JP7440316B2 - Substrate processing method and substrate processing apparatus - Google Patents

Description

The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Substrates to be processed include, for example, semiconductor wafers, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates, as well as liquid crystal display devices, plasma displays, and Includes substrates such as substrates for FPDs (Flat Panel Displays) such as organic EL (Electroluminescence) display devices.

In the manufacturing process of semiconductor devices, various contaminants adhering to the substrate, residues of processing liquids and resists used in previous processes, and various particles (hereinafter sometimes collectively referred to as "objects to be removed") are removed. The process is carried out.
Specifically, by supplying deionized water (DIW) or the like to the substrate, the object to be removed can be removed by the physical action of DIW, or a chemical solution that chemically reacts with the object to be removed can be applied to the substrate. It is common to chemically remove the object to be removed by supplying it.

However, the concavo-convex patterns formed on substrates are becoming increasingly finer and more complex. Therefore, it is becoming difficult to remove the object to be removed using DIW or a chemical solution while suppressing damage to the uneven pattern.
Therefore, by supplying a processing liquid to the surface of the substrate and solidifying the processing liquid on the substrate to form a holding layer that holds the object to be removed on the substrate, a stripping liquid is supplied to the upper surface of the substrate. , a method has been proposed in which the holding layer is peeled off and removed from the surface of the substrate along with the object to be removed (see Patent Document 1 below).

JP2019-62171A

In Patent Document 1, a stripping liquid enters into the holding layer by forming an entry path for the stripping liquid. However, depending on the surface condition of the substrate, the stripping liquid may not be able to sufficiently enter the interface between the substrate and the holding layer, and the holding layer may not be sufficiently peeled from the surface of the substrate.
Therefore, there is a need for a method for effectively peeling off the holding layer holding the object to be removed from the substrate. SUMMARY OF THE INVENTION Accordingly, one object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can effectively peel off a processing film holding an object to be removed from a surface of a substrate.

One embodiment of the present invention includes a hydrophilization step of making the surface of a substrate hydrophilic, a treatment liquid supply step of supplying a treatment liquid to the surface of the substrate that has been made hydrophilic, and a treatment liquid supplied to the surface of the substrate. a treatment film forming step of solidifying or hardening the liquid to form a treatment film on the surface of the substrate that retains the object to be removed present on the surface of the substrate; and supplying a stripping liquid to the surface of the substrate; The present invention provides a substrate processing method including a peeling step of peeling off the processing film holding the object to be removed from the surface of the substrate. The stripping step includes a through hole forming step of partially dissolving the treated film in the stripping solution to form a through hole in the treated film.

The inventors of the present invention have discovered that the peeling action of a stripping liquid to peel a treated film from a substrate changes depending on the surface condition of the substrate. Specifically, the higher the hydrophilicity of the surface of the substrate, the easier it is to peel off the treated film with a stripping solution. More specifically, the higher the hydrophilicity of the surface of the substrate, the more easily the stripping liquid acts on the interface between the treated film and the substrate, and the more effectively the treated film can be stripped from the surface of the substrate.

Therefore, if a treated film is formed on the surface of a substrate that has been made hydrophilic and a stripping solution is supplied toward the surface of the substrate on which the treated film is formed, the treated film can be effectively peeled off from the substrate. can.
Furthermore, since the stripping solution supplied toward the surface of the substrate forms the through-hole in the treated film, the stripping solution can reach the interface between the treated film and the substrate via the through-hole. This allows the stripping liquid to act on the interface between the substrate and the portion surrounding the through-hole in the treated film. Therefore, compared to a method in which the stripping solution permeates into the treated film without forming through holes in the treated film and reaches the interface between the treated film and the substrate, The stripping solution can be applied quickly. Although the treated membrane is partially dissolved by the stripping solution to form the through-holes, the remaining portion remains in a solid state. Therefore, the treated film holding the object to be removed can be effectively peeled off from the surface of the substrate.

In this way, most of the treated film can be maintained in a solid state while the stripping solution acts quickly on the interface between the treated film and the substrate, so that the treated film holding the object to be removed can be effectively removed from the substrate. It can be peeled off.
In one embodiment of the present invention, the stripping step includes a stripping solution introduction step of introducing a stripping solution between the surface of the substrate and the treated film.

The inventors of the present application have discovered that the higher the hydrophilicity of the surface of the substrate, the higher the wettability (affinity) of the stripping solution to the substrate, and the easier it is for the stripping solution to enter between the substrate and the treated film. Therefore, if there is a method in which a treated film is formed on the surface of a substrate that has been made hydrophilic and a stripping solution is supplied toward the surface of the substrate on which the treated film is formed, the stripping solution can be applied between the substrate and the treated film. It is possible to enter the target. Thereby, the treated film can be effectively peeled off from the surface of the substrate.

In one embodiment of the present invention, the hydrophilization step includes a step of making the surface of the substrate hydrophilic by supplying a liquid hydrophilization liquid to the surface of the substrate. By supplying the liquid hydrophilic liquid to the surface of the substrate, the hydrophilic liquid spreads on the surface of the substrate, and the hydrophilic liquid can be distributed over the entire surface of the substrate. Therefore, the entire surface of the substrate can be made evenly hydrophilic. Since the entire surface of the substrate is made hydrophilic, the stripping solution tends to act on the interface between the treated film and the substrate over the entire surface of the substrate in the subsequent stripping process. Therefore, uneven peeling of the treated film on the surface of the substrate can be reduced.

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

On the other hand, when an oxidizing liquid is used as the hydrophilizing liquid, a portion near the surface of the substrate is oxidized. 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 made hydrophilic regardless of the presence of organic substances. When an oxidizing liquid is used as the hydrophilizing liquid, the surface of the substrate can be made hydrophilic regardless of the presence of organic matter. In other words, even if organic substances that are difficult to dissolve in organic solvents are present on the surface of the substrate, the surface of the substrate can be made hydrophilic. Therefore, when an oxidizing liquid is used as the hydrophilizing liquid, the hydrophilicity of the surface of the substrate can be further improved.

In one embodiment of the invention, at least one of Si, SiN, SiO ₂ , 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 the hydrophilization process.
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 hydrophilic liquid is an oxidizing liquid. An oxide film can be formed on the surface of the TiN layer by supplying an oxidizing liquid such as hydrofluoric acid (HF, DHF) or an ammonia/hydrogen peroxide solution mixture (SC1) to the surface of the substrate as a hydrophilic liquid. 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 reducing step of reducing the contact angle of pure water 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 a substrate becomes smaller as the hydrophilicity of the surface of the substrate increases. The inventors of the present application have found that when the contact angle of pure water with respect to the surface of the substrate is smaller than 41.7°, the stripping liquid sufficiently acts on the interface between the substrate and the treated film.

Therefore, by making the surface of the substrate hydrophilic and reducing the contact angle so that the contact angle of pure water with the surface of the substrate is smaller than 41.7°, the stripping solution can be applied to the interface between the substrate and the treated film sufficiently. It can be made to work. Thereby, the treated film holding the object to be removed can be effectively peeled off from the substrate.
In one embodiment of the present invention, the contact angle of pure water with respect to the treated membrane is greater than 52° and smaller than 61°. The inventors of the present invention have found that when the contact angle of pure water with respect to the treated film is greater than 52° and smaller than 61°, the stripping liquid can sufficiently act on the interface between the substrate and the treated film.

Therefore, if the contact angle of pure water with respect to the treated film is larger than 52° and smaller than 61°, the stripping solution can sufficiently act on the interface between the substrate and the treated film, and the treated film can be effectively peeled off. .
In one embodiment of the invention, the processing liquid contains a solvent and a solute. The solute has a high solubility component and a low solubility component that has lower solubility in the stripping solution than the high solubility component. The treated film forming step includes a step of forming the treated film having a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component. Then, in the peeling step, the highly soluble solid is dissolved in the stripping liquid, and the treated film holding the object to be removed is peeled off 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 low soluble component in the stripping solution. Therefore, a highly soluble solid formed by a highly soluble component is more easily dissolved in the stripping solution than a low soluble solid formed by a low soluble component.
Therefore, gaps are formed in the treated film by supplying a stripping solution to the surface of the substrate and dissolving the highly soluble solid in the stripping solution. On the other hand, low-solubility solids are not dissolved in the stripping solution and are maintained in a solid state.

Therefore, while the highly soluble solids are dissolved in the stripping solution, the low soluble solids can be maintained in a solid state without being dissolved in the stripping solution. Therefore, the stripping liquid reaches the interface between the substrate and the low-solubility solid through a gap (path) formed by dissolving the high-solubility solid.
Therefore, the stripping liquid can be applied to the interface between the low-solubility solid and the substrate while holding the object to be removed with the low-solubility solid. As a result, the treated film can be quickly peeled off from the substrate, and the object to be removed can be efficiently removed from the substrate together with the treated film.

One embodiment of the present invention includes a hydrophilization step of making the surface of a substrate hydrophilic, a treatment liquid supply step of supplying a treatment liquid to the surface of the substrate that has been made hydrophilic, and a treatment liquid supplied to the surface of the substrate. a treatment film forming step of solidifying or hardening the liquid to form a treatment film on the surface of the substrate that retains the object to be removed present on the surface of the substrate; and supplying a stripping liquid to the surface of the substrate; and a peeling step of peeling off the treated film holding the object to be removed from the surface of the substrate, and the hydrophilization step is performed when the contact angle of pure water with the surface of the substrate is less than 41.7°. Provided is a substrate processing method including a contact angle reducing step of reducing the contact angle.

According to this method, a treated film is formed on the surface of a substrate that has been rendered hydrophilic, and a stripping liquid is supplied toward the surface of the substrate on which the treated film is formed. As described above, the higher the hydrophilicity of the surface of the substrate, the more easily the stripping liquid acts on the interface between the treated film and the substrate, and the more effectively the treated film can be stripped from the surface of the substrate. In this method, the surface of the substrate is made hydrophilic such that the contact angle of pure water with the surface of the substrate is less than 41.7°. Therefore, the stripping liquid can be sufficiently applied to the interface between the substrate and the treated film. Thereby, the treated film holding the object to be removed can be effectively peeled off from the substrate.

