Substrate processing method, substrate processing apparatus, and processing liquid

Abstract

A substrate processing method includes: a treatment film forming step of supplying a treatment liquid to a surface of a substrate and solidifying or hardening the treatment liquid on the surface of the substrate, thereby forming a treatment film on the surface of the substrate; an etching promoting step of performing etching function exhibiting treatment on the treatment film, thereby promoting etching of a surface layer portion of the substrate based on the treatment film; and an etching moderating step of performing etching function disappearing treatment on the treatment film, thereby moderating etching of the surface layer portion of the substrate based on the treatment film in a state where the treatment film is maintained on the substrate.

Description

Technical Field

[0001] This invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid used in the substrate processing method and the substrate processing apparatus. Substrates that are the objects of processing include, for example, semiconductor wafers, optical disc substrates, magnetic disk substrates, optical disc substrates, photomask substrates, ceramic substrates, solar cell substrates, and substrates for flat panel displays (FPDs) such as liquid crystal display devices, plasma displays, and organic EL (electroluminescence) display devices. Background Technology

[0002] Hydrofluoric acid is used as the etching solution to etch the surface of the substrate (see Patent Document 1 below). After treating the substrate with the etching solution, the surface of the substrate is cleaned with a rinse solution such as DIW (deionized water).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent document 1: U.S. Patent Application Publication No. 2012 / 260949. Summary of the Invention

[0006] The problem the invention aims to solve

[0007] In the substrate processing described in Patent Document 1, the substrate is etched through a liquid flow process. Specifically, etching begins by supplying etchant to the substrate and stops by removing the etchant from the substrate using a rinsing solution. Therefore, even after the rinsing solution is supplied, etching does not stop until the etchant is removed from the substrate. Consequently, the timing of etching cessation is unclear, raising concerns about the inability to precisely etch the surface layer of the substrate.

[0008] Therefore, one object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid that can improve the controllability of etching of the surface layer of a substrate.

[0009] means for solving problems

[0010] One embodiment of the present invention provides a substrate processing method, comprising: a processing film forming step, wherein a processing liquid is supplied to the surface of a substrate and the processing liquid on the surface of the substrate is solidified or hardened, thereby forming a processing film on the surface of the substrate; an etching promotion step, wherein the processing film is subjected to an etching function demonstration process, thereby promoting etching of the surface portion of the substrate based on the processing film; and an etching mitigation step, wherein the etching function of the processing film is removed, thereby mitigating etching of the surface portion of the substrate based on the processing film while the processing film is maintained on the substrate.

[0011] According to this substrate processing method, etching of the surface layer of the substrate based on the processing film does not begin during the formation of the processing film, but is promoted by the opportunity presented by the etching function of the processing film. Furthermore, there is no need to remove the processing film to mitigate etching; instead, the etching is mitigated by maintaining the processing film on the substrate and the opportunity presented by the disappearance of the etching function of the processing film. Therefore, the state of etch promotion and the state of etch mitigation can be switched according to the processing of the processing film. Thus, the timing of etch promotion and the timing of etch mitigation are easily controlled. Therefore, the controllability of etching on the surface layer of the substrate can be improved.

[0012] The term "etching promotion" refers to both: initiating etching from a state where etching has completely stopped; and increasing the rate of etching that has already begun. Similarly, the term "etching mitigation" refers to both: completely stopping the progress of etching; and reducing the rate of etching that is progressing.

[0013] In one embodiment of the present invention, the aforementioned etching function enhancement process includes: a heat strengthening process to enhance the heating of the aforementioned treated film. The aforementioned etching function disappearance process includes: a heat weakening process to reduce the heating of the aforementioned treated film.

[0014] According to this substrate processing method, etching is promoted by increasing the heating of the processing film. On the other hand, etching is mitigated by decreasing the heating of the processing film. Since the promotion and mitigation of etching are initiated by actively changing the intensity of heating, it is easy to control the timing of the promotion and mitigation of etching. Therefore, the controllability of etching on the surface layer of the substrate can be improved.

[0015] In one embodiment of the present invention, the aforementioned etching function manifestation process includes: a pH adjustment process, in which a pH adjustment solution is supplied to the aforementioned treatment film on the aforementioned substrate to adjust the pH of the aforementioned treatment film to be acidic or alkaline. Furthermore, the aforementioned etching function disappearance process includes: a neutralization process, in which a neutralizing solution is supplied to the aforementioned treatment film on the aforementioned substrate to make the pH of the aforementioned treatment film closer to neutral than the pH of the aforementioned treatment film after the aforementioned pH adjustment process.

[0016] According to this substrate processing method, a pH-adjusting solution is supplied to the processing film, thereby adjusting the pH value of the liquid components contained in the processing film to acidic or alkaline, thus promoting etching. On the other hand, by supplying a neutralizing solution to the processing film, the pH value of the liquid components contained in the processing film is brought close to neutral, thereby moderating etching. Since the promotion and de-escalation of etching are triggered by an active process of changing the pH, it is easy to control the timing of etching promotion and the timing of etching de-escalation. Therefore, the controllability of etching on the surface layer of the substrate can be improved.

[0017] In one embodiment of the present invention, a processing film containing a functional display component is formed in the aforementioned processing film formation process, and the aforementioned functional display component displays an etching function through the aforementioned etching function display process. Therefore, by etching the surface portion of the substrate with a processing film in which the amount of functional display component has been adjusted, the etching amount of the surface portion of the substrate can be controlled.

[0018] In one embodiment of the present invention, the aforementioned functional exhibiting component is a polymer in which protons are released into the aforementioned processed film through the aforementioned etching functional exhibiting process, and protons are taken from the aforementioned processed film through the aforementioned etching functional disappearance process. The aforementioned etching promotion process includes the step of releasing the aforementioned protons from the aforementioned polymer through the aforementioned etching functional exhibiting process, thereby promoting the etching of the surface layer of the aforementioned substrate. Moreover, the aforementioned etching mitigation process includes the step of imparting the aforementioned protons to the aforementioned polymer through the aforementioned etching functional disappearance process, thereby mitigating the etching of the surface layer of the aforementioned substrate.

[0019] Etching of the substrate surface is promoted by protons released from the polymer, and etching of the substrate surface is mitigated by the polymer taking over the protons.

[0020] Therefore, as long as the polymer releases protons through etching and accepts protons through etching removal, the etching of the substrate surface can be accelerated or decelerated by switching the processing performed on the film. Examples of such polymers include copolymers of N-isopropylacrylamide, N,N'-methylenebisacrylamide, and acrylic acid.

[0021] In one embodiment of the present invention, the aforementioned functional exhibiting component is a polymer having a plurality of constituent units and including an organic acid as one of the constituent units. The aforementioned etching promotion process includes the following steps: decomposing the aforementioned polymer through the aforementioned etching functional exhibiting treatment to form a plurality of monomers including a monomeric organic acid, thereby promoting the etching of the surface layer of the aforementioned substrate. Furthermore, the aforementioned etching mitigation process includes the following steps: polymerizing the plurality of monomers in the aforementioned treated film through the aforementioned etching functional disappearance treatment to form the aforementioned polymer, thereby mitigating the etching of the surface layer of the aforementioned substrate.

[0022] Since the acidity of the monomeric organic acid is higher than that of the organic acid that forms the building blocks of the polymer, it can etch the surface layer of the substrate. Therefore, as long as the polymer is decomposed by etching to form a plurality of monomers and then polymerized by etching to form a polymer, the etching of the substrate surface layer can be controlled by switching the processing of the film. Examples of such polymers include copolymers of N-isopropylacrylamide and acrylic acid, where acrylic acid is the organic acid.

[0023] In one embodiment of the present invention, the etching process is performed cyclically multiple times, wherein the etching process includes the etching acceleration step and the etching mitigation step as a single cycle. Therefore, the etching amount of the surface layer of the substrate can be precisely controlled by the number of etching cycles performed.

[0024] In one embodiment of the present invention, the aforementioned substrate processing method further includes a processing film removal step, wherein a removal liquid is supplied to the surface of the processing film, thereby removing the processing film from the surface of the substrate. By removing the processing film with the removal liquid, the surface of the substrate can be cleaned.

[0025] In one embodiment of the present invention, the aforementioned treatment film removal process includes a dissolution removal process, in which the aforementioned removal liquid dissolves the aforementioned treatment film, thereby removing the aforementioned treatment film from the surface of the aforementioned substrate. According to this substrate processing method, the removal liquid dissolves the treatment film, thereby enabling rapid removal of the treatment film from the surface of the substrate.

[0026] In one embodiment of the present invention, the aforementioned treatment film removal process includes a peeling removal process, wherein the aforementioned treatment film is peeled off from the surface of the aforementioned substrate using the aforementioned removal liquid, thereby removing the aforementioned treatment film from the surface of the aforementioned substrate.

[0027] According to this substrate processing method, the processing film is not removed from the substrate surface by being dissolved by a stripping liquid, but rather peeled off from the substrate surface. Therefore, in cases where particles or other substances to be removed are attached to the substrate surface, the processing film is peeled off from the substrate surface while still containing these substances. As a result, the substances to be removed can be peeled off and removed from the substrate surface.

[0028] In one embodiment of the present invention, the aforementioned processing film is formed in the aforementioned processing film formation step, comprising a low-soluble component in a solid state and a high-soluble component in a solid state, wherein the high-soluble component in the solid state has higher solubility in the aforementioned removal liquid than the low-soluble component. Furthermore, the aforementioned peel-off removal step includes the step of selectively dissolving the high-soluble component in the aforementioned removal liquid while maintaining the low-soluble component in a solid state, thereby peeling the aforementioned processing film off from the surface of the aforementioned substrate.

[0029] According to this substrate processing method, highly soluble components in the solid state of the processed film are selectively dissolved by the removal liquid. The phrase "selectively dissolved highly soluble components in the solid state" does not mean that only highly soluble components in the solid state are dissolved. Rather, it means that while less soluble components in the solid state are also slightly dissolved, the majority of the highly soluble components in the solid state are dissolved.

[0030] By selectively dissolving highly soluble components in a solid state, gaps are formed in the treated film, through which the removal liquid reaches the contact interface between the treated film and the substrate. Meanwhile, the less soluble components in the treated film are maintained in a solid state. Therefore, when the object to be removed is present on the surface of the substrate, the object to be removed can be held in place by the less soluble components in a solid state while the removal liquid acts on the contact interface between the less soluble components in a solid state and the substrate. As a result, the treated film can be rapidly removed from the surface of the substrate, and the object to be removed along with the treated film can be efficiently removed from the surface of the substrate.

[0031] In one embodiment of the present invention, the surface layer of the aforementioned substrate is etched, thereby forming etching residue held by the aforementioned processing film. Furthermore, the aforementioned processing film removal process includes the following step: removing the aforementioned etching residue together with the aforementioned processing film while the aforementioned etching residue is held by the aforementioned processing film.

