier layer 153 has a shape following the uneven pattern.
7 shows another example of details of the surface layer of the substrate W to be processed by the substrate processing apparatus 1. As shown in FIG. 7, the surface layer 150 of the substrate W to be processed by the substrate processing apparatus 1 may be provided with a metal layer 156 in addition to the semiconductor layer 151, the insulating layer 152, and the barrier layer 153. The metal layer 156 is, for example, a tungsten layer formed of W (tungsten), and is formed by a CVD (chemical vapor deposition) method or the like. The metal layer 156 fills the contact hole 155 and covers the barrier layer 153. Therefore, the surface of the metal layer 156 is a flat surface. The metal constituting the metal layer 156 is exposed on the surface of the substrate W shown in FIG. 7. If the metal layer 156 is formed of tungsten, tungsten is exposed on the surface of the substrate W.

<Substrate Processing by Substrate Processing Apparatus>
Fig. 8 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus 1. Fig. 8 mainly shows processing that is realized by the controller 3 executing a program. Figs. 9A to 9I are schematic diagrams for explaining the state of each step of the substrate processing.
In the substrate processing by the substrate processing apparatus 1, for example, as shown in FIG. 8, a substrate loading step (step S1), a hydrophilization step (step S2), a first rinsing step (step S3), a substitution step (step S4), a processing liquid supply step (step S5), a processing film formation step (step S6), a peeling step (step S7), a second rinsing step (step S8), a residue removal step (step S9), a spin drying step (step S10), and a substrate unloading step (step S11) are performed in this order.

In the following, reference will be made mainly to Figures 2 and 8. Reference will also be made to Figures 9A to 9I as appropriate.
First, an unprocessed substrate W is carried into the processing unit 2 from the carrier C by the transport robots IR, CR (see FIG. 1) and handed over to the spin chuck 5 (step S1). As a result, the substrate W is held horizontally by the spin chuck 5 (substrate holding step). When the substrate W is carried in, the opposing member 6 is retracted to the upper position.

The spin chuck 5 continues to hold the substrate W until the spin dry process (step S10) is completed. During the period from the start of the substrate holding process to the end of the spin dry process (step S10), the guard lifting unit 74 adjusts the height positions of the first guard 71A and the second guard 71B so that at least one guard 71 is located at the upper position.
With the substrate W held by the spin chuck 5, the spin motor 23 rotates the spin base 21. This starts the rotation of the substrate W held horizontally (substrate rotation process). The opposing member rotation unit 62 may rotate the opposing member 6 synchronously with the spin base 21. Synchronous rotation means rotating the opposing member 6 in the same rotation direction and at the same rotation speed as the spin base 21.

Next, after the transport robot CR retreats outside the processing unit 2, the hydrophilization process (step S2) is started. In the hydrophilization process, first, with the opposing member 6 located at the retreat position, the first nozzle movement unit 35 moves the first moving nozzle 9 to the processing position. The processing position of the first moving nozzle 9 is, for example, the central position. When the opposing member 6 is located at the retreat position, each moving nozzle can move horizontally between the opposing member 6 and the substrate W. The retreat position may be the upper position.

Then, the hydrophilic liquid valve 50 is opened. As a result, as shown in FIG. 9A, hydrophilic liquid such as hydrofluoric acid is supplied (discharged) from the first moving nozzle 9 toward the central region of the upper surface of the rotating substrate W (hydrophilic liquid supply process, hydrophilic liquid discharge process). The hydrophilic liquid supplied to the upper surface of the substrate W spreads radially due to centrifugal force and permeates the entire upper surface of the substrate W. As a result, the upper surface of the substrate W is hydrophilized, and the contact angle of pure water with the upper surface of the substrate W becomes smaller than 41.7° (contact angle reduction process).

The supply of the hydrophilization liquid from the first movable nozzle 9 continues for a predetermined time, for example, 30 seconds. In the hydrophilization step, the substrate W is rotated at a predetermined hydrophilization rotation speed, for example, 800 rpm.
Next, a first rinsing step (step S3) is performed to rinse off the hydrophilizing liquid on the substrate W.
Specifically, the hydrophilization liquid valve 50 is closed. This stops the supply of the hydrophilization liquid to the substrate W. Then, the first nozzle moving unit 35 moves the first moving nozzle 9 to the home position. Then, the facing member lifting unit 61 moves the facing member 6 to a processing position between the upper position and the lower position. When the facing member 6 is located at the processing position, the distance between the upper surface of the substrate W and the facing surface 6a is, for example, 30 mm.

With the opposing member 6 in the processing position, the upper rinse liquid valve 51 is opened. As a result, as shown in FIG. 9B, rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the rotating substrate W. The rinse liquid supplied to the upper surface of the substrate W from the central nozzle 12 spreads radially due to centrifugal force, and permeates the entire upper surface of the substrate W. As a result, the hydrophilizing liquid on the upper surface of the substrate W is washed away from the substrate W.

At approximately the same time that the upper rinse liquid valve 51 is opened, the lower rinse liquid valve 86 is opened. As a result, as shown in FIG. 9B, rinse liquid is supplied (discharged) from the lower nozzle 13 toward the central region of the underside of the rotating substrate W. The rinse liquid supplied to the underside of the substrate W from the lower nozzle 13 spreads radially due to centrifugal force, and permeates the entire underside of the substrate W. Even if the hydrophilic liquid that has landed on the upper surface of the substrate W in the hydrophilic process described above splashes off the substrate W and adheres to the underside of the substrate W, the hydrophilic liquid adhering to the underside is washed away by the rinse liquid supplied from the lower nozzle 13.

The discharge of the rinsing liquid from the central nozzle 12 and the lower nozzle 13 continues for a predetermined time, for example, 30 seconds. In the first rinsing step, the substrate W is rotated at a predetermined first rinsing rotation speed, for example, 800 rpm.
Next, the replacement step (step S4) is started. In the replacement step, the rinsing liquid on the substrate W is replaced with an organic solvent (for example, IPA) as a replacement liquid.

Specifically, the upper rinse liquid valve 51 and the lower rinse liquid valve 86 are closed, thereby stopping the supply of the rinse liquid to the upper and lower surfaces of the substrate W. The opposing member 6 is maintained in the processing position.
With the opposing member 6 maintained at the processing position, the organic solvent valve 52 is opened. As a result, as shown in Fig. 9C, an organic solvent is supplied (discharged) as a replacement liquid from the central nozzle 12 toward the central region of the upper surface of the rotating substrate W (replacement liquid supplying step, replacement liquid discharging step). The central nozzle 12 is an example of a replacement liquid nozzle.

The organic solvent supplied from the central nozzle 12 to the upper surface of the substrate W spreads radially due to centrifugal force, and reaches the entire upper surface of the substrate W. As a result, the rinsing liquid on the substrate W is replaced with the organic solvent.
In the replacement step, the discharge of the organic solvent from the central nozzle 12 continues for a predetermined time, for example, 10 seconds. In the replacement step, the substrate W is rotated at a predetermined replacement rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not need to rotate at a constant rotation speed in the replacement step. For example, the spin motor 23 may rotate the substrate W at 300 rpm when the supply of the organic solvent begins, and accelerate the rotation of the substrate W until the rotation speed of the substrate W reaches 1500 rpm while the organic solvent is being supplied to the substrate W.