In one embodiment of the present invention, the contact angle of pure water with respect to the treated membrane is greater than 52° and smaller than 61°. Therefore, the treated film can be effectively peeled off by allowing the stripping liquid to sufficiently act on the interface between the substrate and the treated film.
One embodiment of the present invention includes a hydrophilization step of making the surface of a substrate hydrophilic, a treatment liquid supply step of supplying a treatment liquid to the surface of the substrate that has been made hydrophilic, and a treatment liquid supplied to the surface of the substrate. a treatment film forming step of solidifying or hardening the liquid to form a treatment film on the surface of the substrate that retains the object to be removed present on the surface of the substrate; and supplying a stripping liquid to the surface of the substrate; a peeling step of peeling the treated film holding the object to be removed from the surface of the substrate, the treatment liquid containing a solvent and a solute, and the solute being a highly soluble component. and a low solubility component that has lower solubility in the stripping solution than the high solubility component. In this substrate processing method, the treated film forming step is a step of forming the treated film having a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component. including. Then, in the peeling step, the highly soluble solid is dissolved in the stripping liquid, and the treated film holding the object to be removed is peeled off from the surface of the substrate.

According to this method, a treated film is formed on the surface of a substrate that has been rendered hydrophilic, and a stripping liquid is supplied toward the surface of the substrate on which the treated film is formed. As described above, the higher the hydrophilicity of the surface of the substrate, the more easily the stripping liquid acts on the interface between the treated film and the substrate, and the more effectively the treated film can be stripped from the surface of the substrate. Therefore, the treated film can be effectively peeled off from the substrate.
According to this method, the solubility of the highly soluble component in the stripper is higher than the solubility of the low soluble component in the stripper. Therefore, a highly soluble solid formed by a highly soluble component is more easily dissolved in the stripping solution than a low soluble solid formed by a low soluble component.

Therefore, gaps are formed in the treated film by supplying a stripping solution to the surface of the substrate and dissolving the highly soluble solid in the stripping solution. On the other hand, low-solubility solids are not dissolved in the stripping solution and are maintained in a solid state.
Therefore, while the highly soluble solids are dissolved in the stripping solution, the low soluble solids can be maintained in a solid state without being dissolved in the stripping solution. Therefore, the stripping liquid reaches the interface between the substrate and the low-solubility solid through a gap (path) formed by dissolving the high-solubility solid.

Therefore, the stripping liquid can be applied to the interface between the low-solubility solid and the substrate while holding the object to be removed with the low-solubility solid. Thereby, the treated film holding the object to be removed can be effectively peeled off from the substrate.
As a result, the treated film can be quickly peeled off from the substrate, and the object to be removed can be efficiently removed from the substrate together with the treated 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 the hydrophilization process.
In this substrate processing method, the hydrophilization step includes a contact angle reducing step of reducing the contact angle of pure water to the surface of the substrate so that the contact angle is smaller than 41.7°. Therefore, the stripping liquid can be sufficiently applied to the interface between the substrate and the treated film. Thereby, the treated film holding the object to be removed can be effectively peeled off from the substrate.
In the above substrate processing method, it is preferable that the contact angle of pure water with respect to the processing film is greater than 52° and smaller than 61°.

One embodiment of the present invention includes a hydrophilic liquid supply unit that supplies a hydrophilic liquid to the surface of the substrate, a processing liquid supply unit that supplies a processing liquid to the surface of the substrate, and a hydrophilic liquid supply unit that supplies a hydrophilic liquid that makes the surface of the substrate hydrophilic. a treated film forming unit that solidifies or hardens a treatment liquid in contact with a surface to form a treated film; a stripping liquid supply unit that supplies a stripping liquid that peels off a treated film formed on the surface of the substrate to the surface of the substrate; A substrate processing apparatus is provided, including a controller that controls the hydrophilic 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 makes the surface of the substrate hydrophilic by supplying the hydrophilic liquid from the hydrophilic liquid supply unit to the surface of the substrate, and makes the surface of the substrate hydrophilic. A process of supplying a treatment liquid from the treatment liquid supply unit, solidifying or hardening the treatment liquid supplied to the surface of the substrate by the treatment film forming unit, and retaining the object to be removed present on the surface of the substrate. A film is formed on the surface of the substrate, and a stripping liquid is supplied from the stripping liquid supply unit to the surface of the substrate to peel the treated film holding the object to be removed from the surface of the substrate. The stripping solution is programmed to partially dissolve the treated film and form through holes in the treated film.

According to this configuration, the same effects as the substrate processing method described above can be achieved.
One embodiment of the present invention includes a hydrophilic liquid supply unit that supplies a hydrophilic liquid to the surface of the substrate, a processing liquid supply unit that supplies a processing liquid to the surface of the substrate, and a hydrophilic liquid supply unit that supplies a hydrophilic liquid that makes the surface of the substrate hydrophilic. a treated film forming unit that solidifies or hardens a treatment liquid in contact with a surface to form a treated film; a stripping liquid supply unit that supplies a stripping liquid that peels off a treated film formed on the surface of the substrate to the surface of the substrate; a controller that controls the hydrophilizing liquid supply unit, the treatment liquid supply unit, the treatment film forming unit, and the stripping liquid supply unit, the treatment liquid contains a solvent and a solute, and the solute is It has a highly soluble component and a low soluble component having lower solubility in the stripping solution than the highly soluble component, and the treated film has a highly soluble solid formed by the highly soluble component and the low soluble component. A substrate processing apparatus having a low solubility solid formed by a soluble component is provided.

The controller included in the substrate processing apparatus supplies a hydrophilic liquid to the surface of the substrate from the hydrophilic liquid supply unit to make the surface of the substrate hydrophilic, and the surface of the substrate that has been made hydrophilic is A process of supplying a treatment liquid from the treatment liquid supply unit, solidifying or hardening the treatment liquid supplied to the surface of the substrate by the treatment film forming unit, and retaining the object to be removed present on the surface of the substrate. forming a film on the surface of the substrate, supplying a stripping solution from the stripping solution supply unit to the surface of the substrate, dissolving the highly soluble solid in the stripping solution, and holding the object to be removed; The processing film is programmed to peel off the treated film from the surface of the substrate.

According to this configuration, the same effects as the substrate processing method described above can be achieved.
The hydrophilization preferably reduces the contact angle of pure water to the surface of the substrate such that the contact angle is smaller than 41.7°.
Further, it is preferable that the contact angle of pure water with respect to the treated membrane is larger than 52° and smaller than 61°.

FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus according to an embodiment of the present invention. FIG. 2 is a schematic partial sectional view showing a schematic configuration of a processing unit included in the substrate processing apparatus. FIG. 3 is a schematic diagram of a pure water droplet on a substrate and its surroundings. FIG. 4A is a schematic diagram for explaining how the surface of a 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 solution. FIG. 5 is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus. FIG. 6 is an example of the structure of the surface layer of a substrate to be processed. FIG. 7 shows another example of the structure 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 treatment. 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 supply 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 process (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 removal step (step S9) of the substrate processing. FIG. 10A is a schematic diagram for explaining how the treated film is peeled off from the surface of the substrate. FIG. 10B is a schematic diagram for explaining how the treated film is peeled off from the surface of the substrate. FIG. 10C is a schematic diagram for explaining how the treated 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 the 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 treated film from the experimental substrate. FIG. 13 is a table showing the contact angle of pure water with respect to the surface of an experimental substrate and whether or not a film can be treated with a stripping solution. 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 treated membrane. FIG. 15 is a table showing the contact angle of pure water with respect to the surface of the treated membrane.

Embodiments of the present invention will be described below with reference to the accompanying drawings.
<Configuration of substrate processing equipment>
FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to an 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 has Si (silicon), SiN (silicon nitride), SiO ₂ (silicon oxide), SiGe (silicon germanium), Ge (germanium), SiCN (silicon carbonitride), W (tungsten), TiN ( A substrate in which at least one of titanium nitride), Co (cobalt), Cu (copper), Ru (ruthenium), and aC (amorphous carbon) is exposed can be used. That is, on the surface of the substrate W, only one type of substance among the above-mentioned substances may be exposed, or a plurality of substances among the above-mentioned substances may be exposed.

The substrate processing apparatus 1 includes a plurality of processing units 2 that process substrates W with fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W to be processed by the processing units 2 is placed, and a load port LP. The controller 3 includes transport robots IR and CR that transport the substrate W between the processing unit 2 and the processing unit 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 unit 2. For example, the plurality of processing units 2 have a similar configuration. As will be described in detail later, the processing fluid supplied to the substrate W in the processing unit 2 includes a hydrophilizing liquid, a rinsing liquid, a substitution liquid, a processing liquid, a stripping liquid, a residue removing liquid, a heat medium, and an inert gas (gas ) etc. are included.

Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed within the chamber 4, and processes the substrate W within the processing cup 7. The chamber 4 is formed with an entrance/exit (not shown) through which the substrate W is carried in and the substrate W is carried out by the transfer robot CR. The chamber 4 is equipped with a shutter unit (not shown) that opens and closes the entrance/exit.

FIG. 2 is a schematic diagram for explaining a configuration example of the processing unit 2. As shown in FIG. The processing unit 2 includes a spin chuck 5, a facing member 6, a processing cup 7, a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11, a central nozzle 12, and a bottom nozzle 13. including.
The spin chuck 5 is an example of a substrate holding and rotating unit that rotates the substrate W around the rotation axis A1 (vertical axis) while holding the substrate W horizontally. The rotation axis A1 is a vertical straight 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 rotating shaft 22, and a spin motor 23.