[0032] According to this substrate processing method, the etching residue generated from etching the surface of the substrate is removed from the substrate surface along with the processing film during the processing film removal process. Therefore, there is no need to perform a separate process to remove etching residue after removing the processing film.

[0033] In one embodiment of the present invention, a trench that is circular in shape when viewed from above is formed on the aforementioned substrate, the trench causing a depression in the surface of the aforementioned substrate. The trench has a bottom wall and a side wall, the side wall being connected to the bottom wall and extending in the depth direction of the trench. The side wall has: a bottom wall side portion connected to the aforementioned bottom wall; and an opening side portion dividing the opening of the aforementioned trench. Moreover, the aforementioned processing film forming process includes the following step: forming the aforementioned processing film for covering the aforementioned bottom wall side portion and the aforementioned bottom wall.

[0034] According to this substrate processing method, a processing film is formed that covers the bottom wall and the bottom wall side of the sidewalls, but not the opening side of the sidewalls. Therefore, the surface layer of the substrate can be etched only near the bottom wall within the trench. Therefore, the width of the trench can be expanded only near the bottom wall within the trench. In this way, the area etched on the surface of the substrate can be controlled by controlling the area where the processing film is formed.

[0035] Other embodiments of the present invention provide a substrate processing apparatus, comprising: a processing liquid supply unit for supplying processing liquid toward the surface of a substrate; a processing film forming unit for solidifying or hardening the processing liquid on the surface of the substrate, thereby forming a processing film on the surface of the substrate; a processing film heating unit for heating the processing film; a heating adjustment unit for adjusting the degree of heating of the processing film based on the heating unit; and a controller for controlling the processing liquid supply unit, the processing film forming unit, the processing film heating unit, and the heating adjustment unit.

[0036] The aforementioned controller is programmed to execute: a processing film formation process, supplying processing liquid from the aforementioned processing liquid supply unit toward the surface of the aforementioned substrate, and solidifying or hardening the processing liquid on the surface of the aforementioned substrate by the aforementioned processing film formation unit, thereby forming a processing film on the surface of the aforementioned substrate; an etching promotion process, strengthening the heating of the aforementioned processing film based on the aforementioned processing film heating unit by the aforementioned heating adjustment unit, thereby promoting the etching of the surface portion of the aforementioned substrate based on the aforementioned processing film; and an etching mitigation process, weakening the heating of the aforementioned processing film based on the aforementioned processing film heating unit by the aforementioned heating adjustment unit, thereby mitigating the etching of the surface portion of the aforementioned substrate while maintaining the aforementioned processing film on the aforementioned substrate.

[0037] According to this substrate processing apparatus, etching of the surface layer of the substrate based on the processing film is not promoted during the formation of the processing film, but rather promoted by intensifying the heating of the processing film. Furthermore, it is not necessary to remove the processing film to mitigate etching; instead, the etching is mitigated by reducing the heating of the processing film while it is held on the substrate. That is, the state of etching progress and the state of etch mitigation can be switched according to the intensity of heating the processing film. Therefore, the timing of etching promotion and etching mitigation is easily controlled. Thus, the controllability of etching of the substrate surface layer can be improved.

[0038] Another embodiment of the present invention provides a substrate processing apparatus, comprising: a processing liquid supply unit for supplying processing liquid to the surface of a substrate; a processing film forming unit for solidifying or hardening the processing liquid on the surface of the substrate, thereby forming a processing film on the surface of the substrate; a pH adjusting liquid supply unit for supplying pH adjusting liquid to the surface of the substrate, wherein the pH adjusting liquid adjusts the pH of the processing film to acidic or alkaline; a neutralizing liquid supply unit for supplying neutralizing liquid to the surface of the substrate, wherein the neutralizing liquid makes the pH of the processing film close to neutral; and a controller for controlling the processing liquid supply unit, the processing film forming unit, the pH adjusting liquid supply unit, and the neutralizing liquid supply unit.

[0039] The aforementioned controller is programmed to execute: a processing film formation step, supplying processing liquid from the aforementioned processing liquid supply unit toward the surface of the aforementioned substrate, and solidifying or hardening the processing liquid on the surface of the aforementioned substrate by the aforementioned processing film formation unit, thereby forming a processing film on the surface of the aforementioned substrate; an etching promotion step, supplying the aforementioned pH adjustment liquid from the aforementioned pH adjustment liquid supply unit toward the surface of the aforementioned substrate and adjusting the pH in the aforementioned processing film to acidic or alkaline, thereby promoting etching of the surface portion of the aforementioned substrate based on the aforementioned processing film; and an etching mitigation step, supplying the aforementioned neutralization liquid from the aforementioned neutralization liquid supply unit toward the surface of the aforementioned substrate, making the pH in the aforementioned processing film closer to neutral than the pH in the aforementioned processing film after adjustment by the aforementioned pH adjustment liquid, thereby mitigating etching of the surface portion of the aforementioned substrate while maintaining the aforementioned processing film on the aforementioned substrate.

[0040] According to this substrate processing apparatus, etching of the surface layer of the substrate based on the processing film is not promoted during the formation of the processing film, but rather promoted by adjusting the pH of the processing film to acidic or alkaline using a pH adjusting solution. Furthermore, it is not necessary to remove the processing film to mitigate etching; instead, the pH of the processing film is brought close to neutral using a neutralizing solution, thus mitigating the etching. In other words, the state of etching progress and the state of etch mitigation can be switched according to changes in the pH of the processing film. Therefore, the timing of etching promotion and etching mitigation is easily controlled. Consequently, the controllability of etching on the surface layer of the substrate can be improved.

[0041] Another embodiment of the present invention provides a processing liquid for forming a processing film on the surface of a substrate by curing or hardening. The processing liquid contains a polymer that promotes etching of the surface portion of the substrate based on the aforementioned processing film through an etching function exhibiting process, and mitigates etching of the surface portion of the substrate based on the aforementioned processing film through an etching function disappearing process.

[0042] Based on this configuration, etching of the surface layer of the substrate based on the processing film does not begin during the formation of the processing film, but is promoted by the processing of the etching function of the processing film. Furthermore, there is no need to remove the processing film to mitigate etching; instead, the etching is mitigated by maintaining the processing film on the substrate and then allowing the etching function of the processing film to disappear. Therefore, the state of etch promotion and the state of etch mitigation can be switched according to the processing of the processing film. Thus, the timing of etch promotion and etch mitigation is easily controlled. Therefore, the controllability of etching on the surface layer of the substrate can be improved.

[0043] The above and other objects, features and effects of the present invention will become clearer with reference to the accompanying drawings and through the following description of embodiments. Attached Figure Description

[0044] Figure 1 This is a schematic top view showing the layout of the substrate processing apparatus according to the first embodiment of the present invention.

[0045] Figure 2 This is a schematic partial cross-sectional view showing the general configuration of the processing units included in the aforementioned substrate processing apparatus.

[0046] Figure 3 This is a schematic diagram illustrating the etching mechanism of temperature-responsive polymers.

[0047] Figure 4 This is a schematic diagram illustrating an example of the aforementioned temperature-responsive polymer.

[0048] Figure 5 This is a block diagram showing the electrical configuration of the main parts of the aforementioned substrate processing apparatus.

[0049] Figure 6 This is a flowchart illustrating an example of substrate processing based on the aforementioned substrate processing apparatus.

[0050] Figure 7A This is a schematic diagram illustrating the state of the processing solution supply process (step S2) for the aforementioned substrate processing.

[0051] Figure 7BThis is a schematic diagram illustrating the state of the processing film formation process (step S3) of the aforementioned substrate processing.

[0052] Figure 7C This is a schematic diagram illustrating the state of the aforementioned membrane formation process (step S3).

[0053] Figure 7D This is a schematic diagram illustrating the state of the aforementioned substrate processing etching acceleration process (step S4).

[0054] Figure 7E This is a schematic diagram illustrating the state of the aforementioned substrate processing etching mitigation process (step S5).

[0055] Figure 7F This is a schematic diagram illustrating the state of the aforementioned substrate processing film removal process (step S6).

[0056] Figure 7G This is a schematic diagram illustrating the state of the aforementioned membrane removal process (step S6).

[0057] Figure 7H This is a schematic diagram illustrating the state of the cleaning process (step S7) of the aforementioned substrate treatment.

[0058] Figure 7I This is a schematic diagram illustrating the state of the aforementioned substrate processing residue removal process (step S8).

[0059] Figure 8A This is a schematic diagram used to illustrate the state near the surface of the substrate during the aforementioned substrate processing.

[0060] Figure 8B This is a schematic diagram used to illustrate the state near the surface of the substrate during the aforementioned substrate processing.

[0061] Figure 8C This is a schematic diagram used to illustrate the state near the surface of the substrate during the aforementioned substrate processing.

[0062] Figure 8D This is a schematic diagram used to illustrate the state near the surface of the substrate during the aforementioned substrate processing.

[0063] Figure 8E This is a schematic diagram used to illustrate the state near the surface of the substrate during the aforementioned substrate processing.

[0064] Figure 8F This is a schematic diagram used to illustrate the state near the surface of the substrate during the aforementioned substrate processing.

[0065] Figure 9 This is a schematic diagram illustrating the structure of a substrate with grooves on its surface.

[0066] Figure 10A This is a schematic diagram illustrating the state of the surface layer of the substrate near the trench of the substrate in the aforementioned processing film formation process (step S3).

[0067] Figure 10B This is a schematic diagram illustrating the state of the surface layer of the substrate near the trench after the aforementioned film formation process (step S3).

[0068] Figure 10C This is a schematic diagram illustrating the state of the surface layer of the substrate near the trench after the aforementioned film removal process (step S6).

[0069] Figure 11 This is a schematic partial cross-sectional view showing the general configuration of the processing unit included in the substrate processing apparatus of the second embodiment.

[0070] Figure 12 This is a flowchart illustrating an example of substrate processing based on the substrate processing apparatus of the second embodiment.

[0071] Figure 13A This is a schematic diagram illustrating the state of removing the processing film from the surface of the substrate during the substrate processing in the second embodiment.

[0072] Figure 13B This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the second embodiment.

[0073] Figure 13C This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the second embodiment.

[0074] Figure 13D This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the second embodiment.

[0075] Figure 13E This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the second embodiment.

[0076] Figure 14 This is a schematic diagram showing the general configuration of the processing unit included in the substrate processing apparatus of the third embodiment.

[0077] Figure 15 This is a schematic diagram illustrating an example of a pH-responsive polymer.

[0078] Figure 16A This is a schematic diagram illustrating an example of an etching acceleration step (step S4) in substrate processing of a substrate processing apparatus based on the third embodiment.

[0079] Figure 16B This is a schematic diagram illustrating an example of an etching mitigation process (step S5) in substrate processing of a substrate processing apparatus based on the third embodiment.