Next, a processing liquid supplying step (step S5) is performed to supply processing liquid to the upper surface of the substrate W. Specifically, the organic solvent valve 52 is closed, and the opposing member lifting unit 61 moves the opposing member 6 to the retracted position. With the opposing member 6 in the retracted position, the second nozzle moving unit 36 moves the second moving nozzle 10 to the processing position. The processing position of the second moving nozzle 10 is, for example, the central position. Then, the processing liquid valve 54 is opened. As a result, as shown in FIG. 9D, processing liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the substrate W in a rotating state (processing liquid supplying step, processing liquid discharging step). The processing liquid supplied to the upper surface of the substrate W spreads over the entire substrate W by centrifugal force. As a result, a liquid film 101 of the processing liquid (processing liquid film) is formed on the substrate W (processing liquid film forming step).

The supply of the processing liquid from the second moving nozzle 10 continues for a predetermined time, for example, 2 to 4 seconds. In the processing liquid supplying step, the substrate W is rotated at a predetermined processing liquid rotation speed, for example, 10 to 1500 rpm.
9E and 9F, a processing film forming step (step S8) is performed. In the processing film forming step, the processing liquid on the substrate W is solidified or hardened, and a processing film 100 (see FIG. 9F) that holds the object to be removed present on the substrate W is formed on the upper surface of the substrate W.

In the treatment film forming step, first, a treatment liquid thinning step (treatment liquid spin-off step) is performed to thin the thickness of the liquid film 101 of the treatment liquid on the substrate W. Specifically, the treatment liquid valve 54 is closed. This stops the supply of the treatment liquid to the substrate W. Then, the second nozzle movement unit 36 moves the second moving nozzle 10 to the home position.
9E, in the treatment liquid thinning step, the substrate W rotates with the supply of the treatment liquid to the upper surface of the substrate W stopped, so that a part of the treatment liquid is removed from the upper surface of the substrate W. This makes the thickness of the liquid film 101 on the substrate W appropriate. Even after the second moving nozzle 10 moves to the home position, the opposing member 6 is maintained at the retracted position.

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

In the treatment film formation step, after the treatment liquid thinning step, a treatment liquid solvent evaporation step is performed in which a part of the solvent is evaporated (volatilized) from the liquid film 101 of the treatment liquid. In the treatment liquid solvent evaporation step, the liquid film 101 on the substrate W is heated in order to evaporate a part of the solvent of the treatment liquid on the substrate W.
9F, the opposing member lifting unit 61 moves the opposing member 6 to the close position. The close position may be the lower position. The close position is a position where the distance from the upper surface of the substrate W to the opposing surface 6a is, for example, 1 mm.

Then, the gas valve 53 is opened, whereby 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 supplying step).
The gas is blown onto the liquid film 101 on the substrate W, thereby accelerating the evaporation (volatilization) of the solvent in the liquid film 101 (treatment liquid solvent evaporation step, treatment liquid solvent evaporation promotion step). This makes it possible to shorten the time required to form the treatment film 100. In the treatment film formation step, the central nozzle 12 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the treatment liquid.

Even after a portion of the processing liquid is removed from the substrate W by the liquid film 101 processing liquid thinning process, the opposing member 6 and the substrate W continue to rotate. Therefore, the centrifugal force caused by the rotation of the opposing member 6 and the substrate W acts on the gas discharged from the central nozzle 12. The centrifugal force forms an airflow in which the gas flows from the center side of the substrate W to the periphery side. Therefore, the removal of the gaseous solvent in contact with the liquid film 101 from the space between the opposing member 6 and the substrate W is promoted. This promotes the evaporation of the solvent in the liquid film 101. In this way, the opposing member 6 and the spin motor 23 function as an evaporation unit (evaporation promotion unit) that evaporates (volatilizes) the solvent in the processing liquid. The opposing member 6 may not rotate, and only the substrate W may rotate.

In addition, the heat medium valve 88 is opened. As a result, the heat medium is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the rotating substrate W (heat medium supplying step, heat medium discharging step). The heat medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W spreads radially due to centrifugal force, and reaches the entire lower surface of the substrate W.
The supply of the heat medium to the substrate W continues for a predetermined time, for example, 60 seconds. In the treatment liquid solvent evaporation step, the substrate W is rotated at a predetermined evaporation rotation speed, for example, 1000 rpm. By supplying the heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated through the substrate W. This promotes the evaporation (volatilization) of the solvent in the liquid film 101 (treatment liquid solvent evaporation step, treatment liquid solvent evaporation promotion step). Therefore, the time required for forming the treatment film 100 can be shortened. In the treatment film formation step as well, the lower surface nozzle 13 functions as an evaporation unit (evaporation promotion unit) that evaporates (volatilizes) the solvent in the treatment liquid.

The processing liquid is solidified or hardened by performing the processing liquid thinning step and the processing liquid solvent evaporation step, whereby a processing film 100 that holds the object to be removed is formed on the entire upper surface of the substrate W.
In this manner, the substrate rotation unit (spin motor 23), the opposing member rotation unit 62, the central nozzle 12 and the lower nozzle 13 constitute a treatment film formation unit that solidifies or hardens the treatment liquid to form a solid treatment film 100.

The treated film 100 can be formed quickly by blowing gas, rotating the substrate W, and heating the substrate W, but it is also possible to form the treated film 100 by blowing gas and rotating the substrate W. In other words, heating with a heat medium is not necessarily required to form the treated film 100. Therefore, the supply of a heat medium to the substrate W can be omitted.
In the treatment liquid solvent evaporation step, the substrate W is preferably heated so that the temperature of the substrate W is lower than the boiling point of the solvent. By heating the substrate W to a temperature lower than the boiling point of the solvent, the solvent can be prevented from evaporating completely, and an appropriate amount of the solvent can be left in the treatment film 100. This makes it easier for the stripping liquid to act on the treatment film 100 in the subsequent stripping step (step S6) compared to a case where no solvent remains in the treatment film 100.

Next, a peeling step (step S6) is performed to peel off the processing film 100. Specifically, the heat medium valve 88 is closed. This stops the supply of heat medium to the lower surface of the substrate W. In addition, the gas valve 53 is closed. This stops the supply of gas to the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W.
Then, the opposing member lifting unit 61 moves the opposing member 6 to the retracted position. With the opposing member 6 in the retracted position, the third nozzle moving unit 37 moves the third moving nozzle 11 to the processing position. The processing position of the third moving nozzle 11 is, for example, the central position.

Then, with the third moving nozzle 11 in the processing position, the upper remover valve 55 is opened. As a result, as shown in FIG. 9G, the remover liquid is supplied (discharged) from the third moving nozzle 11 toward the central region of the upper surface of the rotating substrate W (upper remover liquid supply process, upper remover liquid discharge process). The remover liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W due to centrifugal force. As a result, the processing film 100 on the upper surface of the substrate W is peeled off and discharged outside the substrate W together with the remover liquid.

At the same time that the upper remover liquid valve 55 is opened, the lower remover liquid valve 87 is opened. As a result, as shown in Fig. 9G, the remover liquid is supplied (discharged) from the lower nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower remover liquid supplying step, lower remover liquid discharging step). The remover liquid supplied to the lower surface of the substrate W spreads over the entire lower surface of the substrate W due to centrifugal force.
The supply of the stripping liquid to the upper and lower surfaces of the substrate W continues for a predetermined time, for example, 60 seconds. In the stripping step, the substrate W is rotated at a predetermined stripping rotation speed, for example, 800 rpm.