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

The rotation shaft 22 extends vertically along the rotation axis A1. The upper end of the rotating shaft 22 is coupled to the center of the lower surface of the spin base 21 . The spin motor 23 applies rotational force to the rotating shaft 22 . As the rotating shaft 22 is rotated by the spin motor 23, the spin base 21 is rotated. Thereby, the substrate W is rotated around the rotation axis A1. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

The spin chuck 5 is not limited to a clamping type chuck that brings a plurality of chuck pins 20 into contact with the peripheral end surface of the substrate W, but also a vacuum 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. It may be a type chuck.
The facing member 6 faces the substrate W held by the spin chuck 5 from above. The opposing member 6 is formed into a disk shape having approximately the same diameter as the substrate W or a larger diameter. The facing member 6 has a facing surface 6a facing the upper surface (upper surface) of the substrate W. The opposing surface 6a is arranged above the spin chuck 5 and substantially along a horizontal plane.

A hollow shaft 60 is fixed to the opposite side of the facing member 6 from the facing surface 6a. A communication hole 6b that vertically passes 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 the internal space 60a of the hollow shaft 60.
The facing member 6 blocks the atmosphere in the space between the facing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the opposing member 6 is also referred to as a blocking plate.

The processing unit 2 further includes a facing member lifting unit 61 that drives the facing member 6 up and down, and a facing member rotation unit 62 that rotates the facing member 6 around the rotation axis A1.
The opposing member elevating unit 61 can vertically position the opposing member 6 at any position (height) from the lower position to the upper position. The lower position is a position where the opposing surface 6a is closest to the substrate W in 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 in the movable range of the opposing member 6. When the opposing member 6 is in the upper position, the transfer robot CR can access the spin chuck 5 for loading and unloading the substrate W.

The opposing member lifting/lowering 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 driving force to the ball screw mechanism. ). The facing member lifting unit 61 is also referred to as a facing member lifter (blocking plate 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 scattered outward from the substrate W held by the spin chuck 5, a plurality of cups 72 for receiving the liquid guided downward by the plurality of guards 71, and a plurality of cups 72 for receiving the liquid guided downward by the plurality of guards 71. A cylindrical outer wall member 73 surrounding a guard 71 and a plurality of cups 72 is included.
This embodiment shows an example in which two guards 71 (first guard 71A and second guard 71B) and two cups 72 (first cup 72A and second cup 72B) are provided.

Each of the first cup 72A and the second cup 72B has an annular groove that is open upward.
The first guard 71A is arranged to surround the spin base 21. The second guard 71B is arranged so as to surround the spin base 21 outside the first guard 71A.

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

The processing unit 2 includes a guard raising/lowering unit 74 that vertically raises and lowers a first guard 71A and a second guard 71B separately. The guard raising/lowering unit 74 raises and lowers the first guard 71A between a lower position and an upper position. The guard raising/lowering unit 74 raises and lowers the second guard 71B between the lower position and the upper position.
When both the first guard 71A and the second guard 71B are located in the upper position, the liquid scattered from the substrate W is received by the first guard 71A. When the first guard 71A is located at the lower position and the second guard 71B is located at the upper position, the liquid scattered from the substrate W is received by the second guard 71B. When the first guard 71A and the second guard 71B are both located at the lower position, the transfer robot CR can access the spin chuck 5 for loading and unloading 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, and a second ball screw mechanism (not shown). It includes a second ball screw mechanism (not shown) coupled to the guard 71B and a second motor (not shown) that provides driving force to the second ball screw mechanism. The guard lifting unit 74 is also referred to as a guard lifter.

The first moving nozzle 9 is an example of a hydrophilic liquid nozzle (hydrophilic liquid supply unit) that supplies (discharges) a hydrophilic liquid toward the upper surface of the substrate W held by the spin chuck 5 .
The first moving nozzle 9 is moved horizontally and vertically by the first nozzle moving unit 35. The first movable nozzle 9 can be moved in the horizontal direction between a center position and a home position (retreat position). The first movable nozzle 9 faces the central region of the upper surface of the substrate W when located at the center position. The central region of the upper surface of the substrate W is a region on the upper surface of the substrate W that includes the rotation center of the substrate W and its surroundings.

When the first movable 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 plan view. The first movable nozzle 9 can approach the top surface of the substrate W or retreat upward from the top surface of the substrate W by moving in the vertical direction.
The first nozzle moving unit 35 includes, for example, an arm (not shown) that is coupled to the first moving nozzle 9 and extends horizontally, a rotation shaft (not shown) that is coupled to the arm and extends vertically, and a rotating shaft (not shown) that is coupled to the arm and extends in the vertical direction. It includes a rotating shaft drive unit (not shown) that raises and lowers and rotates the moving shaft.

The rotation shaft drive unit swings the arm by rotating the rotation shaft around a vertical rotation axis. Furthermore, the rotation shaft drive unit raises and lowers the arm by raising and lowering the rotation shaft along the vertical direction. The first movable nozzle 9 moves in the horizontal and vertical directions in accordance with the swinging and elevation of the arm.
The first moving nozzle 9 is connected to a hydrophilic liquid pipe 40 that guides the hydrophilic liquid. When the hydrophilic liquid valve 50 installed in the hydrophilic liquid pipe 40 is opened, the hydrophilic liquid is discharged downward from the first moving nozzle 9 in a continuous flow. When the hydrophilic liquid valve 50 is opened when the first movable nozzle 9 is located at the center position, the hydrophilic liquid is supplied to the central region of the upper surface of the substrate W.

Hydrophilic liquids include, for example, hydrofluoric acid (HF, DHF), oxidizing liquids such as aqueous ammonia/hydrogen peroxide mixture (SC1), and sulfuric acid/hydrogen peroxide mixture (SPM), and organic liquids such as isopropyl alcohol (IPA). Examples include solvents and hydrochloric acid (HCl). The hydrophilic liquid is a liquid for making the surface of the substrate W hydrophilic (increasing hydrophilicity).
The oxidizing liquid is a liquid containing a substance with oxidizing power (oxidizing agent). For example, SC1 contains hydrogen peroxide as an oxidizing agent, and hydrofluoric acid contains hydrogen fluoride as an oxidizing agent. 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. The contact angle is a numerical value that represents the degree of swelling of a droplet (height of the liquid) that is formed when a liquid is dropped onto a certain solid. Specifically, the contact angle is the angle between the liquid level and the solid surface when the liquid adhering to the solid surface 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.

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

Next, a description will be given of how the surface of the substrate W is made hydrophilic. FIGS. 4A and 4B are schematic diagrams for explaining how the surface of the substrate W is made hydrophilic by the hydrophilic liquid.
When an organic solvent such as IPA is used as the hydrophilizing liquid, the surface of the substrate W is made hydrophilic by removing the hydrophobic organic matter 170 adhering to the surface of the substrate W. Specifically, as shown in FIG. 4A, the hydrophobic organic matter 170 present on the surface of the substrate W is dissolved in an organic solvent to make the surface of the substrate W hydrophilic. Therefore, the organic substance 170A that is difficult to dissolve in the hydrophilic liquid may remain on the surface of the substrate W. Therefore, hydrophilization by the organic solvent is influenced by the type of organic substance 170 present on the surface of the substrate W.

The organic substances are part of the objects to be removed that exist on the surface of the substrate W, and even if the organic substances are removed using an organic solvent, the removal of the objects cannot be said to be sufficient. 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 treated film, as will be described later.
On the other hand, when an oxidizing solution such as hydrofluoric acid or SC1 is used as the hydrophilic solution, the surface of the substrate W is oxidized and an oxide film 171 is formed on the surface of the substrate W, as shown in FIG. 4B. As the surface of the substrate W is oxidized, oxygen atoms bond to substances exposed from the surface of the substrate W. Since oxygen atoms are bonded to the substance 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 the organic substance 170. In other words, even if the organic substance 170A that is difficult to dissolve 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 improved more efficiently than when using an organic solvent as the hydrophilizing liquid.

If the substrate W has a surface exposed to at least one of Si, SiN, SiO ₂ , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and a-C, it can be made hydrophilic with a hydrophilic solution. be able to. In particular, a substrate W having a surface exposed to at least one of Si, SiN, SiO ₂ , W, TiN, Co, Cu, Ru, and a-C is easily made hydrophilic by a hydrophilic solution; If the substrate W has a surface where any one of SiN, SiO ₂ , W, TiN, Co, and Cu is exposed, it is more likely to be made hydrophilic by the hydrophilic liquid.

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

When the second movable 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 plan view. The second movable nozzle 10 can approach the top surface of the substrate W or retreat upward from the top surface of the substrate W by moving in the vertical direction.
The second nozzle moving unit 36 has a similar configuration to the first nozzle moving unit 35. That is, the second nozzle moving unit 36 includes an arm (not shown) that is coupled to the second moving nozzle 10 and extends horizontally, a rotation shaft (not shown) that is coupled to the arm and extends vertically, and a rotating shaft (not shown) that is coupled to the arm and extends in the vertical direction. It may also include a rotating shaft drive unit (not shown) that raises and lowers and rotates the moving shaft.

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

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

The treatment liquid discharged from the second moving nozzle 10 may contain a corrosion-preventing component. As will be described in detail later, the corrosion-inhibiting component is, for example, BTA (benzotriazole).
As the low-solubility component and the high-solubility component, substances having different solubility in the stripping solution described below can be used. The low solubility component is, for example, novolac. A highly soluble component is, for example, 2,2-bis(4-hydroxyphenyl)propane.

The solvent contained in the treatment liquid may be any liquid that can dissolve 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 is the property of two types of liquids to dissolve and mix with each other.
The treated membrane is mainly composed of a solid-state low-solubility component and a solid-state high-solubility component. A solvent may remain in the treated membrane. Details of each component (solvent, low-solubility component, high-solubility component, and corrosion-inhibiting component) contained in the treatment liquid will be described later.

If the contact angle of pure water with respect to the treated film is greater than 52° and smaller than 61°, the stripping solution described below can be sufficiently applied to the interface between the substrate W and the treated film. By using the treatment liquid described below, it is possible to form a treatment film 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 stripping liquid such as ammonia water in a continuous flow toward the upper surface of the substrate W held by the spin chuck 5. The stripping liquid is a liquid for stripping the treated film holding the object to be removed from the upper surface of the substrate W.