[0080] Figure 17A This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the third embodiment.

[0081] Figure 17B This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the third embodiment.

[0082] Figure 17C This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the third embodiment.

[0083] Figure 17D This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the third embodiment.

[0084] Figure 17E This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the third embodiment.

[0085] Figure 17F This is a schematic diagram illustrating the state near the surface of the substrate during substrate processing in the third embodiment. Detailed Implementation

[0086] [First Implementation Method]

[0087] Figure 1 This is a schematic top view showing the layout of the substrate processing apparatus 1 according to the first embodiment of the present invention.

[0088] The substrate processing apparatus 1 is a leaf-type apparatus used to process substrates W, such as silicon wafers, one by one. In this embodiment, the substrate W is a circular plate-shaped substrate. As the substrate W, a substrate with an etchable component exposed on its surface can be used. Preferably, a substrate W with at least one of SiO2 (silicon oxide), TiN (titanium nitride), Cu (copper), and Ru (ruthenium) exposed on its surface is used. Only one of these substances may be exposed on the surface of the substrate W, or multiple substances may be exposed. Etcable substances other than those mentioned above may also be exposed on the surface of the substrate W.

[0089] The substrate processing apparatus 1 includes: a plurality of processing units 2 for fluid processing of substrates W; a loadport LP for a carrier C to hold the plurality of substrates W processed by the processing units 2; a transport robot IR and a transport robot CR for transporting substrates W between the loadport LP and the processing units 2; and a controller 3 for controlling the substrate processing apparatus 1.

[0090] The transport robot IR transports the substrate W between the carrier C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing unit 2. A plurality of processing units 2 have, for example, the same configuration. More specifically, as described later, the fluid supplied to the substrate W within the processing unit 2 includes a processing liquid, a stripping removal liquid, a dissolving removal liquid, a cleaning liquid (neutralizing liquid), a pH adjusting liquid, a residue removal liquid, etc.

[0091] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed within the chamber 4, and performs processing on the substrate W within the processing cup 7. An entrance / exit (not shown) is formed in the chamber 4 for the substrate W to be moved in and out by a transport robot CR. A shutter unit (not shown) is provided in the chamber 4 to open and close the entrance / exit.

[0092] Figure 2 This is a schematic diagram illustrating an example of the configuration of the processing unit 2. The processing unit 2 includes a spin-in-the-loop fixture 5, a heater unit 6, a processing hood 7, a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11, and a fourth moving nozzle 12.

[0093] The rotating clamp 5 is an example of a substrate holding and rotating unit, used to hold the substrate W horizontally while rotating the substrate W about a rotation axis A1 (vertical axis). The rotation axis A1 is a vertical straight line passing through the center of the substrate W. The rotating clamp 5 includes a plurality of chuck pins 20, a spin base 21, a rotation shaft 22, and a spin motor 23.

[0094] The rotating base 21 has a circular plate shape along the horizontal direction. On the upper surface of the rotating base 21, a plurality of clamping pins 20 for holding the periphery of the substrate W are arranged at intervals around the circumference of the rotating base 21.

[0095] A plurality of clamping pins 20 are opened and closed by the pin opening and closing unit 24. When the plurality of clamping pins 20 are set to the closed state by the pin opening and closing unit 24, the substrate W is held horizontally. When the plurality of clamping pins 20 are set to the open state by the pin opening and closing unit 24, the substrate W is released. When the plurality of clamping pins 20 are in the open state, the substrate W is supported from below.

[0096] The self-rotating base 21 and a plurality of clamping pins 20 constitute a substrate holding unit for horizontally holding the substrate W. The substrate holding unit is also called a substrate holder.

[0097] A rotating shaft 22 extends vertically along the rotation axis A1. The upper end of the rotating shaft 22 is attached to the center of the lower surface of the rotating base 21. A rotating motor 23 applies a rotational force to the rotating shaft 22. The rotating shaft 22 is rotated by the rotating motor 23, thereby rotating the rotating base 21. As a result, the substrate W rotates about the rotation axis A1. The rotating motor 23 is an example of a substrate rotation unit used to rotate the substrate W about the rotation axis A1.

[0098] Heater unit 6 is an example of a substrate heating unit used to heat the entire substrate W. Heater unit 6 has the shape of a circular heating plate. Heater unit 6 is disposed between the upper surface of the rotating base 21 and the lower surface of the substrate W. Heater unit 6 has a facing surface 6a that faces the lower surface of the substrate W from below.

[0099] The heater unit 6 includes a plate body 61 and a heater 62. The plate body 61 is slightly smaller than the substrate W when viewed from above. The upper surface of the plate body 61 forms a facing surface 6a. The heater 62 may also be a resistor built into the plate body 61. The facing surface 6a is heated by energizing the heater 62. The facing surface 6a is heated to, for example, 195°C.

[0100] Processing unit 2 includes: a heater energizing unit 64 that supplies power to heater 62 via power supply line 63; and a heater lifting unit 65 that raises and lowers heater unit 6 relative to rotating base 21. The heater energizing unit 64 is, for example, a power source. The heater lifting unit 65 includes, for example, a ball screw mechanism (not shown); and an electric motor (not shown) that provides driving force to the ball screw mechanism. The heater lifting unit 65 is also referred to as a heater lift.

[0101] A lifting shaft 66 is attached to the lower surface of the heater unit 6, and the lifting shaft 66 extends vertically along the rotation axis A1. The lifting shaft 66 is inserted through a through hole 21a formed in the center of the rotating base 21 and a hollow rotating shaft 22. The power supply line 63 passes through the lifting shaft 66.

[0102] The heater lifting unit 65 raises and lowers the heater unit 6 via the lifting shaft 66. The heater unit 6 can be raised and lowered by the heater lifting unit 65 and can be located in a lower position and an upper position. The heater lifting unit 65 can not only position the heater unit 6 in the lower position and the upper position, but also position the heater unit 6 in any position between the lower position and the upper position.

[0103] The heater unit 6 is able to pick up the substrate W from the plurality of clamping pins 20 in the open state when it is raised. The heater unit 6 is positioned at a position that contacts or is close to the lower surface of the substrate W by means of the heater lifting unit 65, thereby heating the substrate W.

[0104] The processing cover 7 includes: a plurality of guards 71 ​​for catching liquid that splashes outward from the substrate W held by the rotating clamp 5; a plurality of cups 72 for catching liquid that is guided downward through the plurality of guards 71; and a cylindrical outer wall member 73 surrounding the plurality of guards 71 ​​and the plurality of cups 72.

[0105] In this embodiment, an example is shown where two protective covers 71 (first protective cover 71A and second protective cover 71B) and two covers 72 (first cover 72A and second cover 72B) are provided.

[0106] The first cover 72A and the second cover 72B each have an annular groove that opens upwards.

[0107] The first protective cover 71A is configured to surround the rotating base 21. The second protective cover 71B is configured to surround the rotating base 21 further outward than the first protective cover 71A.

[0108] The first protective cover 71A and the second protective cover 71B are each generally cylindrical in shape. The upper end of each protective cover 71 is inclined inward toward the rotating base 21.

[0109] The first cover 72A catches the liquid that is guided downward through the first protective cover 71A. The second cover 72B is integrally formed with the first protective cover 71A and catches the liquid that is guided downward through the second protective cover 71B.

[0110] Processing unit 2 includes: a protective cover lifting unit 74, which causes the first protective cover 71A and the second protective cover 71B to rise and fall in the vertical direction, respectively. The protective cover lifting unit 74 causes the first protective cover 71A to rise and fall between a lower position and an upper position. The protective cover lifting unit 74 causes the second protective cover 71B to rise and fall between a lower position and an upper position.

[0111] When both the first protective cover 71A and the second protective cover 71B are in the upper position, liquid splashed from the substrate W is caught by the first protective cover 71A. When the first protective cover 71A is in the lower position and the second protective cover 71B is in the upper position, liquid splashed from the substrate W is caught by the second protective cover 71B. When both the first protective cover 71A and the second protective cover 71B are in the lower position, the handling robot CR can access the rotating gripper 5 in order to load and unload the substrate W.

[0112] The protective cover lifting unit 74 includes, for example: a first ball screw mechanism (not shown) coupled to a first protective cover 71A; a first motor (not shown) providing driving force to the first ball screw mechanism; a second ball screw mechanism (not shown) coupled to a second protective cover 71B; and a second motor (not shown) providing driving force to the second ball screw mechanism. The protective cover lifting unit 74 is also referred to as a protective cover lift.

[0113] The first moving nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) used to supply (spray) processing liquid toward the upper surface (upper side surface) of the substrate W held by the rotating clamp 5.

[0114] The first moving nozzle 9 moves horizontally and vertically via the first nozzle moving unit 35. The first moving nozzle 9 can move horizontally between a center position and a starting position (home position) (retreat position). When in the center position, the first moving nozzle 9 faces the central region of the upper surface of the substrate W.

[0115] When in the initial position, the first moving nozzle 9 is not facing the upper surface of the substrate W, but is located outside the processing cover 7 when viewed from above. The first moving nozzle 9 can approach the upper surface of the substrate W and retreat from the upper surface of the substrate W to the upper surface by moving in the vertical direction.

[0116] The first nozzle moving unit 35 may also include: an arm (not shown) coupled to the first moving nozzle 9 and extending horizontally; a rotating shaft (not shown) coupled to the arm and extending vertically; and a rotating shaft driving unit (not shown) for raising, lowering or rotating the rotating shaft.

[0117] The rotation shaft drive unit causes the rotation shaft to rotate about a vertical rotation axis, thereby causing the arm to swing. Furthermore, the rotation shaft drive unit causes the rotation shaft to move up and down in the vertical direction, thereby causing the arm to rise and fall. Based on the arm's swinging and rising / falling motion, the first moving nozzle 9 moves in both the horizontal and vertical directions.

[0118] The first movable nozzle 9 is connected to the processing fluid piping 40, which guides the processing fluid to the first movable nozzle 9. When the processing fluid valve 50, which is clamped to the processing fluid piping 40, is opened, the processing fluid is continuously ejected downward from the first movable nozzle 9. When the first movable nozzle 9 is in the central position, when the processing fluid valve 50 is open, the processing fluid is supplied to the central region of the upper surface of the substrate W.

[0119] The processing solution contains a solute and a solvent. The processing solution solidifies or hardens by the evaporation (evaporation) of at least a portion of the solvent contained in the processing solution. The processing solution solidifies or hardens on the substrate W, thereby forming a solid processing film. During the solidification or hardening of the processing solution, the processing film captures and retains the object to be removed from the substrate W. The object to be removed is, for example, foreign matter such as particles adhering to the surface of the substrate W.