Here, the processing liquid supplied to the upper surface of the substrate W in the processing liquid supply process (step S5) shown in Figure 9D runs along the periphery of the substrate W and adheres to the lower surface of the substrate W, and the processing liquid adhered to the lower surface of the substrate W may solidify or harden to form a solid.
9G, while the stripping liquid is being supplied to the upper surface of the substrate W in the stripping process (step S6), the stripping liquid is supplied (discharged) from the lower surface nozzle 13 to the lower surface of the substrate W. Therefore, even if a solid of the processing liquid is formed on the lower surface of the substrate W, the solid can be stripped and removed from the lower surface of the substrate W.

After the stripping process (step S6), a second rinsing process (step S7) is performed in which the stripping liquid is rinsed off from the substrate W with a rinsing liquid. Specifically, the upper stripping liquid valve 55 and the lower stripping liquid valve 87 are closed. This stops the supply of stripping liquid to the upper and lower surfaces of the substrate W. Then, the third nozzle movement unit 37 moves the third moving nozzle 11 to the home position. Then, as shown in FIG. 9H, the opposing member lifting unit 61 moves the opposing member 6 to the processing position.

Then, with the opposing member 6 in the processing position, the upper rinse liquid valve 51 is opened. As a result, as shown in FIG. 9H, rinse liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the rotating substrate W (upper rinse liquid supply process, upper rinse liquid discharge process). The rinse liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W due to centrifugal force. As a result, the stripping liquid adhering to the upper surface of the substrate W is washed away by the rinse liquid (rinsing process).

At the same time that the upper rinse liquid valve 51 is opened, the lower rinse liquid valve 86 is opened. As a result, as shown in FIG. 9H, rinse liquid is supplied (discharged) from the lower nozzle 13 toward the central region of the lower surface of the rotating substrate W (lower rinse liquid supply process, lower rinse liquid discharge process). As a result, the stripping liquid adhering to the lower surface of the substrate W is washed away with the rinse liquid.

The supply of the rinsing liquid to the upper and lower surfaces of the substrate W continues for a predetermined time, for example, 30 seconds. In the second rinsing step, the substrate W is rotated at a predetermined second rinsing rotation speed, for example, 800 rpm.
Next, a residue removal step (step S8) is performed. In the residue removal step, residues of the processing film 100 remaining on the upper surface of the substrate W after the peeling step are removed by an organic solvent (e.g., IPA) as a residue removal liquid. Specifically, the upper rinse liquid valve 51 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, with the opposing member 6 in the processing position, the organic solvent valve 52 is opened. As a result, as shown in Fig. 9I, an organic solvent as a residue removing liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the rotating substrate W (residue removing liquid supplying step, residue removing liquid discharging step).
The organic solvent supplied from the central nozzle 12 to the upper surface of the substrate W spreads radially due to centrifugal force, and permeates the entire upper surface of the substrate W. After dissolving the residue of the processing film remaining on the upper surface of the substrate W, the organic solvent is discharged from the periphery of the upper surface of the substrate W. The central nozzle 12 is an example of a residue removal liquid nozzle.

In the residue removal step, the organic solvent is continuously discharged from the central nozzle 12 for a predetermined time, for example, 30 seconds. In the residue removal step, the substrate W is rotated at a predetermined residue removal rotation speed, for example, 300 rpm.
Next, a spin dry process (step S10) is performed in which the substrate W is rotated at high speed to dry the upper surface of the substrate W.

Specifically, the organic solvent valve 52 is closed. This stops the supply of organic solvent to the upper surface of the substrate W. Then, the opposing member lifting unit 61 moves the opposing member 6 to a drying position below the processing position. When the opposing member 6 is located at the drying position, the distance between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 53 is opened. This supplies gas to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6.

Then, the spin motor 23 accelerates the rotation of the substrate W, rotating it at high speed. In the spin dry process, the substrate W is rotated at a drying speed, for example, 1500 rpm. The spin dry process is performed for a predetermined time, for example, 30 seconds. As a result, a large centrifugal force acts on the organic solvent on the substrate W, and the organic solvent on the substrate W is scattered around the substrate W. In the spin dry process, evaporation of the organic solvent is promoted by supplying gas to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

Then, the spin motor 23 stops the rotation of the substrate W. The guard lifting unit 74 moves the first guard 71A and the second guard 71B to the lower position. The gas valve 53 is closed. Then, the opposing member lifting unit 61 moves the opposing member 6 to the upper position.
The transport robot CR enters the processing unit 2, scoops up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S11). The substrate W is handed over from the transport robot CR to the transport robot IR, and is stored in the carrier C by the transport robot IR.

<Peeling of treated film>
10A to 10C, the removal of the treated film 100 will be described in detail. FIGS. 10A to 10C are schematic views for explaining the state in which the treated film 100 is peeled off from the substrate W.
10A, the processing film 100 holds the object to be removed 103 adhering to a surface layer 150 of the substrate W. The processing film 100 has a highly soluble solid 110 (a highly soluble component in a solid state) and a low solubility solid 111 (a low solubility component in a solid state). The highly soluble solid 110 and the low solubility solid 111 are formed by evaporation of at least a part of the solvent contained in the processing liquid.

The treated film 100 contains a mixture of a highly soluble solid 110 and a low solubility solid 111. Strictly speaking, the treated film 100 does not have the highly soluble solid 110 and the low solubility solid 111 uniformly distributed throughout the treated film 100. The treated film 100 has a portion where the highly soluble solid 110 is unevenly distributed and a portion where the low solubility solid 111 is unevenly distributed.
10B , the highly soluble solid 110 is dissolved by the stripping solution. That is, the treatment film 100 is partially dissolved (dissolving step, partial dissolving step). By dissolving the highly soluble solid 110, through holes 102 are formed in the portions of the treatment film 100 where the highly soluble solid 110 is unevenly distributed (through hole forming step).

The through-holes 102 are particularly likely to be formed in portions where the highly soluble solid 110 extends in the thickness direction T of the treatment film 100. The through-holes 102 have a diameter of, for example, several nm in plan view. The through-holes 102 are gaps formed in the treatment film 100 by dissolving the highly soluble solid 110.
Here, when an appropriate amount of solvent remains in the treatment film 100, the remover solution dissolves in the solvent remaining in the treatment film 100 and partially dissolves the treatment film 100. More specifically, the remover solution dissolves in the solvent remaining in the highly soluble solid 110 in the treatment film 100 and dissolves the highly soluble solid 110 in the treatment film 100 to form the through-holes 102. Therefore, the remover solution easily enters the treatment film 100 (dissolution and entry process).

The stripping liquid passes through the through holes 102, reaches the interface between the processing film 100 and the substrate W, and acts on this interface. The stripping liquid acts on the interface between the processing film 100 and the substrate W means that the stripping liquid slightly dissolves the portion of the processing film 100 in contact with the substrate W, thereby stripping the processing film 100 from the substrate W.
The solubility of the low-solubility component in the stripping solution is low, and the low-solubility solid 111 is hardly dissolved by the stripping solution. Therefore, the low-solubility solid 111 is only slightly dissolved near its surface by the stripping solution. Therefore, the stripping solution that has reached the vicinity of the upper surface of the substrate W via the through hole 102 slightly dissolves the portion of the low-solubility solid 111 near the upper surface of the substrate W. As a result, as shown in the enlarged view of FIG. 10B, the stripping solution gradually dissolves the low-solubility solid 111 near the upper surface of the substrate W and enters the gap G1 between the processing film 100 and the upper surface of the substrate W (stripping solution entry process).