The third moving nozzle 11 is moved horizontally and vertically by the third nozzle moving unit 37. The third movable nozzle 11 can be moved between the center position and the home position (retreat position) in the horizontal direction.
The third moving nozzle 11 faces the central region of the upper surface of the substrate W when located at the center position. When the third movable 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 plan view. The third movable nozzle 11 can approach the top surface of the substrate W or retreat upward from the top surface of the substrate W by moving in the vertical direction.

The third nozzle moving unit 37 has the same configuration as the first nozzle moving unit 35. That is, the third nozzle moving unit 37 includes an arm (not shown) that is coupled to the third moving nozzle 11 and extends horizontally, and a rotation shaft (not shown) that is coupled to the arm and extends vertically. It may also include a rotation shaft drive unit (not shown) that raises, lowers, or rotates the rotation 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 the upper stripping liquid valve 55 interposed in the upper stripping liquid pipe 45 is opened, the stripping liquid is discharged downward from the discharge port of the third moving nozzle 11 in a continuous flow. When the upper stripping liquid valve 55 is opened when the third moving nozzle 11 is located at the center position, the stripping liquid is supplied to the central region of the upper surface of the substrate W.

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

It is preferable that the stripping solution is alkaline. The pH of the stripping solution is preferably 7 to 13. Specifically, the pH of the stripping solution is preferably 8 to 13, more preferably 10 to 13, even more preferably 11 to 12.5. It is preferable to measure the pH after degassing in order to avoid the influence of dissolution of carbon dioxide in the air.

Most of the solvent in the stripping solution is pure water. The proportion of pure water in the solvent of the stripping 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 more More preferably, it is 99 to 100% by mass). "% by mass" is 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 stripping solution is 0.1% to 10% (preferably 0.2% to 8%, more preferably 0.3% to 6%).

The central nozzle 12 is accommodated in the internal space 60a of the hollow shaft 60 of the opposing member 6. The 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 upper 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 surrounding the plurality of tubes. The plurality of tubes and 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 second tube 32, and the third tube 33.

The first tube 31 (center 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 (center 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 (center nozzle 12) is an example of a gas supply unit that supplies gas such as nitrogen gas (N ₂ ) between the upper surface of the substrate W and the facing surface 6a of the facing member 6. The central nozzle 12 is also a rinse liquid nozzle, an organic solvent nozzle, and a gas nozzle.

The first tube 31 is connected to an upper rinse liquid pipe 41 that guides the rinse liquid to the first tube 31 . When the upper rinse liquid valve 51 installed in the upper rinse liquid pipe 41 is opened, the rinse liquid is discharged in a continuous flow from the first tube 31 (center nozzle 12) toward the central region of the upper surface of the substrate W. .
The rinsing liquid is a liquid that washes away liquid adhering to the surface of the substrate W. Examples of the rinsing liquid include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid water at a dilute concentration (for example, about 1 ppm to 100 ppm), ammonia water at a dilute concentration (for example, about 1 ppm to 100 ppm), reduced water (hydrogen water), etc. Can be mentioned.

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 the organic solvent valve 52 installed in the organic solvent pipe 42 is opened, the organic solvent is discharged in a continuous flow from the second tube 32 (center 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 processed film remaining on the upper surface of the substrate W after being peeled off and removed from the upper surface of the substrate W by the stripping liquid. do. Therefore, the residue removing solution is also referred to as a residue dissolving solution.

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

Further, it is preferable that the organic solvent discharged from the second tube 32 is a low surface tension liquid whose surface tension is lower than that of the rinsing liquid. In the substrate processing described later, the upper surface of the substrate W is not dried by shaking off the rinsing liquid on the substrate W, but after the rinsing liquid on the substrate W is replaced with an organic solvent, the organic solvent on the substrate W is removed. The upper surface of the substrate W is dried by shaking off the solvent. Therefore, if the organic solvent is a low surface tension liquid, the surface tension acting on the top surface of the substrate W can be reduced when the top surface of the substrate W is dried.

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

The third tube 33 is connected to a gas pipe 43 that guides gas to the third tube 33. When the gas valve 53 installed in the gas pipe 43 is opened, gas is discharged downward from the third tube 33 (center nozzle 12) in a continuous flow.
The gas discharged from the third tube 33 is, for example, an inert gas such as nitrogen gas. The gas discharged from the third tube 33 may be air. The inert gas is not limited to nitrogen gas, but refers to 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 21 a that opens at the center of the upper surface of the spin base 21 . The discharge port 13a of the lower nozzle 13 is exposed from the upper surface of the spin base 21. The discharge port 13a of the lower surface nozzle 13 faces a central region of the lower surface (lower surface) of the substrate W from below. The central region of the lower surface of the substrate W is a region on the lower surface of the substrate W that includes the rotation center of the substrate W.

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

The lower nozzle 13 is an example of a lower rinsing liquid supply unit that supplies the rinsing liquid to the lower surface of the substrate W. Further, the lower surface nozzle 13 is an example of a lower stripping liquid supply unit that supplies the stripping liquid to the lower surface of the substrate W. Further, the lower surface nozzle 13 is an example of a heating medium supply unit that supplies a heating medium for heating the substrate W to 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 surface nozzle 13 is the same as the rinsing liquid discharged from the center nozzle 12, so a description thereof will be omitted. The stripping liquid discharged from the lower surface nozzle 13 is the same as the stripping liquid discharged from the third movable nozzle 11, so 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 treatment liquid is IPA, DIW at 60° C. to 80° C. is used as the heating medium, for example. The heat medium discharged from the lower nozzle 13 is not limited to high-temperature DIW, but may be a high-temperature gas such as a high-temperature inert gas or high-temperature air whose temperature is higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid. It's okay.

FIG. 5 is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus 1. As shown in FIG. The controller 3 includes a microcomputer and controls the control 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 execute various controls for substrate processing by the processor 3A executing a control program.

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

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

The insulating layer 152 is made of, for example, SiO ₂ (silicon oxide). A contact hole 155 penetrating through the insulating layer 152 is provided above the impurity region 154 .
Barrier layer 153 is formed on the upper surface of insulating layer 152 and on the inner surface of 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 in the insulating layer 152 at equal intervals, and the insulating layer 152 and the contact holes 155 may form a fine uneven pattern. In this case, the barrier layer 153 has a shape that follows the uneven pattern.
FIG. 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 includes a metal layer in addition to a semiconductor layer 151, an insulating layer 152, and a barrier layer 153. 156 may be provided. The metal layer 156 is, for example, a tungsten layer made of W (tungsten), and is formed by a CVD (chemical vapor deposition) method or the like. Metal layer 156 fills contact hole 155 and covers barrier layer 153. Therefore, the surface of metal layer 156 is a flat surface. The metal forming the metal layer 156 is exposed on the surface of the substrate W shown in FIG. When the metal layer 156 is made of tungsten, tungsten is exposed on the surface of the substrate W.

<Substrate processing using substrate processing equipment>
FIG. 8 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus 1. As shown in FIG. FIG. 8 mainly shows processing realized by the controller 3 executing a program. 9A to 9I are schematic diagrams for explaining the state of each step of 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 replacement step (step S4), Treatment liquid supply step (Step S5), treatment film formation step (Step S6), stripping step (Step S7), second rinsing step (Step S8), residue removal step (Step S9), spin drying step (Step S10), and The substrate unloading step (step S11) is executed in this order.

In the following, FIG. 2 and FIG. 8 will be mainly referred to. Refer to FIGS. 9A to 9I as appropriate.
First, an unprocessed substrate W is carried into the processing unit 2 from the carrier C by the transfer robots IR and CR (see FIG. 1), and is passed to the spin chuck 5 (step S1). Thereby, 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 holding of the substrate W by the spin chuck 5 is continued until the spin drying process (step S10) is completed. From the start of the substrate holding process until the end of the spin drying process (step S10), the guard lifting unit 74 moves the first guard 71A and the second guard so that at least one guard 71 is located in the upper position. Adjust the height position of 71B.
With the substrate W held on the spin chuck 5, the spin motor 23 rotates the spin base 21. As a result, rotation of the horizontally held substrate W is started (substrate rotation step). The opposing member rotation unit 62 may rotate the opposing member 6 in synchronization with the spin base 21. Synchronous rotation refers to rotating the facing member 6 in the same rotational direction and at the same rotational 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, the first nozzle moving unit 35 moves the first moving nozzle 9 to the processing position with the opposing member 6 located at the retracted 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 retracted position, each movable nozzle can move horizontally between the opposing member 6 and the substrate W. The retracted position may be an upper position.

Then, the hydrophilic liquid valve 50 is opened. As a result, as shown in FIG. 9A, a 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 substrate W in a rotating state (hydrophilic liquid supply step). , hydrophilic liquid discharge step). The hydrophilic liquid supplied to the upper surface of the substrate W spreads radially under the influence of centrifugal force and spreads over the entire upper surface of the substrate W. As a result, the upper surface of the substrate W is made hydrophilic, and the contact angle of pure water with the upper surface of the substrate W becomes smaller than 41.7° (contact angle reduction step).

The supply of the hydrophilic liquid from the first moving nozzle 9 is continued for a predetermined period of 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 wash away the hydrophilic liquid on the substrate W.
Specifically, the hydrophilic liquid valve 50 is closed. As a result, the supply of the hydrophilic liquid to the substrate W is stopped. 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 opposing member 6 is located at the processing position, the distance between the upper surface of the substrate W and the opposing 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, the rinsing liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the substrate W in the rotating state. The rinsing liquid supplied from the central nozzle 12 to the upper surface of the substrate W spreads radially under centrifugal force and spreads over the entire upper surface of the substrate W. As a result, the hydrophilic 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, the rinsing liquid is supplied (discharged) from the lower surface nozzle 13 toward the central region of the lower surface of the substrate W in the rotating state. The rinsing liquid supplied from the lower surface nozzle 13 to the lower surface of the substrate W spreads radially under the influence of centrifugal force, and spreads over the entire lower surface 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 from the substrate W and adheres to the lower surface of the substrate W, the rinsing liquid supplied from the lower nozzle 13 prevents the hydrophilic liquid from adhering to the lower surface. The hydrophilic solution is washed away.