[0120] Here, "solidification" refers to the solidification of a solute, for example, through forces acting between molecules and atoms accompanying the evaporation of the solvent. "Hardening" refers to the solidification of a solute, for example, through chemical changes such as polymerization or cross-linking. Therefore, "solidification or hardening" refers to the solidification of a solute due to various factors.

[0121] Furthermore, the treatment membrane does not need to be composed solely of solid components. As long as the membrane maintains a fixed overall shape, it can also be a semi-solid membrane composed of both solid and liquid components. That is, solvent residue can remain in the treatment membrane without completely removing the solvent from the treatment solution.

[0122] The treatment solution contains functional components that act as solutes, components with low solubility, and components with high solubility.

[0123] The functional exhibiting component comprises a component that exhibits (enhances) etching function through a predetermined etching function exhibiting treatment, and that causes the etching function to disappear (weaken) through a predetermined etching function disappearance treatment. In the first embodiment, the functional exhibiting component is a temperature-responsive polymer. The temperature-responsive polymer has the property that it exhibits (enhances) etching function by strengthening heating, and causes etching function to disappear (weaken) by weakening heating. That is, the etching function exhibiting treatment is a heat enhancement treatment to strengthen the heating of the processed film, and the etching function disappearance treatment is a heat weakening treatment to weaken the heating of the processed film. The so-called weakening heating can be either stopping heating or cooling. The temperature-responsive polymer can also be a copolymer having a plurality of constituent units.

[0124] Figure 3 This is a schematic diagram illustrating the etching mechanism of temperature-responsive polymers. Temperature-responsive polymers contain functional groups such as carboxyl groups within their molecules that can release protons.

[0125] In order to enable the temperature-responsive polymer to release protons, the treatment membrane is not formed solely of solid components, but is preferably a semi-solid (gel-like) mixture of liquid and solid components, with water being the preferred liquid component.

[0126] Temperature-responsive polymers are enhanced by heat treatment to increase proton (H) levels. + The liquid components released into the treated film exhibit etching function. Temperature-responsive polymers, through a heating weakening treatment, take protons from the liquid components in the treated film, thereby eliminating the etching function.

[0127] For example, the temperature of a temperature-responsive polymer can be increased to above 40°C through a heat-enhancing treatment, thereby releasing protons and promoting etching. Conversely, the temperature of a temperature-responsive polymer can be decreased to below 40°C through a heat-weakening treatment, thereby accepting protons and moderating etching.

[0128] The term "etching promotion" refers to both: initiating etching from a state where etching has completely stopped; and increasing the rate of etching that has already begun. Similarly, the term "etching mitigation" refers to both: completely stopping the progress of etching; and reducing the rate of etching that is progressing.

[0129] Figure 4 This is a schematic diagram illustrating a method for synthesizing a temperature-responsive polymer. As a temperature-responsive polymer, a copolymer of N-isopropylacrylamide, acrylic acid, and N,N'-methylenebisacrylamide (the first copolymer) can be used. N-isopropylacrylamide, acrylic acid, and N,N'-methylenebisacrylamide are the building blocks of the first copolymer. The first copolymer is a hydrogel containing water as a liquid component. Acrylic acid is an organic acid contained in the first copolymer as a building block.

[0130] The first copolymer is formed, for example, by reacting N-isopropylacrylamide, N,N'-methylenebisacrylamide, and acrylic acid in the presence of APS (ammonium persulfate) and TMEDA (tetramethylethylenediamine) at room temperature. N,N'-methylenebisacrylamide acts as a crosslinking agent.

[0131] As a highly soluble component contained as a solute in the treatment solution, a substance with high solubility in the stripping and removal solution described later can be used. An example of a highly soluble component is 2,2-bis(4-hydroxyphenyl)propane. However, the highly soluble component is not limited to 2,2-bis(4-hydroxyphenyl)propane. A detailed description of highly soluble components is provided later.

[0132] As a low-soluble component contained as a solute in the treatment solution, a substance with lower solubility in the stripping and removal solution described later than the high-soluble component can be used. An example of a low-soluble component is phenolic varnish (novolac).

[0133] The solvent contained in the treatment solution only needs to be a liquid used to dissolve the functional components, low-soluble components, and high-soluble components. Preferably, the solvent contained in the treatment solution is a liquid with miscibility (miscibility) with the stripping and removal liquid. Miscibility refers to the property of two liquids to dissolve and mix with each other. Examples of solvents contained in the treatment solution include alcohols such as isopropanol (IPA).

[0134] The treatment membrane is mainly composed of functional components in a solid state (functionally manifested solids), low-soluble components in a solid state (low-soluble solids), and highly soluble components in a solid state (high-soluble solids). The solid state is not limited to a state composed solely of solid components; it also includes a gel state containing liquid components. Detailed descriptions of the solvents, low-soluble components, and highly soluble components contained in the treatment solution are provided later.

[0135] Refer again Figure 2 The second moving nozzle 10 is an example of a stripping removal liquid nozzle (stripping removal liquid supply unit), used to continuously supply (spray) stripping removal liquid such as ammonia towards the upper surface of the substrate W held by the rotating clamp 5. The stripping removal liquid is a liquid used to peel off the treatment film formed on the substrate W from the upper surface of the substrate W.

[0136] The second movable nozzle 10 moves in both the horizontal and vertical directions via the second nozzle moving unit 36. The second movable nozzle 10 can move in the horizontal direction between a center position and a starting position (retreat position).

[0137] When the second moving nozzle 10 is in the center position, it faces the central region of the upper surface of the substrate W. When the second moving nozzle 10 is in the initial position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 when viewed from above. The second moving nozzle 10 can approach the upper surface of the substrate W and retreat from the upper surface of the substrate W to the upper surface by moving in the vertical direction.

[0138] The second nozzle moving unit 36 ​​has the same configuration as the first nozzle moving unit 35. That is, the second nozzle moving unit 36 ​​may also include: an arm (not shown) connected to the second moving nozzle 10 and extending horizontally; a rotating shaft (not shown) connected to the arm and extending in a vertical direction; and a rotating shaft drive unit (not shown) to raise, lower, or rotate the rotating shaft.

[0139] The second movable nozzle 10 is connected to the stripping fluid piping 41, which guides the stripping fluid to the second movable nozzle 10. When the stripping fluid valve 51, which is clamped in the stripping fluid piping 41, is open, the stripping fluid is continuously sprayed downwards from the nozzle outlet of the second movable nozzle 10. When the second movable nozzle 10 is in the central position and the stripping fluid valve 51 is open, the stripping fluid is supplied to the central region of the upper surface of the substrate W.

[0140] The stripping and removal fluid ejected from the second moving nozzle 10 can be a liquid that makes highly soluble components more easily soluble than low-soluble components.

[0141] The stripping and removal liquid sprayed from the second movable nozzle 10 is, for example, an alkaline aqueous solution (alkaline liquid) such as ammonia. Specific examples of alkaline aqueous solutions include ammonia, SC1 liquid (Standard Clean-1; the first standard cleaning solution, i.e., an ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide) aqueous solution, choline aqueous solution, and any combination of these solutions.

[0142] The third movable nozzle 11 is an example of a cleaning fluid nozzle (cleaning fluid supply unit), used to continuously supply (spray) cleaning fluid such as pure water to the upper surface of the substrate W held by the rotating clamp 5. The cleaning fluid is a liquid used to rinse the surface of the substrate W.

[0143] The third moving nozzle 11 moves in both the horizontal and vertical directions via the third nozzle moving unit 37. The third moving nozzle 11 can move in the horizontal direction between the center position and the starting position (retreat position).

[0144] When the third moving nozzle 11 is in the center position, it faces the central region of the upper surface of the substrate W. When the third moving nozzle 11 is in the starting position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 when viewed from above. The third moving nozzle 11 can approach the upper surface of the substrate W and retreat from the upper surface of the substrate W to the top by moving in the vertical direction.

[0145] 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 may also include: an arm (not shown) connected to the third moving nozzle 11 and extending horizontally; a rotating shaft (not shown) connected to the arm and extending in a vertical direction; and a rotating shaft drive unit (not shown) to raise or lower or rotate the rotating shaft.

[0146] The third movable nozzle 11 is connected to the cleaning fluid pipe 42, which guides the cleaning fluid to the third movable nozzle 11. When the cleaning fluid valve 52, which is clamped in the cleaning fluid pipe 42, is opened, the cleaning fluid is continuously sprayed downward from the nozzle outlet of the third movable nozzle 11. When the third movable nozzle 11 is in the central position, when the cleaning fluid valve 52 is open, the cleaning fluid is supplied to the central region of the upper surface of the substrate W.

[0147] Examples of cleaning solutions include pure water (such as DIW), carbonated water, electrolyzed ionized water, hydrochloric acid with a dilution concentration (e.g., about 1 ppm to 100 ppm), ammonia with a dilution concentration (e.g., about 1 ppm to 100 ppm), and reduced water (hydrogen water).

[0148] The fourth moving nozzle 12 is an example of a residue removal liquid nozzle (residue removal liquid supply unit), used to continuously supply (spray) residue removal liquid such as organic solvents toward the upper surface of the substrate W held by the rotating clamp 5.

[0149] The fourth moving nozzle 12 moves in both the horizontal and vertical directions via the fourth nozzle moving unit 38. The fourth moving nozzle 12 can move between a center position and a starting position (retreat position) in the horizontal direction.

[0150] When the fourth moving nozzle 12 is in the center position, it faces the central region of the upper surface of the substrate W. When the fourth moving nozzle 12 is in the initial position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 when viewed from above. The fourth moving nozzle 12 can approach the upper surface of the substrate W and retreat from the upper surface of the substrate W to the upper surface by moving in the vertical direction.

[0151] The fourth nozzle moving unit 38 has the same configuration as the first nozzle moving unit 35. That is, the fourth nozzle moving unit 38 may also include: an arm (not shown) connected to the fourth moving nozzle 12 and extending horizontally; a rotating shaft (not shown) connected to the arm and extending in a vertical direction; and a rotating shaft drive unit (not shown) to raise or lower or rotate the rotating shaft.

[0152] The fourth movable nozzle 12 is connected to the residue removal liquid piping 43, which guides the residue removal liquid to the fourth movable nozzle 12. When the residue removal liquid valve 53, which is clamped in the residue removal liquid piping 43, is opened, the residue removal liquid is continuously sprayed downward from the nozzle outlet of the fourth movable nozzle 12. When the fourth movable nozzle 12 is in the central position, when the residue removal liquid valve 53 is open, the residue removal liquid is supplied to the central region of the upper surface of the substrate W.

[0153] The residue removal solution is a liquid that, after being supplied to the substrate W, washes away and removes the slight residue of the processed film remaining on the substrate W from its upper surface. Therefore, the residue removal solution is miscible with the stripping solution. After being peeled off from the upper surface of the substrate W by the stripping solution and removed, the residue removal solution dissolves and removes the residue of the processed film remaining on the upper surface of the substrate W. For example, an organic solvent can be used as the residue removal solution. The residue removal solution is also called a residue dissolving solution.