Then, for example, the processing film 100 splits starting from the periphery of the through hole 102 to become film pieces 105, and as shown in FIG. 10C, the film pieces 105 of the processing film 100 are peeled off from the substrate W while holding the object to be removed 103 (processing film splitting process, processing film peeling process).
Then, by continuing to supply the treatment film remover liquid, the treatment film 100 that has become the film pieces 105 is washed away by the remover liquid while still holding the object to be removed 103. In other words, the film pieces 105 holding the object to be removed 103 are pushed out of the substrate W and removed from the upper surface of the substrate W (treatment film removing step, removal object removing step). This allows the upper surface of the substrate W to be cleaned satisfactorily.

Summary of the embodiment
The strength of the peeling action (peeling force) of the stripping liquid to peel the treatment film 100 from the substrate W varies depending on the surface condition of the upper surface of the substrate W. Specifically, the higher the hydrophilicity of the upper surface of the substrate W, the easier it is for the treatment film 100 to be peeled off by the stripping liquid. More specifically, the higher the hydrophilicity of the upper surface of the substrate W, the higher the wettability (affinity) of the stripping liquid to the substrate W, and the easier it is for the stripping liquid to penetrate between the substrate W and the treatment film 100. In other words, the higher the hydrophilicity of the upper surface of the substrate W, the easier it is for the treatment film 100 to be peeled off from the upper surface of the substrate W.

According to this embodiment, the treated film 100 is formed on the hydrophilized upper surface of the substrate W, and the treated film 100 is peeled off by the peeling liquid. Therefore, the treated film 100 can be effectively peeled off from the substrate W.
When the processing film 100 is peeled off, the peeling liquid forms a through hole 102 in the processing film 100. Therefore, the peeling liquid can reach the interface between the processing film 100 and the substrate W through the through hole 102. This allows the peeling liquid to enter between the portion of the processing film 100 surrounding the through hole 102 and the upper surface of the substrate W. Therefore, compared to a configuration in which the peeling liquid is made to penetrate into the processing film 100 without forming the through hole 102 in the processing film 100 and the peeling liquid reaches the interface between the processing film 100 and the substrate W, the peeling liquid can be made to act quickly on the interface between the processing film 100 and the substrate W. Although the processing film 100 is partially dissolved by the peeling liquid to form the through hole 102, the remaining portion is maintained in a solid state. Therefore, the processing film 100 in a state in which the removal target 103 is held can be effectively peeled off from the upper surface of the substrate W.

In this way, the stripping liquid can be quickly applied to the interface between the processing film 100 and the substrate W while maintaining most of the processing film 100 in a solid state, so that the processing film 100 that is still holding the object to be removed 103 can be effectively stripped from the substrate W.
According to the present embodiment, the solubility of the highly soluble component in the stripping liquid is higher than the solubility of the low solubility component in the stripping liquid, so that the highly soluble solid 110 dissolves more easily in the stripping liquid than the low solubility solid 111.

Therefore, by supplying a stripping liquid to the upper surface of the substrate W and dissolving the highly soluble solid 110 in the stripping liquid, the through-holes 102 are formed in the treatment film 100. On the other hand, the low-solubility solid 111 is not dissolved in the stripping liquid and remains in a solid state.
Therefore, the highly soluble solid 110 is dissolved in the stripping liquid, while the low solubility solid 111 is maintained in a solid state without being dissolved in the stripping liquid. Therefore, the stripping liquid passes through the through hole 102 formed by the dissolution of the highly soluble solid 110 and reaches the interface between the substrate W and the low solubility solid 111.

Therefore, while the object 103 to be removed is held by the low-solubility solid 111, the stripping liquid can be applied to the interface between the low-solubility solid 111 and the substrate W. As a result, the processing film 100 can be quickly stripped from the substrate W, and the object 103 to be removed together with the processing film 100 can be efficiently removed from the substrate W.
Moreover, according to the present embodiment, the stripping liquid can effectively enter between the substrate W and the treatment film 100 while slightly dissolving the low-solubility solid 111 contained in the treatment film 100 in the stripping liquid. Therefore, the treatment film 100 can be effectively stripped.

According to this embodiment, the upper surface of the substrate W is hydrophilized by supplying a hydrophilizing liquid to the upper surface of the substrate W. By supplying the hydrophilizing liquid to the upper surface of the substrate W, the hydrophilizing liquid spreads over the upper surface of the substrate W, and the hydrophilizing liquid can be distributed over the entire upper surface of the substrate W. Therefore, the entire upper surface of the substrate W can be made hydrophilic evenly. Since the entire upper surface of the substrate W has been made hydrophilic, in the subsequent peeling process, the peeling liquid can easily act on the interface between the treatment film 100 and the substrate W over the entire upper surface of the substrate W. Therefore, the treatment film 100 can be peeled off evenly from the entire upper surface of the substrate W.

According to this embodiment, the upper surface of the substrate W is made hydrophilic so that the contact angle of pure water with respect to the upper surface of the substrate W is smaller than 41.7°. This allows the stripping liquid to act sufficiently on the interface between the substrate W and the processing film 100. This allows the processing film 100, which is holding the object to be removed 103, to be effectively stripped from the substrate W.
According to this embodiment, the contact angle of pure water with the processing film 100 is greater than 52° and smaller than 61°. If the contact angle of pure water with the processing film 100 is within this range, the affinity between the stripping liquid and the processing film 100 is sufficiently high. Therefore, the stripping liquid can be sufficiently introduced between the substrate W and the processing film 100, so that the processing film 100 can be effectively stripped from the substrate W.

According to this embodiment, at least one of Si, SiN, _SiO2 , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the upper surface of the substrate W, so that the upper surface of the substrate W can be made hydrophilic by the hydrophilization step. For example, when the surface layer 150 of the substrate W includes a TiN layer (barrier layer 153), if an oxidizing liquid is used as the hydrophilizing liquid, an oxide film 171 is formed on the surface of the TiN layer, thereby making the upper surface of the substrate W hydrophilic. By making the upper surface of the substrate W hydrophilic in advance in this manner, the processing film 100 can be effectively peeled off from the substrate W.

<Another Example of Substrate Processing>
FIG. 11 is a flow chart for explaining another example of substrate processing by the substrate processing apparatus 1. The substrate processing shown in FIG. 11 differs from the substrate processing shown in FIG. 8 in that the first rinse step (step S3) and the replacement step (step S4) are omitted. If the hydrophilizing liquid used in the hydrophilizing step is a liquid compatible with the processing liquid, as shown in FIG. 11, the first rinse step (step S3) and the replacement step (step S4) can be omitted. It is preferable that the hydrophilizing liquid is the same liquid as the solvent contained in the processing liquid. The same liquid means that it is composed of the same substance. An example of a hydrophilizing liquid compatible with the processing liquid is an organic solvent such as IPA.

<Treatment film peeling experiment>
The following describes the results of a treatment film peeling experiment conducted to investigate the relationship between the contact angle of pure water on a substrate and whether or not the treatment film can be peeled off. Fig. 12A is a schematic diagram for explaining the procedure for measuring the contact angle of pure water on the surface of an experimental substrate 200. Fig. 12B is a schematic diagram for explaining the procedure for peeling off a treatment film from an experimental substrate 200.