The discharge of the rinse liquid from the center nozzle 12 and the lower surface nozzle 13 is continued for a predetermined period of 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, a replacement process (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. As a result, the supply of the rinsing liquid to the upper and lower surfaces of the substrate W is stopped. The counter member 6 is maintained in the processing position.
The organic solvent valve 52 is opened while the opposing member 6 is maintained in the processing position. As a result, as shown in FIG. 9C, the organic solvent as the replacement liquid is supplied (discharged) from the center nozzle 12 toward the central region of the upper surface of the substrate W in the rotating state (substitution liquid supply step, substitution liquid discharge process). The central nozzle 12 is an example of a displacement liquid nozzle.

The organic solvent supplied from the central nozzle 12 to the upper surface of the substrate W spreads radially under the influence of centrifugal force, and spreads over the entire upper surface of the substrate W. As a result, the rinsing liquid on the substrate W is replaced by the organic solvent.
In the replacement step, the organic solvent is continuously discharged from the central nozzle 12 for a predetermined period of 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 be rotated at a constant rotation speed in the replacement process. For example, the spin motor 23 may rotate the substrate W at 300 rpm when starting to supply the organic solvent, and may accelerate the rotation of the substrate W until the rotation speed of the substrate W reaches 1500 rpm while supplying the organic solvent to the substrate W. .

Next, a processing liquid supply step (step S5) of supplying the processing liquid onto the upper surface of the substrate W is performed. Specifically, the organic solvent valve 52 is closed, and the opposing member elevating unit 61 moves the opposing member 6 to the retracted position. With the opposing member 6 located at 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, the processing liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the substrate W in the rotating state (processing liquid supply step, processing liquid discharging step). . The processing liquid supplied to the upper surface of the substrate W spreads over the entire substrate W due to centrifugal force. As a result, a liquid film 101 (processing liquid film) of the processing liquid is formed on the substrate W (processing liquid film forming step).

The supply of the processing liquid from the second moving nozzle 10 is continued for a predetermined period of time, for example, 2 seconds to 4 seconds. In the treatment liquid supply step, the substrate W is rotated at a predetermined treatment liquid rotation speed, for example, 10 rpm to 1500 rpm.
Next, a treated film forming step (step S8) shown in FIGS. 9E and 9F is performed. In the treatment film forming step, the treatment liquid on the substrate W is solidified or hardened, and a treatment 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 process, first, a treatment liquid thinning process (treatment liquid spin-off process) is performed to reduce the thickness of the liquid film 101 of the treatment liquid on the substrate W. Specifically, the processing liquid valve 54 is closed. As a result, the supply of the processing liquid to the substrate W is stopped. Then, the second moving nozzle 10 is moved to the home position by the second nozzle moving unit 36.
As shown in FIG. 9E, in the processing liquid thinning process, since the substrate W is rotated while the supply of the processing liquid to the upper surface of the substrate W is stopped, a part of the processing liquid is removed from the upper surface of the substrate W. Ru. Thereby, the thickness of the liquid film 101 on the substrate W becomes appropriate. Even after the second movable nozzle 10 moves to the home position, the opposing member 6 is maintained at the retracted position.

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

In the treatment film forming step, after the treatment liquid thinning step, a treatment liquid solvent evaporation step is performed to evaporate (volatize) a part of the solvent 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 part of the solvent of the treatment liquid on the substrate W.
Specifically, as shown in FIG. 9F, the facing member elevating unit 61 moves the facing member 6 to the close position. The close position may be a 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. As a result, gas is supplied to the space between the upper surface of the substrate W (the upper surface of the liquid film 101) and the opposing surface 6a of the opposing member 6 (gas supply step).
By blowing gas onto the liquid film 101 on the substrate W, evaporation (volatilization) of the solvent in the liquid film 101 is promoted (processing liquid solvent evaporation step, processing liquid solvent evaporation promotion step). Therefore, the time required to form the treated film 100 can be shortened. In the treatment film forming 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 processing liquid thinning step of the liquid film 101, the rotation of the opposing member 6 and the substrate W continues. Therefore, centrifugal force caused by the rotation of the facing member 6 and the substrate W acts on the gas discharged from the central nozzle 12. Due to the action of centrifugal force, an airflow is formed in which the gas moves from the center side of the substrate W toward the peripheral edge side. Therefore, removal of the gaseous solvent in contact with the liquid film 101 from the space between the facing member 6 and the substrate W is facilitated. This promotes evaporation of the solvent in the liquid film 101. In this way, the facing member 6 and the spin motor 23 function as an evaporation unit (evaporation promotion unit) that evaporates (volatizes) the solvent in the processing liquid. The opposing member 6 may not be rotating, and only the substrate W may be rotating.

Also, the heat medium valve 88 is opened. Thereby, the heat medium is supplied (discharged) from the bottom nozzle 13 toward the central region of the bottom surface of the substrate W in the rotating state (heat medium supply process, heat medium discharge process). The heating medium supplied from the lower surface nozzle 13 to the lower surface of the substrate W spreads radially under the influence of centrifugal force, and spreads over the entire lower surface of the substrate W.
The supply of the heat medium to the substrate W is continued for a predetermined period of time, for example, 60 seconds. In the treatment liquid solvent evaporation process, the substrate W is rotated at a predetermined evaporation rotation speed, for example, 1000 rpm.A heating medium is supplied to the lower surface of the substrate W, so that the liquid film on the substrate W is formed through the substrate W. 101 is heated. Thereby, evaporation (volatilization) of the solvent in the liquid film 101 is promoted (processing liquid solvent evaporation step, processing liquid solvent evaporation promotion step). Therefore, the time required to form the treated film 100 can be shortened. Also in the treatment film forming step, 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 executing the processing liquid thinning step and the processing liquid solvent evaporation step. As a result, the processing film 100 holding the object to be removed is formed over the entire upper surface of the substrate W.
In this way, the substrate rotation unit (spin motor 23), the opposing member rotation unit 62, the center nozzle 12, and the bottom nozzle 13 constitute a treated film forming unit that solidifies or hardens the treatment liquid to form the solid treated film 100. are doing.

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

Next, a peeling process (step S6) for peeling off the treated film 100 is performed. Specifically, the heat medium valve 88 is closed. As a result, the supply of the heat medium to the lower surface of the substrate W is stopped. Additionally, the gas valve 53 is closed. As a result, the supply of gas to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W is stopped.
Then, the facing member elevating unit 61 moves the facing member 6 to the retracted position. With the opposing member 6 located at 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 movable nozzle 11 located at the processing position, the upper stripping liquid valve 55 is opened. As a result, as shown in FIG. 9G, the stripping liquid is supplied (discharged) from the third moving nozzle 11 toward the central region of the upper surface of the substrate W in the rotating state (upper stripping liquid supply step, upper stripping liquid discharge). process). The stripping liquid supplied to the top surface of the substrate W spreads over the entire top surface of the substrate W due to centrifugal force. As a result, the treated film 100 on the upper surface of the substrate W is peeled off and discharged to the outside of the substrate W together with the peeling liquid.

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

Here, the processing liquid supplied to the upper surface of the substrate W in the processing liquid supply step (step S5) shown in FIG. 9D adheres to the lower surface of the substrate W along the periphery of the substrate W. Processing liquids may solidify or harden to form solids.
As shown in FIG. 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 solids of the processing liquid are formed on the lower surface of the substrate W, the solids can be peeled off and removed from the lower surface of the substrate W.

After the stripping step (step S6), a second rinsing step (step S7) is performed in which the stripping solution is washed away from the substrate W with a rinsing solution. Specifically, the upper stripping liquid valve 55 and the lower stripping liquid valve 87 are closed. As a result, the supply of the stripping liquid to the upper and lower surfaces of the substrate W is stopped. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to the home position. Then, as shown in FIG. 9H, the facing member elevating unit 61 moves the facing member 6 to the processing position.

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

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

The supply of the rinsing liquid to the upper and lower surfaces of the substrate W is continued for a predetermined period of 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 process, the residue of the treated film 100 remaining on the upper surface of the substrate W after the peeling process is removed by an organic solvent (for example, IPA) as a residue removal liquid. Specifically, the upper rinse liquid valve 51 and the lower rinse liquid valve 86 are closed. As a result, the supply of the rinsing liquid to the upper and lower surfaces of the substrate W is stopped.

Then, with the opposing member 6 located at the processing position, the organic solvent valve 52 is opened. As a result, as shown in FIG. 9I, the organic solvent as the residue removing liquid is supplied (discharged) from the central nozzle 12 toward the central region of the upper surface of the substrate W in the rotating state (residue removing liquid supply step, residue removing liquid). removal liquid discharge process).
The organic solvent supplied from the central nozzle 12 to the upper surface of the substrate W spreads radially under the influence of centrifugal force, and spreads over the entire upper surface of the substrate W. After the organic solvent dissolves the residue of the processed film remaining on the upper surface of the substrate W, it 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 process, the organic solvent is continued to be discharged from the central nozzle 12 for a predetermined period of time, for example, 30 seconds. In the residue removal process, the substrate W is rotated at a predetermined residue removal rotation speed, for example, 300 rpm.
Next, a spin drying 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. As a result, the supply of the organic solvent to the upper surface of the substrate W is stopped. Then, the facing member lifting unit 61 moves the facing member 6 to the drying position below the processing position. When the opposing member 6 is located in 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. As a result, gas is supplied to the space between the upper surface of the substrate W and the facing surface 6a of the facing member 6.

Then, the spin motor 23 accelerates the rotation of the substrate W, causing the substrate W to rotate at high speed. The substrate W in the spin drying process is rotated at a drying speed of, for example, 1500 rpm. The spin drying process is performed for a predetermined period of 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 drying 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. Gas valve 53 is closed. Then, the facing member lifting unit 61 moves the facing 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 passed from the transfer robot CR to the transfer robot IR, and is stored in the carrier C by the transfer robot IR.