[0154] The residue removal liquid is preferably a low surface tension liquid with a lower surface tension than the cleaning liquid. In the substrate processing described later, the upper surface of the substrate W is not dried by swinging the cleaning liquid off the substrate W, but rather by replacing the cleaning liquid on the substrate W with the residue removal liquid and then swinging the residue removal liquid off the substrate W, thereby drying the upper surface of the substrate W. Therefore, as long as the residue removal liquid is a low surface tension liquid, the surface tension acting on the upper surface of the substrate W can be reduced when drying the upper surface of the substrate W.

[0155] Organic solvents that function as residue removal liquids and low surface tension liquids include liquids containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (Propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.

[0156] Organic solvents that function as residue removal liquids and low surface tension liquids do not necessarily have to be composed of a single component; they can also be liquids mixed with other components. For example, they can be mixtures of IPA and DIW, or mixtures of IPA and HFE.

[0157] Figure 5 This is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus 1. The controller 3 is equipped with a microcomputer and controls the controlled objects of the substrate processing apparatus 1 according to a predetermined control program.

[0158] Specifically, the controller 3 includes a processor (CPU (Central Processing Unit)) 3A and a memory 3B storing control programs. The controller 3 is configured to execute various controls for substrate processing by executing the control programs through the processor 3A.

[0159] Specifically, controller 3 is programmed to control the handling robot IR, CR, self-rotating motor 23, pin opening / closing unit 24, first nozzle moving unit 35, second nozzle moving unit 36, third nozzle moving unit 37, fourth nozzle moving unit 38, heater energizing unit 64, heater lifting unit 65, protective cover lifting unit 74, processing fluid valve 50, stripping removal fluid valve 51, cleaning fluid valve 52, and residue removal fluid valve 53. The controller 3 controls the valves, thereby controlling whether processing fluid is ejected from the corresponding nozzle and the flow rate of the processing fluid ejected from the corresponding nozzle.

[0160] Figure 6 This is a flowchart illustrating an example of substrate processing based on substrate processing apparatus 1. Figure 6 This mainly refers to the processing achieved by executing the program through controller 3. Figures 7A to 7I This is a schematic diagram used to illustrate the state of each step in the substrate processing.

[0161] like Figure 6 As shown, in the substrate processing based on the substrate processing apparatus 1, for example, the following steps are performed sequentially: substrate loading process (step S1), processing liquid supply process (step S2), processing film formation process (step S3), etching start process (step S4), etching stop process (step S5), processing film removal process (step S6), cleaning process (step S7), residue removal process (step S8), spin drying process (step S9), and substrate unloading process (step S10).

[0162] The etching start process (step S4) and the etching stop process (step S5) are performed as a single etching cycle N times (N = 0, 1, 2, 3, ...). That is, the etching process can be performed in only one cycle or in multiple cycles.

[0163] The following mainly refers to Figure 2 as well as Figure 6 Appropriate reference Figures 7A to 7I .

[0164] First, the untreated substrate W is transported by the IR and CR robots (see reference). Figure 1 The substrate W is moved from the carrier C to the processing unit 2 and then transferred to the rotating fixture 5 (step S1). The substrate W is thus held horizontally by the rotating fixture 5 (substrate holding process).

[0165] When the substrate W is being moved in, the heater unit 6 is positioned in a non-heating position while the heater 62 is energized. The non-heating position is a position where the substrate W is not heated. For example, the lower position is a non-heating position. The non-heating position is simply a position where the substrate W is removed without its temperature rising.

[0166] The substrate W held by the rotating clamp 5 continues until the spin-drying process (step S9) ends. During the period from the start of the substrate holding process until the end of the spin-drying process (step S9), the protective cover lifting unit 74 adjusts the height of the first protective cover 71A and the second protective cover 71B so that at least one protective cover 71 is in the upper position. While the substrate W is held by the rotating clamp 5, the rotating motor 23 rotates the rotating base 21. This initiates the rotation of the horizontally held substrate W (substrate rotation process).

[0167] Next, after the transport robot CR retreats to the outside of the processing unit 2, a processing liquid supply process (step S2) is performed to supply processing liquid to the upper surface of the substrate W. Specifically, the first nozzle moving unit 35 moves the first moving nozzle 9 to the processing position. The processing position of the first moving nozzle 9 is, for example, the central position.

[0168] With the first moving nozzle 9 in the processing position, the processing fluid valve 50 is opened. Thus, as... Figure 7A As shown, a processing liquid is supplied (ejected) from the first moving nozzle 9 toward the central region of the upper surface of the rotating substrate W (processing liquid supply process, processing liquid ejection process). The processing liquid supplied to the upper surface of the substrate W is spread to the entire substrate W by centrifugal force. As a result, a liquid film 101 of the processing liquid (processing liquid film) is formed on the substrate W (processing liquid film formation process).

[0169] The processing liquid is supplied from the first moving nozzle 9 for a predetermined time, for example, for 2 to 4 seconds. During the processing liquid supply process, the substrate W rotates at a predetermined processing liquid rotation speed, for example, from 10 rpm to 1500 rpm.

[0170] Next, execute Figure 7B as well as Figure 7C The processing film formation process shown is step S3. In the processing film formation process, the processing liquid on the substrate W is solidified or hardened to form a processing film 100 on the upper surface of the substrate W (see reference). Figure 7C ).

[0171] In the film formation process, the thickness of the liquid film 101 of the processing solution on the substrate W is reduced (processing solution thinning process, processing solution spin-off process). Specifically, the processing solution valve 50 is closed. Thus, as... Figure 7B As shown, the supply of processing liquid to the substrate W is stopped. Next, the first moving nozzle 9 is moved to the starting position by the first nozzle moving unit 35.

[0172] like Figure 7B As shown, in the liquid film formation process, since the substrate W is rotated while the liquid supply to the upper surface of the substrate W is stopped, a portion of the liquid is discharged from the upper surface of the substrate W. As a result, the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness.

[0173] The centrifugal force caused by the rotation of substrate W not only displaces the processing liquid from the upper surface of substrate W, but also acts on the gas in contact with the liquid film 101. Therefore, through the action of centrifugal force, an airflow of this gas is formed from the center side of substrate W towards the periphery. Through this airflow, the solvent in gaseous form in contact with the liquid film 101 is displaced from the atmosphere in contact with substrate W. This promotes the evaporation (evaporation) of the solvent from the processing liquid on substrate W, thereby... Figure 7C The treatment film 100 is shown to be formed (solvent evaporation process). In the treatment film formation process, the rotating motor 23 functions as an evaporation unit (evaporation promotion unit) to evaporate the solvent in the treatment liquid. The rotating motor 23 is an example of a treatment film formation unit.

[0174] In the film formation process, the rotating motor 23 changes the rotation speed of the substrate W to a predetermined film formation speed. The film formation speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept constant within the range of 300 rpm to 1500 rpm, or it can be appropriately changed within the range of 300 rpm to 1500 rpm during the film formation process. The film formation process is performed for a predetermined time, for example, 30 seconds.

[0175] Unlike this type of substrate processing, in the processing film formation process, the removal of the processing liquid based on centrifugal force may not be performed, and the processing film 100 may be formed simply by solvent evaporation. In this case, the consumption of processing liquid can be suppressed.

[0176] Next, the etching promotion process (step S4) is performed, in which a heat strengthening process is carried out to enhance the heating of the treatment film 100, thereby promoting the etching of the surface layer of the substrate W.

[0177] Specifically, the heater lifting unit 65 positions the heater unit 6 in a heating position. This heating position is, for example, an isolated heating position, used to heat the substrate W from a position already removed from the lower surface of the substrate W. Thus, as... Figure 7D As shown, the heating treatment film 100 is heated via the substrate W by the heater unit 6 (treatment film heating process). The heater unit 6 is an example of a treatment film heating unit.

[0178] The heat treatment film 100 is then heated, causing the temperature-responsive polymer to exhibit etching capabilities, thereby promoting etching of the upper surface of the substrate W covered by the treatment film 100 (etching promotion process). Specifically, the temperature-responsive polymer releases protons into the liquid components of the treatment film 100, thereby promoting etching.

[0179] During the period when the proton concentration in the liquid component of the processing film 100 is above a predetermined threshold (pH is below a predetermined threshold), etching of the surface portion of the substrate W continues (etching process). For example, etching of the surface portion of the substrate W continues when the pH is below 4.

[0180] In cases where etching completely stops before the start of heat treatment of the film 100, the etching promotion process is also called the etching start process.

[0181] Next, an etching mitigation process (step S5) is performed, in which a heat weakening process is performed to reduce the heating of the processing film 100, thereby mitigating the etching of the surface portion of the substrate W.

[0182] Specifically, the heater lifting unit 65 positions the heater unit 6 in a non-heating position. Thus, as... Figure 7E As shown, heater unit 6 stops heating the processing film 100 (processing film heating stop process). This reduces the etching function of the temperature-responsive polymer, mitigating etching of the upper surface of the substrate W covered by the processing film 100 (etching mitigation process). Specifically, the temperature-responsive polymer takes protons from the liquid component in the processing film 100, thereby mitigating etching. For example, etching of the surface portion of the substrate W is performed by changing the pH to a value greater than 4. Thus, heater lifting unit 65 is an example of a heating adjustment unit used to adjust the heating level of the processing film 100 based on heater unit 6 (processing film heating unit).

[0183] In cases where etching is completely stopped by stopping the heating process of the film 100, thereby completely eliminating the etching function of the temperature-responsive polymer, the etching process is also called the etching stop process.

[0184] In the case where the etching process, which combines the etching acceleration process and the etching mitigation process into a single cycle, is performed only once, the processing film removal process (step S6) is then performed.

[0185] On the other hand, in the case of performing multiple etching processes, after the etching mitigation process (step S5), the etching acceleration process (step S4) and the etching mitigation process (step S5) are performed again. After repeating the etching acceleration process (step S4) and the etching mitigation process (step S5) a predetermined number of times, the processed film removal process (step S6) is performed.

[0186] In cases where etching acceleration and etching mitigation processes are performed multiple times, the initial etching acceleration process (step S4) may be the etching start process, and the final etching mitigation process (step S5) may be the etching stop process. That is, etching may be completely stopped before the initial etching acceleration process (step S4) and after the final etching stop process (step S5).

[0187] In the process of removing the processing film (step S6), the processing film 100 is peeled off and removed from the upper surface of the substrate W by supplying a stripping and removal liquid to the upper surface of the substrate W (strictly speaking, the surface of the processing film 100).

[0188] Specifically, the second nozzle moving unit 36 ​​moves the second moving nozzle 10 to a processing position. The processing position of the second moving nozzle 10 is, for example, the central position.