In this experiment, a substrate having any of Si (bare silicon: Bare-Si), SiN, SiO2, W, TiN, Co, Cu, Ru, and amorphous carbon (a-C) exposed on its surface was used as the experimental substrate 200, and any of hydrochloric acid, SC1, hydrofluoric acid, SPM, and IPA was used as the hydrophilization liquid.
The experimental substrate 200 used in this experiment was a small square substrate with each side measuring 3 cm in plan view.

The mass percent concentration of hydrogen chloride in the hydrochloric acid used in this experiment was 0.4%. SC1 used in this experiment was a mixture of ammonia water with a mass percent concentration of ammonia of 0.4% and hydrogen peroxide water with a mass percent concentration of hydrogen peroxide of 3.5%.
The mass percent concentration of hydrogen fluoride in the hydrofluoric acid used in this experiment was 0.5%. The SPM used in this experiment was a mixture of heated dilute sulfuric acid with a mass percent concentration of sulfuric acid of 64.0% and hydrogen peroxide solution with a mass percent concentration of hydrogen peroxide of 10.0%. The pure water used in this experiment was DIW.

The experiments were carried out for various combinations of substrate and hydrophilizing liquid.
In order to measure the contact angle of pure water with the experimental substrate 200, the experimental substrate 200 was immersed in a hydrophilizing liquid as shown in Fig. 12A. Thereafter, although not shown, the experimental substrate 200 was washed with DIW to remove the hydrophilizing liquid from the experimental substrate 200. A droplet 202 of pure water (DIW) was formed on the hydrophilized experimental substrate 200, and the contact angle θ1 of the droplet 202 was measured.

In order to check whether the treated film 201 could be peeled off from the experimental substrate 200, as shown in FIG. 12B, the untreated experimental substrate 200 was immersed in a hydrophilizing liquid. After that, the experimental substrate 200 was washed with pure water and/or IPA as necessary, although not shown. After that, the experimental substrate 200 was rotated at 10 rpm for about 2 seconds while supplying the treatment liquid to the experimental substrate 200, and then rotated at 1500 rpm for 30 seconds to form the treated film 201. While rotating the experimental substrate 200 on which the treated film 201 was formed at 800 rpm, a stripping liquid was supplied to the experimental substrate 200. The surface of the experimental substrate 200 was observed both before and after the supply of the treatment liquid, and it was determined whether the treated film could be peeled off. Ammonia water with a mass percent concentration of 0.4% was used as the stripping liquid.

The treatment liquid used in the treatment film peeling experiment contains, as solutes, at least one low solubility component selected from the low solubility components described below and at least one high solubility component selected from the high solubility components described below. The treatment liquid used in the treatment film peeling experiment is treatment liquid PL4 used in the contact angle measurement experiment described below with reference to Figures 14 and 15.

Fig. 13 is a table showing the contact angle θ1 of pure water with respect to the surface of the experimental substrate 200, and the suitability of the treatment film 201 with the stripping solution. Fig. 13 is a table summarizing the results of the treatment film stripping experiment.
The table shown in FIG. 13 includes columns for "substrate surface,""hydrophilizingliquid,""contact angle of pure water (°)," and "peeling of treatment film."

Each line in "Substrate surface" lists the name of the material exposed from the surface of the experimental substrate 200. Each line in "Hydrophilizaton liquid" lists the name of the material of the hydrophilic liquid used to hydrophilize the experimental substrate 200. A line with "-" in "Hydrophilizaton liquid" indicates that the treatment film peeling experiment was performed on a substrate that had not been hydrophilized.
Each line of "Contact angle of pure water (°)" indicates the contact angle θ1 of pure water with respect to the experimental substrate 200 which has been made hydrophilic using the hydrophilizing liquid shown in the same line.

Each line of "peeling of treated film" indicates whether the treated film 201 was peeled off by the peeling liquid from the experimental substrate 200 that was hydrophilized using the hydrophilization liquid shown in the same line. "OK" means that the treated film 201 was sufficiently peeled off, and "NG" means that the peeling of the treated film 201 was insufficient.
For example, the first row of the table in Figure 13 shows that after the experimental substrate 200, which has exposed SiN on its surface, is made hydrophilic with HCl, the contact angle θ1 of pure water with the experimental substrate 200 is 4.8°, and that the treatment film 201 is sufficiently peeled off from the experimental substrate 200 by the peeling solution.

As shown in FIG. 13, when the contact angle θ1 of pure water was 41.7° or more, the treatment film 201 was not sufficiently peeled off.
As shown in Fig. 13, even if the material exposed from the surface of the experimental substrate 200 is the same, if the hydrophilizing liquid is different, the contact angle θ1 of pure water with respect to the surface of the experimental substrate 200 is different. For example, when the experimental substrate 200 with TiN exposed from the surface is hydrophilized using HF as the hydrophilizing liquid, the contact angle θ1 of pure water is 15.2°, and the treatment film 201 is sufficiently removed. When the experimental substrate 200 with TiN exposed from the surface is hydrophilized using SC1 as the hydrophilizing liquid, the contact angle θ1 of pure water is 28.3°, and the treatment film 201 is sufficiently removed. On the other hand, when the experimental substrate 200 with TiN exposed from the surface is hydrophilized using IPA as the hydrophilizing liquid, the contact angle θ1 of pure water is 41.7°, and the treatment film 201 is not sufficiently removed.

Therefore, it is presumed that the use of an oxidizing liquid as the hydrophilic liquid can enhance the hydrophilicity of the substrate surface more than the use of an organic solvent as the hydrophilic liquid, for the following reasons.
When an organic solvent is used as the hydrophilizing liquid, the hydrophobic organic matter adhering to the surface of the substrate is dissolved in the organic solvent, and the surface of the substrate is made hydrophilic. Depending on the type of organic matter adhering to the surface of the substrate, some organic matter may not be dissolved in the organic solvent. Therefore, not all organic matter is removed.

On the other hand, when an oxidizing liquid is used as the hydrophilizing liquid, the portion near the surface of the substrate is oxidized to form an oxide film on the surface of the substrate, and therefore the hydrophilicity of the surface of the substrate can be efficiently increased regardless of the type of organic matter attached to the surface of the substrate.
In addition, when hydrophilization was not performed, the contact angle of pure water with the experimental substrate 200 with TiN exposed from the surface was 59.6°. Therefore, the experimental substrate 200 with TiN exposed from the surface was hydrophilized regardless of whether the hydrophilization liquid IPA, HF, or SC1 was used.

<Contact angle measurement experiment for treated film>
Next, the results of a contact angle measurement experiment in which the contact angle of pure water with respect to a treatment film formed on the surface of an experimental substrate was measured will be described. Fig. 14 is a schematic diagram for explaining the procedure for measuring the contact angle of pure water with respect to the surface of a treatment film.
In this experiment, a substrate with exposed Si (bare silicon: Bare-Si) on the surface was used as the experimental substrate 203, and IPA was used as the hydrophilizing liquid. Four types of treatment liquids PL1 to PL4 were used as the treatment liquids. Each of the treatment liquids PL1 to PL4 contains IPA as a solvent. Each of the treatment liquids PL1 to PL4 contains, as solutes, at least one type of low solubility component selected from the low solubility components described below, and at least one type of high solubility component selected from the high solubility components described below. The low solubility components contained in the treatment liquids PL1 to PL4 are the same. The high solubility components contained in the treatment liquids PL1 to PL4 are different substances from each other.