<Peeling of treated film>
The manner in which the treated film 100 is removed will be explained in detail using FIGS. 10A to 10C. 10A to 10C are schematic diagrams for explaining how the treated film 100 is peeled off from the substrate W.
The processing film 100 holds the object to be removed 103 attached to the surface layer 150 of the substrate W, as shown in FIG. 10A. The treatment membrane 100 includes a highly soluble solid 110 (highly soluble component in a solid state) and a low soluble solid 111 (a low soluble component in a solid state). Highly soluble solid 110 and lowly soluble solid 111 are formed by evaporation of at least a portion of the solvent contained in the treatment liquid.

In the treated film 100, highly soluble solids 110 and low soluble solids 111 coexist. Strictly speaking, in the treated film 100, the highly soluble solids 110 and the low soluble solids 111 are not 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 soluble solid 111 is unevenly distributed.
Referring to FIG. 10B, highly soluble solid 110 is dissolved by the stripping liquid. That is, the treated film 100 is partially dissolved (dissolution step, partial dissolution step). By dissolving the highly soluble solid 110, through holes 102 are formed in the portions of the treated membrane 100 where the highly soluble solids 110 are unevenly distributed (through hole forming step).

The through holes 102 are particularly likely to be formed in the portions of the treated film 100 where the highly soluble solids 110 extend in the thickness direction T. The through hole 102 has a diameter of, for example, several nm in plan view. The through hole 102 is a gap formed in the treated film 100 when the highly soluble solid 110 is dissolved.
Here, if a suitable amount of solvent remains in the treated film 100, the stripping liquid partially dissolves the treated film 100 while dissolving into the solvent remaining in the treated film 100. Specifically, the stripping liquid dissolves the highly soluble solid 110 in the treated film 100 while dissolving in the solvent remaining in the highly soluble solid 110, thereby forming the through holes 102. Therefore, the stripping liquid easily enters into the treated film 100 (dissolution entry step).

The stripping liquid passes through the through hole 102, reaches the interface between the processing film 100 and the substrate W, and acts on this interface. The stripping liquid acting on the interface between the treated film 100 and the substrate W means that the stripping liquid slightly dissolves the portion in contact with the substrate W, thereby peeling the treated 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 liquid that has reached the vicinity of the top surface of the substrate W through the through hole 102 slightly dissolves the portion of the low-solubility solid 111 near the top surface of the substrate W. As a result, as shown in the enlarged view of FIG. 10B, the stripping liquid gradually dissolves the low-solubility solid 111 near the top surface of the substrate W, and fills the gap G1 between the processed film 100 and the top surface of the substrate W. (stripping liquid entry process).

Then, for example, the processing film 100 splits into film pieces 105 starting from the periphery of the through hole 102, and as shown in FIG. It is peeled off from the substrate W (processed film splitting process, processed film peeling process).
Then, by continuing to supply the treated film stripping liquid, the treated membrane 100 that has become a membrane piece 105 is washed away with the stripping liquid while holding the object 103 to be removed. In other words, the film piece 105 holding the object to be removed 103 is pushed out of the substrate W and removed from the upper surface of the substrate W (processed film removal step, object to be removed step). Thereby, the upper surface of the substrate W can be cleaned well.

<Summary of embodiments>
The strength of the peeling action (peeling force) with which the peeling liquid peels off the processed 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 treated film 100 to be peeled off by the peeling 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 enter between the substrate W and the treated film 100. That is, the higher the hydrophilicity of the upper surface of the substrate W, the easier it is to peel off the treated film 100 from the upper surface of the substrate W.

According to this embodiment, the treated film 100 is formed on the top surface of the substrate W that has been made hydrophilic, and the treated film 100 is peeled off using a stripping solution. Therefore, the treated film 100 can be effectively peeled off from the substrate W.
When the treated film 100 is peeled off, through holes 102 are formed in the treated film 100 by the stripping liquid. Therefore, the stripping liquid can reach the interface between the processing film 100 and the substrate W through the through hole 102. This allows the stripping liquid to enter between the portion of the treated film 100 surrounding the through hole 102 and the upper surface of the substrate W. Therefore, compared to a configuration in which the stripping solution is allowed to penetrate into the processing film 100 and reach the interface between the processing film 100 and the substrate W without forming the through holes 102 in the processing film 100, the processing film 100 is The stripping liquid can be quickly applied to the interface with the substrate W. Although the treated film 100 is partially dissolved by the stripping solution to form the through holes 102, the remaining portion is maintained in a solid state. Therefore, the processing film 100 holding the removal target 103 can be effectively peeled off from the upper surface of the substrate W.

In this way, most of the treated film 100 can be maintained in a solid state while the stripping liquid acts quickly on the interface between the treated film 100 and the substrate W. 100 can be effectively peeled off from the substrate W.
According to this embodiment, the solubility of the highly soluble component in the stripping solution is higher than the solubility of the low soluble component in the stripping solution. Therefore, the highly soluble solid 110 is more easily dissolved in the stripper than the low soluble solid 111.

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

Therefore, the stripping liquid can be applied to the interface between the low-solubility solid 111 and the substrate W while the object 103 to be removed is held by the low-solubility solid 111. As a result, the object to be removed 103 can be efficiently removed from the substrate W along with the processing film 100 while quickly peeling the processing film 100 from the substrate W.
Furthermore, according to the present embodiment, the stripping solution can be effectively introduced between the substrate W and the processing film 100 while slightly dissolving the low-solubility solid 111 contained in the processing film 100 in the stripping solution. I can do it. Therefore, the treated film 100 can be effectively peeled off.

According to this embodiment, the top surface of the substrate W is made hydrophilic by supplying the hydrophilic liquid to the top surface of the substrate W. By supplying the hydrophilic liquid to the upper surface of the substrate W, the hydrophilic liquid spreads on the upper surface of the substrate W, and the hydrophilic liquid can be spread over the entire upper surface of the substrate W. Therefore, the entire upper surface of the substrate W can be made evenly hydrophilic. Since the entire upper surface of the substrate W is made hydrophilic, the stripping liquid tends to act on the interface between the treated film 100 and the substrate W over the entire upper surface of the substrate W in the subsequent stripping process. Therefore, the treated 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°. Therefore, the stripping liquid can be sufficiently applied to the interface between the substrate W and the treated film 100. Thereby, the processing film 100 holding the object to be removed 103 can be effectively peeled off from the substrate W.
According to this embodiment, the contact angle of pure water with respect to the treated membrane 100 is greater than 52° and smaller than 61°. If the pure contact angle with respect to the treated film 100 is within this range, the affinity between the stripping solution and the treated film 100 is sufficiently high. Therefore, the stripping liquid can sufficiently enter between the substrate W and the treated film 100, and the treated film 100 can be effectively peeled off from the substrate W.

According to the present embodiment, at least one of Si, SiN, SiO ₂ , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the upper surface of the substrate W. The upper surface of the substrate W can be made hydrophilic by the hydrophilization process. For example, when the surface layer 150 of the substrate W includes a TiN layer (barrier layer 153), if an oxidizing solution is used as the hydrophilic solution, the upper surface of the substrate W is can be made hydrophilic. By making the upper surface of the substrate W hydrophilic in advance in this manner, the treated 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 rinsing step (step S3) and the replacement step (step S4) are omitted. If the hydrophilic liquid used in the hydrophilic process is compatible with the treatment liquid, the first rinsing process (step S3) and the replacement process (step S4) can be omitted, as shown in FIG. It is possible. It is preferable that the hydrophilizing liquid is the same liquid as the solvent contained in the treatment liquid. The same liquid means that it is composed of the same substance. An example of a hydrophilizing liquid that is compatible with the treatment liquid is an organic solvent such as IPA.

<Treatment film peeling experiment>
Below, the results of a treated film peeling experiment conducted to investigate the relationship between the contact angle of pure water with respect to the substrate and whether or not the treated film can be peeled off will be described. FIG. 12A is a schematic diagram for explaining the procedure for measuring the contact angle of pure water with respect to the surface of the experimental substrate 200. FIG. 12B is a schematic diagram for explaining the procedure for peeling off the treated film from the experimental substrate 200.

In this experiment, one of Si (Bare-Si), SiN, SiO ₂ , W, TiN, Co, Cu, Ru, and amorphous carbon (a-C) was used as the experimental substrate 200 from the surface. Using the exposed substrate, one of hydrochloric acid, SC1, hydrofluoric acid, SPM, and IPA was used as a hydrophilic liquid.
The experimental substrate 200 used in this experiment is a small square piece substrate with a side length of 3 cm in plan view.

The mass percent concentration of hydrogen chloride in the hydrochloric acid used in this experiment is 0.4%. SC1 used in this experiment is a mixed liquid of aqueous ammonia having an ammonia mass percent concentration of 0.4% and hydrogen peroxide water having a hydrogen peroxide mass percent concentration 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 sulfuric acid mass percent concentration of 64.0% and a hydrogen peroxide solution with a hydrogen peroxide mass percent concentration of 10.0%. The pure water used in this experiment was DIW.

This experiment was performed on various combinations of substrate and hydrophilizing liquid.
In order to measure the contact angle of pure water on the experimental substrate 200, the experimental substrate 200 was immersed in a hydrophilic solution as shown in FIG. 12A. Thereafter, although not shown, the experimental substrate 200 was cleaned using DIW to remove the hydrophilic 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.

Then, in order to investigate whether the treated film 201 could be peeled off from the experimental substrate 200, the untreated experimental substrate 200 was immersed in a hydrophilic solution, as shown in FIG. 12B. Thereafter, although not shown, the experimental substrate 200 was cleaned with pure water and/or IPA as necessary. Furthermore, 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 the treated film 201 was formed by rotating the experimental substrate 200 at 1500 rpm for 30 seconds. A stripping solution was supplied to the experimental substrate 200 while rotating the experimental substrate 200 on which the treated film 201 was formed at 800 rpm. The surface of the experimental substrate 200 was observed both before the treatment solution was supplied and after the stripping solution was supplied to determine whether the treated film could be stripped. As the stripping solution, ammonia water having a mass percent concentration of 0.4% was used.