[0189] With the second moving nozzle 10 in the processing position, the stripping removal liquid valve 51 is opened. Thus, as... Figure 7F As shown, a stripping removal liquid is supplied (ejected) from the second moving nozzle 10 toward the central region of the upper surface of the rotating substrate W (stripping removal liquid supply process, stripping removal liquid ejection process). The stripping removal liquid supplied to the upper surface of the substrate W is spread to the entire substrate W by centrifugal force. The stripping removal liquid supplied to the upper surface of the substrate W dissolves highly soluble components in the treatment film 100 while reaching the interface between the upper surface of the substrate W and the treatment film 100 and entering between the treatment film 100 and the upper surface of the substrate W. Figure 7G As shown, a stripping and removal liquid is continuously supplied, thereby peeling and removing the treatment film 100 from the upper surface of the substrate W (treatment film removal process). The second moving nozzle 10 is an example of a treatment film removal unit.

[0190] In the film removal process (step S6), the substrate W rotates at a predetermined removal rotation speed, for example, at 800 rpm.

[0191] Next, a cleaning process (step S7) is performed, in which the stripping removal liquid is rinsed off from the upper surface of the substrate W. Specifically, the second nozzle moving unit 36 ​​moves the second moving nozzle 10 to a retracted position. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to a processing position. The processing position of the third moving nozzle 11 is, for example, the central position.

[0192] Next, with the third moving nozzle 11 in the processing position, the cleaning fluid valve 52 is opened. Thus, as... Figure 7H As shown, cleaning fluid is supplied (ejected) from the third moving nozzle 11 toward the central region of the upper surface of the rotating substrate W (cleaning fluid supply process, cleaning fluid ejection process). The cleaning fluid supplied to the upper surface of the substrate W is distributed throughout the entire upper surface of the substrate W by centrifugal force. As a result, the peeling removal fluid adhering to the upper surface of the substrate W is discharged together with the cleaning fluid to the outside of the substrate W and replaced by cleaning fluid (cleaning process, peeling removal fluid discharge process).

[0193] Cleaning solution is supplied to the upper and lower surfaces of substrate W for a predetermined time, for example, 30 seconds. In the cleaning process (step S7), substrate W is rotated at a predetermined cleaning rotation speed, for example, 800 rpm.

[0194] Next, a residue removal process (step S8) is performed, in which an organic solvent or other residue removal liquid is supplied and the residue of the treatment film 100 is removed from the upper surface of the substrate W.

[0195] Specifically, the third nozzle moving unit 37 moves the third moving nozzle 11 to the retracted position. Then, the fourth nozzle moving unit 38 moves the fourth moving nozzle 12 to the processing position. The processing position of the fourth moving nozzle 12 is, for example, the central position.

[0196] Next, with the fourth moving nozzle 12 in the processing position, the residue removal liquid valve 53 is opened. Thus, as... Figure 7I As shown, a residue removal liquid is supplied (ejected) from the fourth moving nozzle 12 toward the central region of the upper surface of the rotating substrate W (residue removal liquid supply process, residue removal liquid ejection process).

[0197] The residue removal liquid supplied from the fourth moving nozzle 12 to the upper surface of the substrate W is radially expanded and spread throughout the entire upper surface of the substrate W under centrifugal force. A problem arises: even after the treatment film 100 is peeled off from and removed from the substrate W by the stripping removal liquid, residue of the treatment film 100 remains on the upper surface of the substrate W. The residue removal liquid supplied to the upper surface of the substrate W dissolves this residue of the treatment film 100 (residue dissolution process). Using centrifugal force, the residue removal liquid, having dissolved the residue of the treatment film 100, is discharged from the periphery of the upper surface of the substrate W. Thus, the residue of the treatment film 100 on the substrate W is removed (residue removal process).

[0198] In the residue removal liquid supply process, the residue removal liquid is sprayed from the fourth moving nozzle 12 for a predetermined time, for example, 30 seconds. In the residue removal process (step S8), the substrate W rotates at a predetermined residue removal rotation speed, for example, 300 rpm.

[0199] Next, a spin-drying process (step S9) is performed, in which the substrate W is rotated at high speed to dry the upper surface of the substrate W. Specifically, the residue removal liquid valve 53 is closed. This stops the supply of residue removal liquid to the upper surface of the substrate W. Then, the fourth nozzle moving unit 38 moves the fourth moving nozzle 12 to the starting position.

[0200] Next, the self-rotating motor 23 accelerates the rotation of the substrate W, causing the substrate W to rotate at high speed. The substrate W rotates at a drying speed during the spin-drying process, for example, 1500 rpm. The spin-drying process is performed for a predetermined time, for example, 30 seconds. As a result, a large centrifugal force acts on the residue removal liquid on the substrate W, causing the residue removal liquid on the substrate W to be thrown away and dispersed around the substrate W.

[0201] Next, the self-rotating motor 23 stops the base plate W from rotating. The protective cover lifting unit 74 moves the first protective cover 71A and the second protective cover 71B to the lower position.

[0202] The transport robot CR enters the processing unit 2, picks up the processed substrate W from the clamping pin 20 of the rotating gripper 5, and moves it out of the processing unit 2 (step S10). The substrate W is transferred from the transport robot CR to the transport robot IR, and is then received by the transport robot IR into the carrier C.

[0203] Next, use Figures 8A to 8F The state of the upper surface 151 of the substrate W during substrate processing is described in detail. Figures 8A to 8F This is a schematic diagram illustrating the state near the upper surface 151 of substrate W during substrate processing. For ease of explanation, in... Figure 8B as well as Figure 8C From Figure 2The size relationship between heater unit 6 and substrate W is changed (described later). Figure 15 B and Figure 15 The same applies to C).

[0204] like Figure 8A As shown, the processed film 100 formed in the processed film formation process (step S3) retains particles 103 attached to the surface portion 150 of the substrate W. Before the etching function demonstration process, the processed film 100 contains a temperature-responsive polymer 110, a low-solubility component 111, and a high-solubility component 112. The temperature-responsive polymer 110, the low-solubility component 111, and the high-solubility component 112 become solid by evaporation of at least a portion of the solvent contained in the processing liquid.

[0205] Temperature-responsive polymer 110, low-soluble component 111, and high-soluble component 112 are mixed in the treatment membrane 100. Strictly speaking, the temperature-responsive polymer 110, low-soluble component 111, and high-soluble component 112 are not uniformly distributed throughout the treatment membrane 100. There are regions in the treatment membrane 100 where the temperature-responsive polymer 1100, the low-soluble component 111, and the high-soluble component 112 are concentrated.

[0206] Next, refer to Figure 8B Protons 113 are released from the temperature-responsive polymer 110 through a heat-enhancing treatment. Specifically, the release of protons 113 into the treatment film 100 promotes etching of the surface portion 150 of the substrate W (etching promotion process). Due to the generation (increase) of protons 113, the acidity of the liquid component in the treatment film 100 is enhanced, and the etching of the surface portion 150 of the substrate W continues to progress. As etching continues, the upper surface 151 of the substrate W recedes.

[0207] like Figure 8C As shown, by retraction of the upper surface 151 of the substrate W (etching of the surface portion 150 of the substrate W), the particles 103 float from the upper surface 151 of the substrate W. Thus, the particles 103 are encapsulated by the processing film 100 (especially the low-solubility component 111) and are thus more effectively retained. Etching of the surface portion 150 of the substrate W forms etching residue 104. The processing film 100 (especially the low-solubility component 111) retains the etching residue 104 together with the particles 103 that were already attached to the upper surface 151 of the substrate W before the etching process. The particles 103 and the etching residue 104 are collectively referred to as the object to be removed 105.

[0208] Next, refer to Figure 8DThrough a heat-weakening treatment, the temperature-responsive polymer 110 accepts protons 113 present in the liquid component of the treated film 100. As the number of protons 113 in the treated film 100 decreases, the acidity of the liquid component in the treated film 100 weakens. That is, the pH of the liquid component in the treated film 100 approaches neutral. This mitigates the etching of the surface portion 150 of the substrate W (etch mitigation process). Through the mitigation of etching, the retreat of the upper surface of the substrate W is mitigated or stopped.

[0209] Next, refer to Figure 8E The highly soluble component 112 is selectively dissolved by the stripping and removal liquid. That is, the treated membrane 100 is locally dissolved (dissolution process, local dissolution process).

[0210] The phrase "the highly soluble component 112 in the solid state is selectively dissolved" does not mean that only the highly soluble component 112 in the solid state is dissolved. Rather, it means that although the less soluble component 111 in the solid state is also slightly dissolved, most of the highly soluble component 112 in the solid state is dissolved.

[0211] Taking the selective dissolution of the highly soluble component 112 as an opportunity, through holes 106 are formed in the portion of the treated membrane 100 where the highly soluble component 112 is concentrated (through hole formation process).

[0212] The portion containing the highly soluble component 112 also contains the less soluble component 111, rather than only containing the highly soluble component 112. Because the stripping solution dissolves not only the highly soluble component 112 but also the less soluble component 111 surrounding it, through-holes 106 are formed. When viewed from above, the through-holes 106 are, for example, a few nm in diameter.

[0213] The through-hole 106 does not need to be so clearly defined that the terrain becomes observable. That is, the through-hole 106 only needs to form a path in the processing film 100 that allows the stripping removal liquid to move from the upper surface of the processing film 100 to the upper surface 151 of the substrate W, and this path only needs to penetrate the processing film 100.

[0214] Here, when a moderate amount of solvent remains in the treated membrane 100, the stripping remover dissolves into the solvent remaining in the treated membrane 100 while partially dissolving the treated membrane 100. Specifically, the stripping remover dissolves into the solvent remaining in the treated membrane 100 while dissolving the highly soluble component 112 in the treated membrane 100, thereby forming through-holes 106. Therefore, the stripping remover can easily enter the treated membrane 100 (dissolution entry process).

[0215] The stripping and removal liquid that has reached the upper surface 151 of the substrate W acts on the interface between the treatment film 100 and the substrate W and peels off the treatment film 100, thereby removing the peeled treatment film 100 from the upper surface of the substrate W (stripping and removal process).

[0216] In detail, the low-soluble component 111 has low solubility in the stripping solution, and most of the low-soluble component 111 remains in a solid state. Therefore, the stripping solution reaching the vicinity of the upper surface 151 of the substrate W via the through-hole 106 only partially dissolves the low-soluble component 111 in the vicinity of the upper surface 151 of the substrate W. Thus, as... Figure 8E As shown in the enlarged view, the stripping removal liquid slowly dissolves the low-solubility component 111 in the solid state near the upper surface of the substrate W and gradually enters the gap G between the treatment film 100 and the upper surface 151 of the substrate W (stripping removal liquid entry process).