As shown in FIG. 15, the experimental substrate 203 was immersed in IPA as a hydrophilic liquid. After that, the experimental substrate 203 was cleaned using DIW (not shown). Then, a treatment liquid was dropped onto the surface of the experimental substrate 203. The solvent in the treatment liquid was then evaporated to form a treatment film 204 on the surface of the experimental substrate 203. Further, a droplet 205 of pure water (DIW) was formed on the treatment film 204 formed on the experimental substrate 203, and the contact angle θ2 of the droplet 205 was measured.

FIG. 15 is a table showing the contact angle θ2 of pure water with respect to the surface of the treatment film 204 and whether the treatment film 204 can be removed by the remover.
The table shown in FIG. 15 has columns for "treatment liquid" and "contact angle of pure water (°)". Each row of "treatment liquid" indicates which of the treatment liquids PL1 to PL4 was used to form the treatment film 204. Each row of "contact angle of pure water (°)" indicates the contact angle θ2 of pure water with respect to the treatment film 204 formed using the treatment liquid shown in the same row. The contact angle θ2 of pure water with respect to the treatment film 204 was within the range of 52° to 61°. Therefore, it is presumed that the contact angle θ2 of pure water with respect to the treatment film 204 allows the treatment film formed on the hydrophilized substrate to be effectively peeled off using a peeling liquid.

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

When a polymer has multiple types of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When a polymer or resin is shown by a structural formula, n, m, etc. shown in parentheses indicate the number of repeats.
<Low solubility components>
The (A) low solubility component includes at least one of novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonates, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, the (A) low solubility component may include at least one of novolac, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonates, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, the (A) low solubility component may include at least one of novolac, polyhydroxystyrene, polycarbonates, and copolymers of combinations thereof. The novolac may be a phenol novolac.

The treatment liquid may contain one or a combination of two or more of the above preferred examples as the low-solubility component (A). For example, the low-solubility component (A) may contain both novolak and polyhydroxystyrene.
In a preferred embodiment, the low-solubility component (A) is dried to form a film, and the film is peeled off while retaining the object to be removed without being dissolved in the stripping solution for the most part. However, an embodiment in which only a small part of the low-solubility component (A) is dissolved in the stripping solution is acceptable.

Preferably, (A) the low solubility component is free of fluorine and/or silicon, more preferably free of both.
The copolymerization is preferably random copolymerization or block copolymerization.
Although there is no intention to limit the scope of the invention, specific examples of the low-solubility component (A) include the compounds shown in Chemical Formula 1 to Chemical Formula 7 below.

（アスタリスク＊は、隣接した構成単位への結合を示す。）

(An asterisk * indicates a bond to an adjacent building block.)

（ＲはＣ_１～４アルキル等の置換基を意味する。アスタリスク＊は、隣接した構成単位への結合を示す。）

(R represents a substituent such as _C1-4 alkyl. An asterisk * indicates a bond to an adjacent structural unit.)

（Ｍｅは、メチル基を意味する。アスタリスク＊は、隣接した構成単位への結合を示す。）
（Ａ）低溶解性成分の重量平均分子量（Ｍｗ）は好ましくは１５０～５００，０００であり、より好ましくは３００～３００，０００であり、さらに好ましくは５００～１００，０００であり、よりさらに好ましくは１，０００～５０，０００である。

(Me means a methyl group. The asterisk * indicates a bond to the adjacent building block.)
The weight average molecular weight (Mw) of the low-solubility component (A) is preferably 150 to 500,000, more preferably 300 to 300,000, even more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

The low-solubility component (A) can be obtained by synthesis. It can also be purchased. When purchasing, examples of suppliers include the following. It is also possible for the supplier to synthesize the (A) polymer.
Novolac: Showa Kasei Co., Ltd., Asahi Yukizai Co., Ltd., Gun-ei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.
Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.
Polyacrylic acid derivative: Nippon Shokubai Polycarbonate: Sigma-Aldrich Polymethacrylic acid derivative: Sigma-Aldrich Compared to the total mass of the treatment liquid, the low solubility component (A) is 0.1 to 50 mass%, preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, and even more preferably 1 to 10 mass%. In other words, the total mass of the treatment liquid is taken as 100 mass%, and based on this, the low solubility component (A) is 0.1 to 50 mass%. In other words, "compared to" can be rephrased as "based on". The same applies hereinafter unless otherwise specified.

<Highly soluble components>
The (B) highly soluble component is (B') a crack-accelerating component. The (B') crack-accelerating component contains a hydrocarbon and further contains a hydroxyl group (-OH) and/or a carbonyl group (-C(=O)-). When the (B') crack-accelerating component is a polymer, one of the constituent units contains a hydrocarbon on a unit basis 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 enone, and carboxylic acid is preferred.

Without intending to limit the scope of the rights and not being bound by theory, it is believed that when the treatment liquid is dried to form a treatment film on the substrate and the stripping liquid strips the treatment film, the (B) highly soluble component produces a portion that triggers the treatment film to peel off. For this reason, it is preferable that the (B) highly soluble component has a higher solubility in the stripping liquid than the (A) low solubility component. Examples of the (B') crack-promoting component that contains a ketone as a carbonyl group include cyclic hydrocarbons. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

In a more specific embodiment, the highly soluble component (B) is represented by at least one of the following (B-1), (B-2), and (B-3).
(B-1) is a compound containing 1 to 6 (preferably 1 to 4) structural units represented by the following chemical formula 8, and each structural unit is linked by a linking group (linker L ₁ ). Here, the linker L ₁ may be a single bond or a C _1-6 alkylene. The C _1-6 alkylene links the structural units as a linker, and is not limited to a divalent group. It is preferably divalent to tetravalent. The C _1-6 alkylene may be either linear or branched.

Ｃｙ_１はＣ_５～３０の炭化水素環であり、好ましくはフェニル、シクロヘキサンまたはナフチルであり、より好ましくはフェニルである。好適な態様として、リンカーＬ_１は複数のＣｙ_１を連結する。

_Cy1 is a _C5-30 hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. In a preferred embodiment, the linker _L1 connects a plurality of _Cy1's .

Each R ₁ is independently a C _1-5 alkyl, preferably methyl, ethyl, propyl, or butyl. The C _1-5 alkyl may be linear or branched.
n _b1 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. n _b1′ is 0, 1, 2, 3 or 4, and preferably 0, 1 or 2.
The following Chemical Formula 9 is a chemical formula in which the structural unit described in Chemical Formula 8 is expressed using a linker L _9. The linker L ₉ is preferably a single bond, methylene, ethylene, or propylene.

権利範囲を限定する意図はないが、（Ｂ－１）の好適例として、２，２－ビス（４－ヒドロキシフェニル）プロパン、２，２’－メチレンビス（４－メチルフェノール）、２，６－ビス［（２-ヒドロキシ－５－メチルフェニル）メチル］－４－メチルフェノール、１，３－シクロヘキサンジオール、４，４’－ジヒドロキシビフェニル、２，６－ナフタレンジオール、２，５－ジ－ｔｅｒｔ－ブチルヒドロキノン、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン、が挙げられる。これらは、重合や縮合によって得てもよい。

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

As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following chemical formula 10 will be described. In (B-1), this compound has three structural units of chemical formula 8, and the structural units are linked by a linker L ₁ (methylene). _{n b1} =n _b1' =1, and R ₁ is methyl.