The treatment liquid used in the treatment film peeling experiment contains at least one type of low solubility component selected from the low solubility components described below and at least one type selected from the high solubility components described below as the solute. Contains highly soluble components. 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 FIGS. 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 whether or not the film 201 can be treated with the stripping liquid. FIG. 13 is a table summarizing the results of the treated film peeling experiment.
The table shown in FIG. 13 shows columns for "Surface of substrate,""Hydrophilizationliquid,""Contact angle of pure water (°)," and "Peeling of treated film."

In each row of “substrate surface”, the name of a substance exposed from the surface of the experimental substrate 200 is written. In each row of “Hydrophilization liquid”, the name of the substance of the hydrophilization liquid used to hydrophilize the experimental substrate 200 is described. A line in which "-" is written in "hydrophilic solution" means that the treated film peeling experiment was performed on a substrate that was not hydrophilized.
In each row of "contact angle of pure water (°)", the contact angle θ1 of pure water with respect to the experimental substrate 200 made hydrophilic using the hydrophilic liquid shown in the same row is described.

In each line of "Removal of treated film", it is written whether the treated film 201 was peeled off by the stripping liquid from the experimental substrate 200 that was made hydrophilic using the hydrophilic liquid shown in the same line. "OK" means that the treated film 201 was sufficiently peeled off, and "NG" means that the treated film 201 was not sufficiently peeled off.
For example, in the first row of the table in FIG. 13, the contact angle θ1 of pure water with respect to the experimental substrate 200 after the experimental substrate 200 on which SiN is exposed on the surface is made hydrophilic with HCl is 4.8°; It is shown that the treated film 201 was 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 treated film 201 was not sufficiently peeled off.
As shown in FIG. 13, even if the substances exposed from the surface of the experimental substrate 200 are the same, if the hydrophilizing liquids are different, the contact angle θ1 of pure water with the surface of the experimental substrate 200 will be different. For example, when the experimental substrate 200 with TiN exposed from the surface was made hydrophilic using HF as the hydrophilic liquid, the contact angle θ1 of pure water was 15.2°, and the removal of the treated film 201 was sufficient. . When the experimental substrate 200 with TiN exposed from the surface was made hydrophilic using SC1 as the hydrophilic liquid, the contact angle θ1 of pure water was 28.3°, and the treated film 201 was sufficiently removed. On the other hand, when the experimental substrate 200 with TiN exposed from the surface was made hydrophilic using IPA as a hydrophilic liquid, the contact angle θ1 of pure water was 41.7°, indicating that the removal of the treated film 201 was insufficient. Ta.

Therefore, it is inferred that when an oxidizing liquid is used as the hydrophilic liquid, the hydrophilicity of the surface of the substrate can be improved more than when an organic solvent is used as the hydrophilic liquid. The reasons include the following.
When an organic solvent is used as the hydrophilizing liquid, hydrophobic organic matter adhering to the surface of the substrate is dissolved in the organic solvent, thereby making the surface of the substrate hydrophilic. Depending on the type of organic matter adhering to the surface of the substrate, some organic matter cannot be dissolved in the organic solvent. Therefore, not all organic substances are removed.

On the other hand, when an oxidizing solution is used as the hydrophilic solution, a portion near the surface of the substrate is oxidized to form an oxide film on the surface of the substrate. Therefore, the hydrophilicity of the surface of the substrate can be efficiently increased regardless of the type of organic substance adhering to the surface of the substrate.
Note that when no hydrophilization was performed, the contact angle of pure water with respect to the experimental substrate 200 with TiN exposed from the surface was 59.6°. Therefore, regardless of which of the hydrophilizing liquids, IPA, HF, and SC1, was used, the experimental substrate 200 with TiN exposed from the surface was made hydrophilic.

<Contact angle measurement experiment on treated film>
Next, the results of a contact angle measurement experiment in which the contact angle of pure water with respect to a treated film formed on the surface of an experimental substrate will be 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 treated membrane.
In this experiment, a substrate with Si (Bare-Si) exposed from the surface was used as the experimental substrate 203, and IPA was used as the hydrophilic liquid. Four types of processing liquids PL1 to PL4 were used as the processing liquids. Each of the processing liquids PL1 to PL4 contains IPA as a solvent. Each treatment liquid PL1 to PL4 contains at least one type of low-solubility component selected from among the low-solubility components described below and at least one type of high-solubility component selected from the high-solubility components described below as solutes. Contains ingredients. The low solubility components contained in the processing liquids PL1 to PL4 are common. The highly soluble components contained in the processing liquids PL1 to PL4 are different substances.

As shown in FIG. 15, the experimental substrate 203 was immersed in IPA as a hydrophilic liquid. Thereafter, although not shown, the experimental substrate 203 was cleaned using DIW. Thereafter, a treatment liquid was dropped onto the surface of the experimental substrate 203. Thereafter, a treatment film 204 was formed on the surface of the experimental substrate 203 by evaporating the solvent in the treatment liquid. Furthermore, after that, a droplet 205 of pure water (DIW) was formed on the treated 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 treated film 204 and whether or not the treated film 204 can be coated with the stripping liquid.
The table shown in FIG. 15 shows columns for "processing liquid" and "contact angle of pure water (°)." Each row of “processing liquid” describes which processing liquids PL1 to PL4 were used to form the processing film 204. In each row of "contact angle of pure water (°)", the contact angle θ2 of pure water with respect to the treatment film 204 formed using the treatment liquid shown in the same row is described. The contact angle θ2 of pure water with respect to the treated membrane 204 was within the range of 52° or more and 61° or less. Therefore, it is inferred that if the contact angle of pure water to the treated film 204 is θ2, the treated film formed on the hydrophilic substrate can be effectively peeled off using a stripping liquid.

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

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

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

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

（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 structural unit.)

（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 means a substituent such as C _1-4 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 an adjacent structural unit.)
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, even more preferably is 1,000 to 50,000.

(A) The low solubility component can be obtained by synthesis. It can also be purchased. In the case of 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 Yokuzai Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.
Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.
Polyacrylic acid derivative: Nippon Shokubai Polycarbonate Co., Ltd.: Sigma-Aldrich Polymethacrylic acid derivative: Sigma-Aldrich Compared to the total mass of the treatment liquid, (A) the low-solubility component is 0.1 to 50% by mass, preferably is from 0.5 to 30% by weight, more preferably from 1 to 20% by weight, even more preferably from 1 to 10% by weight. That is, the total mass of the treatment liquid is 100% by mass, and (A) the low-solubility component is 0.1 to 50% by mass based on this. In other words, "compared to" can be rephrased as "based on." The same applies to the following unless otherwise specified.

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

Although there is no intention to limit the scope of the rights and there is no intention to limit the scope of the rights, it is believed that when the treatment liquid is dried to form a treatment film on the substrate and the stripping liquid peels off the treatment film, (B) the highly soluble component It is thought that this creates a part that becomes a trigger for peeling off. For this reason, it is preferable that the highly soluble component (B) has a higher solubility in the stripping solution than the low soluble component (A). (B') An embodiment in which the crack promoting component contains a ketone as a carbonyl group includes a cyclic hydrocarbon. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

As a more specific embodiment, 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 of the following chemical formula 8, each of which is bonded to a linking group (linker L ₁ ). Here, the linker L ₁ may be a single bond or C _1-6 alkylene. The C _1-6 alkylene serves as a linker to connect the structural units, and is not limited to a divalent group. Preferably it has a valence of 2 to 4. 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。

Cy ₁ is a C _5-30 hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. In a preferred embodiment, linker L ₁ connects multiple Cy _{1 s} .

Each R ₁ is independently C _1-5 alkyl, preferably methyl, ethyl, propyl, or butyl. The C _1-5 alkyl may be linear or branched.
n _b1 is 1, 2 or 3, preferably 1 or 2, more preferably 1. n _b1' is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.
Chemical formula 9 below is a chemical formula in which the structural unit shown in chemical formula 8 is expressed using a linker _L9 . Preferably, the linker L ₉ is 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 there is no intention to limit the scope of rights, preferred examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6- Bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert- Examples include 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 explained. The compound (B-1) has three structural units of chemical formula 8, and the structural units are bonded with 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, more preferably methyl or ethyl.

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

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

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

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, preferably -H or -COOH. It is also permissible that one (B-3) polymer contains two or more types of structural units each represented by Chemical Formula 12.

Although not intended to limit the scope of rights, preferred examples of the polymer (B-3) include polymers of acrylic acid, maleic acid, or a combination thereof. More preferred examples are 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. The copolymer is included in (B-3) and has two types of constitutional units represented by chemical formula 12, in one constitutional unit R ₂₅ is -H, and in another constitutional unit R ₂₅ is -COOH It is.

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 include both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

(B) The highly soluble component may have a molecular weight of 80 to 10,000. The highly soluble component preferably has a molecular weight of 90 to 5,000, more preferably 100 to 3,000. (B) When the highly soluble component is a resin, polymer, or polymer, the molecular weight is expressed in weight average molecular weight (Mw).
(B) The highly soluble component can be obtained either by synthesis or by purchase. Suppliers include Sigma-Aldrich, Tokyo Kasei Kogyo, 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, compared to the mass of the low soluble component (A). In the treatment liquid, the amount of the highly soluble component (B) is more preferably 1 to 30% by mass compared to the mass of the low soluble component (A).
<Solvent>
(C) It is preferable that the solvent contains an organic solvent. (C) The solvent may be volatile. Having volatility means having high volatility compared to water. For example, the boiling point of the solvent (C) at 1 atm is preferably 50 to 250°C. The boiling point of the solvent at 1 atm is more preferably 50 to 200°C, even more preferably 60 to 170°C. It is even more preferable that the boiling point of the solvent at 1 atm is 70 to 150°C. (C) The solvent may also contain a small amount of pure water. The amount of pure water contained in the solvent (C) is preferably 30% by mass or less compared to the entire solvent (C). The amount of pure water contained in the solvent is 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. It is also a preferable form that the solvent does not contain pure water (0% by mass). Pure water is preferably DIW.

Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Alkyl ether acetates, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc. Alkyl ether acetates, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, N,N-dimethylacetamide, N - Amides such as methylpyrrolidone, lactones such as γ-butyrolactone, and the like. These organic solvents can be used alone or in combination of two or more.

In a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When two types of organic solvents are used in combination, the volume ratio thereof is preferably 20:80 to 80:20, more preferably 30:70 to 70:30.
The amount of the solvent (C) is 0.1 to 99.9% by mass compared to the total mass of the treatment liquid. Compared to the total mass of the treatment liquid, the amount of the solvent (C) is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass. The content of the solvent (C) is more preferably 80 to 99% by weight, even more preferably 85 to 99% by weight, compared to the total weight 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 bactericidal agent, a preservative, or an antifungal agent (preferably a surfactant); It may include any combination of these.

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

<Corrosion prevention ingredient>
(F) In addition to BTA, examples of the corrosion-inhibiting component include uric acid, caffeine, buterin, adenine, glyoxylic acid, glucose, fructose, and mannose.
<Other embodiments>
This invention is not limited to the embodiments described above, and can be implemented in other forms.

For example, the top surface of the substrate W may be made hydrophilic by a method such as UV irradiation, plasma treatment, oxygen ashing, or the like, that is, by a method other than treatment with a hydrophilic liquid.
Furthermore, in the embodiments described above, the same organic solvent is used as the replacement liquid and the residue removal liquid. However, if a nozzle for discharging an organic solvent as a replacement liquid and a nozzle for discharging a residue removal liquid are provided, the organic solvent used as a substitution liquid and the organic solvent as a residue removal liquid can be different organic solvents. I can do it. For example, methanol can be used as the substitution liquid, and IPA can be used as the residue removal liquid.

Further, in the embodiment described above, the through hole 102 is formed by partially dissolving the treated film 100 by the stripping solution, and the stripping solution is supplied to the interface between the treated film 100 and the substrate W through the through hole 102. It is expected to reach However, the visually visible through-holes 102 do not necessarily need to be formed, and the treated film 102 can be removed through the gap formed in the treated film 100 when the highly soluble solid 110 in the treated film 100 is dissolved by the stripping liquid. It is also possible that the particles reach the interface between the substrate and the substrate W.

The nozzles that discharge each processing fluid are not limited to those of the embodiments described above. For example, in the embodiment described above, the processing liquid, the hydrophilizing liquid, and the stripping liquid are discharged from the moving nozzle toward the upper surface of the substrate W, and the rinsing liquid, the organic solvent, and the gas are discharged from the fixed nozzle (center nozzle 12) toward the upper surface of the substrate W. is discharged towards the top surface. However, the configuration may be such that the rinsing liquid, the organic solvent, and the gas are discharged from the moving nozzle, or the processing liquid, the hydrophilizing liquid, and the stripping liquid are also discharged from the central nozzle 12 in addition to the rinsing liquid, the organic solvent, and the gas. may be done.

If all the processing fluid is discharged from a moving nozzle or if all the processing fluid is discharged from a fixed nozzle arranged outside the substrate W in plan view, the facing member 6 is not provided. It's okay.
In this specification, when numerical ranges are indicated using "~" or "-", unless otherwise specified, these ranges include both endpoints and the units are common.

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

1: Substrate processing device 3: Controller 9: First moving nozzle (hydrophilic liquid supply unit)
10: Second moving nozzle (processing liquid supply unit)
11: Third moving nozzle (stripping liquid supply unit)
12: Central nozzle (processing film forming unit)
13: Bottom nozzle (processing film forming unit)
21: Spin base (substrate holding unit)
23: Spin motor (processing film forming unit)
62: Opposing member rotation unit (processing film forming unit)
100: Treatment film 102: Through hole 103: Removal target 110: Highly soluble solid 111: Low soluble solid 150: Surface layer 153: Barrier layer (TiN layer)
W: Substrate θ: Contact angle θ1: Contact angle (contact angle of pure water with the surface of the substrate)
θ2: Contact angle (contact angle of pure water to treated membrane)

Claims (16)

a hydrophilic step of making the surface of the substrate hydrophilic;
a treatment liquid supply step of supplying a treatment liquid to the surface of the substrate that has been made hydrophilic;
a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that retains 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 the treated film holding the object to be removed from the surface of the substrate,
The stripping step includes a through hole forming step of partially dissolving the treated film in the stripping solution to form a through hole in the treated film,
A substrate processing method, wherein the hydrophilization step includes a contact angle reducing step of reducing the contact angle of pure water to the surface of the substrate so that the contact angle is smaller than 41.7° . 2. The substrate processing method according to claim 1, wherein the stripping step includes a stripping solution introduction step of introducing a stripping solution between the surface of the substrate and the treated film. 3. The substrate processing method according to claim 1, wherein the hydrophilization step includes a step of making the surface of the substrate hydrophilic by supplying a hydrophilization liquid to the surface of the substrate. 4. The substrate processing method according to claim 3, wherein the hydrophilizing liquid is an oxidizing liquid or an organic solvent. Any one of claims 1 to 4, wherein at least one of Si, SiN, SiO ₂ , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate. 1. The substrate processing method according to item 1. The surface layer of the substrate includes a TiN layer exposed from the surface of the substrate,
4. The substrate processing method according to claim 3, wherein the hydrophilic liquid is an oxidizing liquid. 7. The substrate processing method according to claim 1, wherein the contact angle of pure water with respect to the processing film is greater than 52° and smaller than 61 °. The processing liquid contains a solvent and a solute,
The solute has a high solubility component and a low solubility component that has lower solubility in the stripping solution than the high solubility component,
The treated film forming step includes a step of forming the treated film having a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component,
Any one of claims 1 to 7 , wherein the peeling step dissolves the highly soluble solid in the stripping liquid and peels the treated film holding the object to be removed from the surface of the substrate. 1. The substrate processing method according to item 1. a hydrophilic step of making the surface of the substrate hydrophilic;
a treatment liquid supply step of supplying a treatment liquid to the surface of the substrate that has been made hydrophilic;
a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that retains 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 the treated film holding the object to be removed from the surface of the substrate,
A substrate processing method, wherein the hydrophilization step includes a contact angle reducing step of reducing the contact angle of pure water to the surface of the substrate so that the contact angle is smaller than 41.7°. 10. The substrate processing method according to claim 9 , wherein the contact angle of pure water with respect to the processing film is greater than 52[deg.] and smaller than 61[deg.]. a hydrophilic step of making the surface of the substrate hydrophilic;
a treatment liquid supply step of supplying a treatment liquid to the surface of the substrate that has been made hydrophilic;
a treatment film forming step of solidifying or hardening the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate that retains 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 the treated 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 high solubility component and a low solubility component that has lower solubility in the stripping solution than the high solubility component,
The treated film forming step includes a step of forming the treated film having a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component,
The hydrophilization step includes a contact angle reduction step of reducing the contact angle so that the contact angle of pure water with respect to the surface of the substrate is smaller than 41.7°,
A substrate processing method, wherein the peeling step dissolves the highly soluble solid in the stripping liquid and peels the treated film holding the object to be removed from the surface of the substrate. The substrate processing according to claim 11 , wherein at least one of Si, SiN, SiO ₂ , SiGe, Ge, SiCN, W, TiN, Co, Cu, Ru, and amorphous carbon is exposed from the surface of the substrate. Method. The substrate processing method according to claim 11 or 12, wherein the contact angle of pure water with respect to the processing film is greater than 52° and smaller than 61°. a hydrophilic liquid supply unit that supplies a hydrophilic liquid to the surface of the substrate to make the surface of the substrate hydrophilic;
a processing liquid supply unit that supplies processing liquid to the surface of the substrate;
a treatment film forming unit that solidifies or hardens the treatment liquid in contact with the 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 treated film formed on the surface of the substrate;
a controller that controls the hydrophilic liquid supply unit, the treatment liquid supply unit, the treatment film forming unit, and the stripping liquid supply unit,
The controller,
The surface of the substrate is made hydrophilic by supplying a hydrophilic liquid from the hydrophilic liquid supply unit to the surface of the substrate,
supplying a processing liquid from the processing liquid supply unit to the surface of the substrate that has been made hydrophilic;
Solidifying or hardening 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 retains the object to be removed present on the surface of the substrate;
supplying a stripping liquid from the stripping liquid supply unit to the surface of the substrate to peel the treated film holding the object to be removed from the surface of the substrate;
The stripping solution is programmed to partially dissolve the treated film and form through holes in the treated film,
A substrate processing apparatus , wherein the hydrophilization reduces the contact angle of pure water with respect to the surface of the substrate such that the contact angle is smaller than 41.7° . a hydrophilic liquid supply unit that supplies a hydrophilic liquid to the surface of the substrate to make the surface of the substrate hydrophilic;
a processing liquid supply unit that supplies processing liquid to the surface of the substrate;
a treatment film forming unit that solidifies or hardens the treatment liquid in contact with the 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 treated film formed on the surface of the substrate;
a controller that controls the hydrophilic 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 high solubility component and a low solubility component that has lower solubility in the stripping solution than the high solubility component,
The treated film formed on the surface of the substrate has a highly soluble solid formed by the highly soluble component and a low soluble solid formed by the low soluble component,
The controller,
The surface of the substrate is made hydrophilic by supplying a hydrophilic liquid from the hydrophilic liquid supply unit to the surface of the substrate,
supplying a processing liquid from the processing liquid supply unit to the surface of the substrate that has been made hydrophilic;
Solidifying or hardening 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 retains the object to be removed present on the surface of the substrate;
A stripping solution is supplied from the stripping solution supply unit to the surface of the substrate, the highly soluble solid is dissolved in the stripping solution, and the treated film holding the object to be removed is removed from the substrate. Programmed to peel away from surfaces
A substrate processing apparatus , wherein the hydrophilization reduces the contact angle of pure water with respect to the surface of the substrate such that the contact angle is smaller than 41.7° . The substrate processing apparatus according to claim 14 or 15, wherein a contact angle of pure water with respect to the processing film is larger than 52° and smaller than 61°.

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