[0217] Next, for example, cracks (cracks) are formed in the treated membrane 100 starting from the periphery of the through-hole 106. Therefore, the highly soluble component 112 is also referred to as the crack-inducing component. The treated membrane 100 splits through the formation of cracks and becomes a membrane sheet 108. For example... Figure 8F As shown, the membrane 108 of the processing membrane 100 is peeled off from the substrate W while holding the object to be removed 105 (processing membrane splitting process, processing membrane peeling process).

[0218] Next, a stripping and removal solution is continuously supplied, thereby rinsing the treatment membrane 100 (film 108) while holding the object to be removed 105. In other words, the film 108 holding the object to be removed 105 is pushed out of the substrate W and removed from the upper surface 151 of the substrate W (treatment membrane removal process, object to be removed process). As a result, the upper surface of the substrate W can be effectively cleaned.

[0219] The low-soluble component 111 functions as a solid state maintenance component to maintain a solid state in the treatment membrane 100 from the formation of the treatment membrane 100 until it is supplied with the stripping and removal liquid.

[0220] According to the first embodiment, the following effects are achieved.

[0221] According to the first embodiment, by performing a heat-strengthening treatment (etching function enhancement treatment) on the processing film 100, the etching of the surface layer 150 of the substrate W based on the processing film 100 is promoted. Moreover, by performing a heat-weakening treatment (etching function disappearance treatment) on the processing film 100, the etching of the surface layer 150 of the substrate W based on the processing film 100 is mitigated while the processing film 100 is maintained on the substrate W.

[0222] Etching of the surface layer 150 of the substrate W based on the processing film 100 does not begin during the formation of the processing film 100, but is promoted by the heat strengthening process of the processing film 100. Furthermore, instead of removing the processing film 100 to mitigate etching, it is mitigated by the heat weakening process of the processing film 100 while it is held on the substrate W. Since the start and stop of etching are triggered by an active process of changing the intensity of heat, it is easy to control the timing of etching promotion and etching mitigation. That is, the state of etch promotion and the state of etch mitigation can be switched according to the processing of the processing film 100. Therefore, it is easy to control the timing of etch promotion and etching mitigation. Thus, the controllability of etching of the surface layer 150 of the substrate W can be improved.

[0223] Unlike this method, in the method of etching the surface layer 150 of the substrate W while continuously supplying an etching solution such as hydrofluoric acid to the upper surface 151 of the substrate W, the etching solution is continuously discharged outward from the substrate W. On the other hand, in the first embodiment, the surface layer 150 of the substrate W is etched with the processing film 100 while maintaining the processing film 100 on the substrate W. Therefore, the consumption of functional components can be reduced.

[0224] Furthermore, according to the first embodiment, a processing film 100 containing a functional display component is formed in the processing film formation process. The functional display component is used to display the etching function through heat strengthening treatment. Therefore, by etching the surface layer 150 of the substrate W using the processing film 100 with the amount of functional display component adjusted, the etching amount of the surface layer 150 of the substrate W can be controlled.

[0225] Furthermore, according to the first embodiment, the temperature-responsive polymer 110, as a functional component, releases protons by intensifying the heating of the processing film 100 and accepts protons by reducing the heating of the processing film 100. The temperature-responsive polymer 110 releases protons through the heat-intensification treatment, thereby promoting the etching of the surface layer 150 of the substrate W. The temperature-weakening treatment imparts protons to the temperature-responsive polymer 110, thereby mitigating the etching of the surface layer 150 of the substrate W.

[0226] The acidity in the treated film 100 increases due to the release of protons 113 from the temperature-responsive polymer 110. Therefore, the etching of the surface portion 150 of the substrate W can be accelerated or decelerated by the release and reception of protons 113 by the temperature-responsive polymer 110.

[0227] Furthermore, according to the first embodiment, a stripping removal liquid is supplied to the surface of the treatment film 100, thereby removing the treatment film 100 from the upper surface 151 of the substrate W. By removing the treatment film 100 with the stripping removal liquid, the upper surface 151 of the substrate W can be cleaned.

[0228] Furthermore, according to the first embodiment, the treatment film 100 is removed not by dissolution, but by peeling. Therefore, when the object to be removed 105 is attached to the upper surface 151 of the substrate W, it is peeled off from the upper surface 151 of the substrate W while still holding the object to be removed 105. As a result, the object to be removed 105 can be peeled off from the upper surface 151 of the substrate W and removed.

[0229] Furthermore, according to the first embodiment, the treatment film 100 contains a low-soluble component 111 in a solid state and a high-soluble component 112 in a solid state, wherein the high-soluble component 112 in the solid state has higher solubility in the stripping removal liquid than the low-soluble component 111. Moreover, while maintaining the low-soluble component 111 in a solid state, the stripping removal liquid selectively dissolves the high-soluble component 112, thereby stripping the treatment film 100 from the upper surface 151 of the substrate W.

[0230] Therefore, the stripping removal liquid dissolves the highly soluble component 112 in its solid state, thereby enabling the stripping removal liquid to act on the contact interface between the treatment film 100 and the substrate W. On the other hand, most of the low-soluble component 111 in the treatment film 100 remains undissolved and is maintained in a solid state. Therefore, when the object to be removed 105 is present on the upper surface 151 of the substrate W, the stripping removal liquid can act on the contact interface between the low-soluble component 111 in its solid state and the substrate W while maintaining the object to be removed 105 in its solid state. As a result, the treatment film 100 can be quickly removed from the upper surface 151 of the substrate W, and the object to be removed 105 and the treatment film 100 can be efficiently removed together from the upper surface 151 of the substrate W.

[0231] Because the low-soluble component 111 is maintained in a solid state, the object to be removed 105 can be retained by the low-soluble component 111 even after the high-soluble component 112 has dissolved. Even when the processing film 100 is removed from the upper surface 151 of the substrate W by the stripping removal liquid, the object to be removed 105 can be maintained by the processing film 100. Therefore, compared with the case where the object to be removed 105 is not retained by the low-soluble component 111, the energy (physical force) received by the object to be removed 105 from the flow of the stripping removal liquid can be increased. As a result, the object to be removed 105 can be effectively removed from the upper surface 151 of the substrate W by the stripping removal liquid.

[0232] Furthermore, according to the first embodiment, the surface layer 150 of the substrate W is etched, thereby forming etching residue 104 that is held by the processing film 100. The etching residue 104 generated by etching is removed together with the processing film 100 while it is held by the processing film 100. Therefore, it is not necessary to perform a separate process to remove the etching residue 104 after removing the processing film 100.

[0233] In the case where an etching process that combines an etching acceleration process and an etching mitigation process as a single cycle is performed multiple times, the etching amount of the surface layer 150 of the substrate W can be precisely controlled by the number of etching cycles performed.

[0234] like Figure 9 As shown, a plurality of trenches 152 may also be formed on the upper surface 151 of the substrate W used in the substrate processing of the first embodiment. Each trench 152 is circular in shape, for example, when viewed from above in the normal direction Z of the upper surface 151 of the substrate W (hereinafter referred to as "top view"). The trenches 152 are provided at equal intervals, and the distance L between adjacent trenches 152 is, for example, 2 μm. The depth D of each trench 152 is, for example, 5 μm.

[0235] Each trench 152 has a bottom wall 153 and a cylindrical sidewall 154, the sidewall 154 being connected to the bottom wall 153 and extending in the depth direction (normal direction Z) of the trench 152. The plurality of trenches 152 are formed, for example, by dry etching. Therefore, each trench 152 is formed with a narrow, tapering front end that tapers towards the bottom wall 153. The sidewall 154 includes: an opening side 154a, dividing an opening 155 into the trench 152; and a bottom wall side 154b, connecting the opening side 154a and the bottom wall 153.

[0236] Next, use Figures 10A to 10C This describes the state of the surface portion 150 of the substrate W near the trench 152 during substrate processing.

[0237] like Figure 10A As shown, in the film formation process (step S3), as the solvent in the treatment solution evaporates, the liquid level 156 of the treatment solution moves toward the bottom wall 153 of the trench 152. As the evaporation of the solvent in the treatment solution further progresses, as... Figure 10B As shown, a processing film 100 is formed in such a way that it covers the bottom wall 153 and the bottom wall side portion 154b within each trench 152. To form the processing film 100 covering the bottom wall 153 and bottom wall side portion 154b of the trench 152, the rotational speed of the substrate W (processing film formation speed) in the processing film formation process is preferably 1500 rpm, and the viscosity of the processing liquid is preferably 3.4 mm. 2 / s low.

[0238] When the processing film 100 covering the bottom wall 153 and the bottom wall side 154b is formed, the surface layer 150 of the substrate W is etched in the bottom wall 153 and the bottom wall side 154b of the trench 152 through a subsequent etching process. Thus, as... Figure 10C As shown by solid lines, the width of the groove 152 can be expanded only near the bottom wall 153. In the case where the groove 152 has a tapered front end, expanding the width of the groove 152 near the bottom wall 153 allows the groove 152 to approach a cylindrical shape. Furthermore, Figure 10C This indicates the state after the treatment film 100 has been removed. A detailed description of the etching of the surface portion 150 of the substrate W based on the treatment film 100 and the removal of the treatment film 100 is provided. Figures 8A to 8F same.

[0239] Thus, the treatment film 100 is formed only on and around the bottom wall 153 within the trench 152, thereby controlling the size of the area etched (etched area) within the trench 152.

[0240] [Second Implementation]

[0241] Figure 11 This is a schematic partial cross-sectional view showing the general configuration of the processing unit 2 included in the substrate processing apparatus 1P of the second embodiment. The substrate processing apparatus 1P of the second embodiment and the substrate processing apparatus 1 of the first embodiment (see reference 1) Figure 2 The main differences are: the treatment solution does not contain highly soluble components as solutes; and the second moving nozzle 10 sprays a dissolution removal solution to dissolve the treatment membrane instead of a stripping removal solution.

[0242] exist Figure 11 In the middle, regarding the above Figures 1 to 10C The configuration shown is equivalent to the configuration given to Figure 1 Equivalent component symbols and omitting descriptions (for those described later). Figures 12 to 13E Same here).

[0243] Similar to the first embodiment, the processing liquid contains a solute and a solvent. The processing liquid solidifies or hardens by the evaporation (evaporation) of at least a portion of the solvent contained in the processing liquid. The processing liquid solidifies or hardens on the substrate W, thereby forming a solid processing film. The processing film, during the solidification or hardening of the processing liquid, takes in and retains the object to be removed from the substrate W.

[0244] The treatment solution contains a functional component as a solute and a low-soluble component. Similar to the first embodiment, in the second embodiment, the functional component is also a temperature-responsive polymer having multiple constituent units. The low-soluble component is, for example, a phenolic varnish.

[0245] The dissolving and removing liquid ejected from the second movable nozzle 10 is, for example, an organic solvent such as IPA. The dissolving and removing liquid is not limited to IPA. Liquids exemplified as solvents contained in the treatment liquid can be used as the dissolving and removing liquid.