（Ｂ－２）は下記化学式１１で表される。

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

Ｒ_２１、Ｒ_２２、Ｒ_２３、およびＲ_２４は、それぞれ独立に水素またはＣ_１～５のアルキルであり、好ましくは水素、メチル、エチル、ｔ－ブチル、またはイソプロピルであり、より好ましくは水素、メチル、またはエチルであり、さらに好ましくはメチルまたはエチルである。

R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently hydrogen or C _1-5 alkyl, preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

The linkers L ₂₁ and L ₂₂ are each independently a C _1-20 alkylene, a C _1-20 cycloalkylene, a C _2-4 alkenylene, a C _2-4 alkynylene, or a C _6-20 arylene. These groups may be substituted with a C _1-5 alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. The linkers L ₂₁ and L ₂₂ are preferably a C _2-4 alkylene, acetylene (C ₂ alkynylene), or phenylene, more preferably a C _2-4 alkylene or acetylene, and even more preferably acetylene.

n _b2 is 0, 1 or 2, preferably 0 or 1, and more preferably 0.
Although there is no intention to limit the scope of the invention, suitable examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, suitable examples of (B-2) include 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.

(B-3) is a polymer containing a structural unit represented by the following chemical formula 12, and has a weight average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

ここで、Ｒ_２５は－Ｈ、－ＣＨ_３、または－ＣＯＯＨであり、好ましくは－Ｈ、または－ＣＯＯＨである。１つの（Ｂ－３）ポリマーが、それぞれ化学式１２で表される２種以上の構成単位を含んでなることも許容される。

Here, R ₂₅ is —H, —CH ₃ , or —COOH, and preferably —H or —COOH. It is also acceptable for one (B-3) polymer to contain two or more types of constitutional units each represented by Chemical Formula 12.

Although there is no intention to limit the scope of the invention, preferred examples of the (B-3) polymer include polymers of acrylic acid, maleic acid, and combinations thereof. More preferred examples include polyacrylic acid and maleic acid-acrylic acid copolymers.
In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

As an example, a maleic acid acrylic acid copolymer shown in the following chemical formula 13 will be described. This copolymer is included in (B-3) and has two types of structural units shown in chemical formula 12, where R ₂₅ in one structural unit is -H and R ₂₅ in the other structural unit is -COOH.

言うまでもないが、処理液は（Ｂ）高溶解性成分として、上記の好適例を１または２以上組み合わせて含んでも良い。例えば、（Ｂ）高溶解性成分は２，２－ビス（４－ヒドロキシフェニル）プロパンと３，６－ジメチル－４－オクチン－３,６－ジオールの双方を含んでも良い。

Needless to say, the treatment liquid may contain one or a combination of two or more of the above preferred examples as the highly soluble component (B). For example, the highly soluble component (B) may contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

The (B) highly soluble component may have a molecular weight of 80 to 10,000. The (B) highly soluble component preferably has a molecular weight of 90 to 5000, more preferably 100 to 3000. When the (B) highly soluble component is a resin, a polymer, or a polymer, the molecular weight is expressed as a weight average molecular weight (Mw).
(B) Highly soluble components can be obtained either synthetically or commercially, and are available from Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

In the treatment liquid, the amount of the highly soluble component (B) is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, based on the mass of the low solubility component (A). In the treatment liquid, the amount of the highly soluble component (B) is further preferably 1 to 30% by mass, based on the mass of the low solubility component (A).
<Solvent>
The (C) solvent preferably contains an organic solvent. The (C) solvent may be volatile. Volatile means that it is more volatile than water. For example, the boiling point of the (C) solvent at 1 atmosphere is preferably 50 to 250°C. The boiling point of the solvent at 1 atmosphere is more preferably 50 to 200°C, and even more preferably 60 to 170°C. The boiling point of the solvent at 1 atmosphere is even more preferably 70 to 150°C. The (C) solvent is also allowed to contain a small amount of pure water. The amount of pure water contained in the (C) solvent is preferably 30% by mass or less compared to the entire (C) solvent. The amount of pure water contained in the solvent is more preferably 20% by mass or less, and even more preferably 10% by mass or less. The amount of pure water contained in the solvent is even more preferably 5% by mass or less. A preferred embodiment is also one in which the solvent does not contain pure water (0% by mass). The pure water is preferably DIW.

Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactate esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These organic solvents can be used alone or in combination of two 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. When two types of organic solvents are combined, the volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.
The content of the (C) solvent is 0.1 to 99.9% by mass relative to the total mass of the treatment liquid. The content of the (C) solvent is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass relative to the total mass of the treatment liquid. The content of the (C) solvent is further preferably 80 to 99% by mass, even more preferably 85 to 99% by mass relative to the total mass of the treatment liquid.

<Other additives>
The treatment liquid of the present invention may further contain (D) other additives. In one embodiment of the present invention, (D) other additives include a surfactant, an acid, a base, an antibacterial agent, a bactericide, a preservative, or an antifungal agent (preferably a surfactant), and may contain any combination of these.

In one embodiment of the present invention, the amount of (D) other additives (if multiple additives are present, their sum) is 0 to 100% by mass (preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass) compared to the mass of (A) low-solubility component in the treatment liquid. It is also one embodiment of the present invention that the treatment liquid does not contain (D) other additives (0% by mass).

<Corrosion prevention ingredients>
(F) Examples of corrosion inhibitors include, in addition to BTA, uric acid, caffeine, buterin, adenine, glyoxylic acid, glucose, fructose, and mannose.
<Other embodiments>
The present invention is not limited to the above-described embodiment, and can be embodied in other forms.

For example, the upper surface of the substrate W may be made hydrophilic by a method such as UV irradiation, plasma treatment, or oxygen ashing, that is, a method other than treatment with a hydrophilizing liquid.
In the above-described embodiment, the same organic solvent is used as the replacement liquid and the residue removal liquid. However, if a nozzle for discharging the organic solvent as the replacement liquid and a nozzle for discharging the residue removal liquid are provided, the organic solvent used as the replacement liquid and the organic solvent used as the residue removal liquid can be different organic solvents. For example, methanol can be used as the replacement liquid, and IPA can be used as the residue removal liquid.

In the above-described embodiment, the treatment film 100 is partially dissolved by the stripping liquid to form a through hole 102, and the stripping liquid reaches the interface between the treatment film 100 and the substrate W through this through hole 102. However, it is not necessary that a visible through hole 102 is formed, and the stripping liquid may reach the interface between the treatment film 100 and the substrate W through a gap formed in the treatment film 100 by dissolving the highly soluble solid 110 in the treatment film 100 with the stripping liquid.

The nozzles that eject each processing fluid are not limited to those in the above-described embodiment. For example, in the above-described embodiment, the processing liquid, hydrophilization liquid, and stripping liquid are ejected from the moving nozzle toward the top surface of the substrate W, and the rinsing liquid, organic solvent, and gas are ejected from the fixed nozzle (central nozzle 12) toward the top surface of the substrate W. However, the rinsing liquid, organic solvent, and gas may be ejected from the moving nozzle, or the processing liquid, hydrophilization liquid, and stripping liquid may be ejected from the central nozzle 12 in addition to the rinsing liquid, organic solvent, and gas.

If all of the processing fluids are discharged from movable nozzles or fixed nozzles arranged outside the substrate W in a plan view, the opposing member 6 does not need to be provided.
In this specification, when numerical ranges are indicated using "to" or "-", they include both endpoints and have the same units, unless otherwise specified and limited.

Various other modifications may be made within the scope of the claims.

1: Substrate processing apparatus 3: Controller 9: First moving nozzle (hydrophilization liquid supply unit)
10: Second moving nozzle (treatment liquid supply unit)
11: Third moving nozzle (stripping liquid supply unit)
12: Central nozzle (treatment film forming unit)
13: Lower nozzle (treatment film forming unit)
21: Spin base (substrate holding unit)
23: Spin motor (treatment film forming unit)
62: Opposing member rotating unit (treated film forming unit)
100: Processing film 102: Through hole 103: Object to be removed 110: Highly soluble solid 111: Lowly soluble solid 150: Surface layer 153: Barrier layer (TiN layer)
W: Substrate θ: Contact angle θ1: Contact angle (contact angle of pure water to the surface of the substrate)
θ2: Contact angle (contact angle of pure water to the treatment film)

Claims (12)

a hydrophilization step of hydrophilizing the surface of the substrate;
a treatment liquid supplying step of supplying a treatment liquid to the hydrophilized surface of the substrate;
a treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate to hold the object to be removed present on the surface of the substrate;
a peeling step of supplying a peeling liquid to the surface of the substrate to peel off the treatment film holding the object to be removed from the surface of the substrate;
the peeling step includes a through-hole forming step of partially dissolving the treatment film in the stripping solution to form a through-hole in the treatment film,
The substrate processing method, wherein a contact angle of pure water with the processing film is greater than 52° and smaller than 61°. The substrate processing method according to claim 1, wherein the stripping step includes a stripping liquid inlet step of injecting a stripping liquid between the surface of the substrate and the processing film. The substrate processing method according to claim 1 or 2, wherein the hydrophilization step includes a step of hydrophilizing the surface of the substrate by supplying a hydrophilization liquid to the surface of the substrate. The substrate processing method according to claim 3, wherein the hydrophilizing liquid is an oxidizing liquid or an organic solvent. The substrate processing method according to any one of claims 1 to 4, wherein at least one of Si, SiN, _SiO2 , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and amorphous carbon is exposed from the surface of the substrate. a surface layer of the substrate includes a TiN layer exposed from a surface of the substrate;
The substrate processing method according to claim 3 , wherein the hydrophilizing liquid is an oxidizing liquid. the processing liquid contains a solvent and a solute,
the solute has a highly soluble component and a low soluble component that is less soluble in the stripping solution than the highly soluble component,
the treatment film forming step includes a step of forming the treatment film having a highly soluble solid formed from the highly soluble component and a low solubility solid formed from the low solubility component,
7. The substrate processing method according to claim 1, wherein the peeling step dissolves the highly soluble solid in the peeling solution to peel off the processing film holding the object to be removed from the surface of the substrate. a hydrophilization step of hydrophilizing the surface of the substrate;
a treatment liquid supplying step of supplying a treatment liquid to the hydrophilized surface of the substrate;
a treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate to hold the object to be removed present on the surface of the substrate;
a peeling step of supplying a peeling liquid to the surface of the substrate to peel off the treatment film holding the object to be removed from the surface of the substrate;
The substrate processing method, wherein a contact angle of pure water with the processing film is greater than 52° and smaller than 61°. a hydrophilization step of hydrophilizing the surface of the substrate;
a treatment liquid supplying step of supplying a treatment liquid to the hydrophilized surface of the substrate;
a treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate to hold the object to be removed present on the surface of the substrate;
a peeling step of supplying a peeling liquid to the surface of the substrate to peel off the treatment film holding the object to be removed from the surface of the substrate;
the processing liquid contains a solvent and a solute,
the solute has a highly soluble component and a low soluble component that is less soluble in the stripping solution than the highly soluble component,
the treatment film forming step includes a step of forming the treatment film having a highly soluble solid formed from the highly soluble component and a low solubility solid formed from the low solubility component,
,
the peeling step dissolves the highly soluble solid in the peeling solution to peel off the treatment film holding the object to be removed from the surface of the substrate;
The substrate processing method, wherein a contact angle of pure water with the processing film is greater than 52° and smaller than 61°. 10. The substrate processing method according to claim 9, wherein at least one of Si, SiN, _SiO2 , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru and amorphous carbon is exposed from the surface of the substrate. a hydrophilization liquid supplying unit that supplies a hydrophilization liquid for hydrophilizing the surface of the substrate to the surface of the substrate;
a processing liquid supply unit that supplies a processing liquid to a surface of the substrate;
a treatment film forming unit for solidifying or curing a treatment liquid in contact with a surface of the substrate to form a treatment film;
a stripping solution supply unit that supplies a stripping solution to the surface of the substrate to strip a treatment film formed on the surface of the substrate;
a controller for controlling the hydrophilization liquid supply unit, the treatment liquid supply unit, the treatment film forming unit and the stripping liquid supply unit,
The controller:
supplying a hydrophilizing liquid from the hydrophilizing liquid supply unit onto the surface of the substrate to hydrophilize the surface of the substrate;
supplying a treatment liquid from the treatment liquid supply unit onto the hydrophilized surface of the substrate;
solidifying or curing the processing liquid supplied to the surface of the substrate by the processing film forming unit to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate;
supplying a stripping liquid from the stripping liquid supply unit onto the surface of the substrate, thereby stripping the treatment film, which is holding the object to be removed, from the surface of the substrate;
the stripping solution is programmed to partially dissolve the treatment film to form through-holes in the treatment film,
The substrate processing apparatus, wherein a contact angle of pure water with the processing film is greater than 52° and smaller than 61°. a hydrophilization liquid supplying unit that supplies a hydrophilization liquid for hydrophilizing the surface of the substrate to the surface of the substrate;
a processing liquid supply unit that supplies a processing liquid to a surface of the substrate;
a treatment film forming unit for solidifying or curing a treatment liquid in contact with a surface of the substrate to form a treatment film;
a stripping solution supply unit that supplies a stripping solution to the surface of the substrate to strip a treatment film formed on the surface of the substrate;
a controller for controlling the hydrophilization liquid supply unit, the treatment liquid supply unit, the treatment film forming unit and the stripping liquid supply unit,
the processing liquid contains a solvent and a solute,
the solute has a highly soluble component and a low soluble component that is less soluble in the stripping solution than the highly soluble component,
a treatment film formed on a surface of a substrate has a highly soluble solid formed from the highly soluble component and a low solubility solid formed from the low solubility component,
The controller:
supplying a hydrophilizing liquid from the hydrophilizing liquid supply unit onto the surface of the substrate to hydrophilize the surface of the substrate;
supplying a treatment liquid from the treatment liquid supply unit onto the hydrophilized surface of the substrate;
solidifying or curing the processing liquid supplied to the surface of the substrate by the processing film forming unit to form a processing film on the surface of the substrate that holds the object to be removed present on the surface of the substrate;
a stripping liquid supply unit supplies a stripping liquid to the surface of the substrate, dissolving the highly soluble solid in the stripping liquid, and stripping the treatment film, which is holding the object to be removed, from the surface of the substrate;
The substrate processing apparatus, wherein a contact angle of pure water with the processing film is greater than 52° and smaller than 61°.

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