[0246] The second movable nozzle 10 is connected to the dissolving and removing liquid pipe 41P, which guides the dissolving and removing liquid to the second movable nozzle 10. When the dissolving and removing liquid valve 51P, which is clamped to the dissolving and removing liquid pipe 41P, is open, the dissolving and removing liquid is continuously sprayed downward from the nozzle outlet of the second movable nozzle 10. When the second movable nozzle 10 is in the central position, and the dissolving and removing liquid valve 51P is open, the dissolving and removing liquid is supplied to the central region of the upper surface of the substrate W.

[0247] The substrate processing apparatus 1P of the second embodiment can also perform the same substrate processing as in the first embodiment (see reference). Figure 6 The same substrate treatment is applied. In the second embodiment, since the removal treatment film 100 is dissolved and removed by a dissolution and removal solution, therefore... Figure 12 The cleaning process (step S7) and the residue removal process (step S8) can also be omitted as shown.

[0248] Next, use Figures 13A to 13E The state of the upper surface 151 of the substrate W in the substrate processing of the second embodiment will be described in detail. Figures 13A to 13E This is a schematic diagram illustrating the state near the upper surface 151 of substrate W during substrate processing.

[0249] like Figure 13A As shown, the processed film 100 formed in the processed film formation process (step S3) retains particles 103 attached to the surface portion 150 of the substrate W. Before the etching function demonstration process, the processed film 100 contains a temperature-responsive polymer 110 and a low-solubility component 111. The temperature-responsive polymer 110 and the low-solubility component 111 become solid by evaporation of at least a portion of the solvent contained in the processing liquid.

[0250] Temperature-responsive polymer 110 and low-soluble component 111 are mixed in the treatment membrane 100. Strictly speaking, the temperature-responsive polymer 110 and low-soluble component 111 are not uniformly distributed throughout the treatment membrane 100. There are regions in the treatment membrane 100 where the temperature-responsive polymer 110 is more concentrated and regions where the low-soluble component 111 is more concentrated.

[0251] Next, refer to Figure 13BProtons 113 are released from the temperature-responsive polymer 110 through a heat-enhancing treatment. Specifically, the release of protons 113 into the treatment film 100 promotes etching of the surface portion 150 of the substrate W (etching promotion process). Due to the generation (increase) of protons 113, the acidity of the liquid component in the treatment film 100 is enhanced, and the etching of the surface portion 150 of the substrate W continues to progress. As etching continues, the upper surface 151 of the substrate W recedes.

[0252] like Figure 13C As shown, by the retraction of the upper surface 151 of the substrate W (etching of the surface portion 150 of the substrate W), the particles 103 float from the upper surface 151 of the substrate W. Thereby, the particles 103 are more strongly held by the processing film 100 (especially the low-solubility component 111). Etching the surface portion 150 of the substrate W forms etching residue 104. The processing film 100 (especially the low-solubility component 111) holds the etching residue 104 together with the particles 103 that were already attached to the upper surface of the substrate W before the etching process.

[0253] Next, refer to Figure 13D Through a heat-weakening treatment, the temperature-responsive polymer 110 accepts protons 113 present in the liquid component of the treated film 100. As the number of protons 113 in the treated film 100 decreases, the acidity of the liquid component in the treated film 100 weakens. That is, the pH of the liquid component in the treated film 100 approaches neutral. This stops the etching of the surface portion 150 of the substrate W (etching stop process). With the cessation of etching, the retraction of the upper surface of the substrate W stops.

[0254] The low-solubility component 111 functions as a solid state maintenance component to maintain a solid state in the treated film 100 during the etching function demonstration treatment and the etching function disappearance treatment.

[0255] Next, refer to Figure 13E The treatment film 100 is dissolved and removed from the substrate W by means of a dissolution and removal solution (dissolution and removal process). Specifically, the low-soluble component 111 and the temperature-responsive polymer 110 are dissolved (dissolution process). The dissolution and removal solution is continuously supplied, thereby the low-soluble component 111 and the temperature-responsive polymer 110 that have been dissolved by the dissolution and removal solution are discharged to the outside of the substrate W together with the dissolution and removal solution.

[0256] Since the object to be removed 105, which is held by the low-soluble component 111, has been peeled off from the upper surface 151 of the substrate W, it is discharged to the outside of the substrate W by the dissolving and removing liquid flowing on the upper surface 151 of the substrate W.

[0257] According to the second embodiment, the treatment film 100 is dissolved by the dissolving and removing solution, thereby quickly removing the treatment film 100 from the upper surface 151 of the substrate W. This effectively cleans the upper surface 151 of the substrate W.

[0258] According to the second embodiment, in addition to the effects described above, the same effects as in the first embodiment can be achieved. However, the effects based on the stripping and removal liquid and the highly soluble components are excluded.

[0259] [Third Implementation Method]

[0260] Figure 14 This is a schematic diagram showing the general configuration of the processing unit 2 included in the substrate processing apparatus 1Q of the third embodiment. The substrate processing apparatus 1Q of the third embodiment and the substrate processing apparatus 1 of the first embodiment (see reference...) Figure 2 The main differences are: the treatment solution contains a pH-responsive polymer as a functional component; and there is no heater unit 6.

[0261] pH-responsive polymers decompose and exhibit (enhance) etching capabilities by adjusting the pH of the treated membrane to acidic or alkaline conditions. The decomposition products of pH-responsive polymers polymerize and form pH-responsive polymers by bringing the pH closer to neutral, thus eliminating (weakening) the etching function.

[0262] The third movable nozzle 11 in the third embodiment sprays out cleaning fluid and pH adjustment fluid. The pH adjustment fluid is a liquid with weak etching power on the surface of the substrate W. Furthermore, the pH adjustment fluid is preferably a liquid that does not etch the surface of the substrate W, that is, preferably a liquid that does not act as an oxidizing agent. The pH adjustment fluid is, for example, an acidifying liquid such as carbonated water or an alkaline liquid such as ammonia. The third movable nozzle 11 is an example of a pH adjustment fluid supply unit.

[0263] The acidifying solution is an aqueous solution supplied to the treated membrane, thereby changing the pH of the liquid components contained in the treated membrane to acidic. The acidifying solution is not limited to carbonated water; phosphoric acid, citric acid, fumaric acid, succinic acid, etc., can also be used.

[0264] The alkalizing solution is an aqueous solution supplied to the treatment membrane, thereby changing the pH of the liquid components contained in the treatment membrane to alkaline. The alkalizing solution is not limited to ammonia; pyridine, diethylamine, ethylenediamine, diethylethanolamine, diisopropylamine, etc., can also be used.

[0265] The liquid component in the treatment membrane is replaced by pH adjustment solution through the supply of pH adjustment solution, and by cleaning solution through the supply of cleaning solution. Therefore, the liquid component in the treatment membrane is mainly an aqueous solution.

[0266] The third movable nozzle 11 is connected to a common piping 45, which guides the cleaning solution and pH adjustment solution to the third movable nozzle 11. A pH adjustment solution piping 44 is connected to the common piping 45 to guide the pH adjustment solution to the common piping 45; and a cleaning solution piping 42 is connected to the common piping 45 to guide the cleaning solution to the common piping 45. When the pH adjustment solution valve 54, which is clamped to the pH adjustment solution piping 44, is opened, the pH adjustment solution is continuously sprayed downwards from the nozzle outlet of the third movable nozzle 11. When the cleaning solution valve 52, which is clamped to the cleaning solution piping 42, is opened, the cleaning solution is continuously sprayed downwards from the nozzle outlet of the third movable nozzle 11.

[0267] The cleaning fluid in the third embodiment is a neutralizing fluid, used to bring the pH of the liquid components contained in the treated membrane close to neutral. The neutralizing fluid is, for example, a neutral liquid such as pure water. As pure water, DIW (distilled water) can be used. The third moving nozzle 11 is also an example of a neutralizing fluid supply unit.

[0268] In the third embodiment, the etching process is a pH adjustment process, in which a pH adjustment solution is supplied to the processing film 100 on the substrate W to adjust the pH of the liquid components in the processing film 100 to be acidic or alkaline. Adjusting the pH to acidic means changing the pH to be close to 1. Adjusting the pH to alkaline means changing the pH to be close to 14.

[0269] In the third embodiment, the etching function disappearance treatment is a neutralization treatment, in which a neutralizing solution is supplied to the treatment film 100 on the substrate W, making the pH of the treatment film 100 closer to neutral than the pH of the treatment film 100 after pH adjustment treatment. In this embodiment, the functional display component is a component that decomposes and displays (enhances) the etching function through the etching function display treatment. The etching function of the functional display component disappears (weakens) until it is reformed through polymerization.

[0270] pH-responsive polymers are decomposed by adjusting the pH of the liquid component in the membrane to either acidic or alkaline conditions. This results in the formation of multiple monomers containing monomeric organic acids. The etching function is enhanced through the formation of these organic acids. Alternatively, the multiple monomers can be polymerized by adjusting the pH of the liquid component in the membrane to near neutral. This causes the organic acids to disappear, thus weakening or eliminating the etching function.

[0271] Furthermore, the organic acids contained as building blocks in pH-responsive polymers are less acidic than the monomeric organic acids. Therefore, even with the inclusion of organic acids as building blocks, pH-responsive polymers do not exhibit etching capabilities.

[0272] The etching function manifests or disappears depending on the pH change of the liquid component in the processing film. Therefore, in the case of etching the surface portion of the substrate W by a pH-responsive polymer, the processing film is preferably a semi-solid (gel-like) mixture of liquid and solid components, and preferably the liquid component in the processing film contains water.

[0273] For example, when using an acidifying solution as a pH adjusting solution, the pH of the liquid component in the treated membrane is adjusted to below 4, thereby promoting etching. On the other hand, the pH of the liquid component in the treated membrane is neutralized to a value higher than 4, thereby mitigating etching.

[0274] When using an alkaline solution as a pH adjustment solution, the pH of the liquid component in the treated membrane is adjusted to 9 or higher, thereby promoting etching. On the other hand, the pH of the liquid component in the treated membrane is neutralized to a value lower than 9, thereby mitigating etching.

[0275] Figure 15 This is a schematic diagram illustrating an example of a pH-responsive polymer. As a pH-responsive polymer, a copolymer of N-isopropylacrylamide and acrylic acid (a second copolymer) can be used. The second copolymer is a hydrogel containing water as a liquid component. N-isopropylacrylamide and acrylic acid are the building blocks of the second copolymer. Acrylic acid is an organic acid contained in the second copolymer as a building block.

[0276] The second copolymer is decomposed by changing the pH of the liquid component in the treatment film to acidic. This forms monomers of acrylic acid and N-isopropylacrylamide. In other words, multiple monomers are formed. The etching function is enhanced through the formation of the acrylic acid monomer. When the pH of the liquid component in the treatment film is changed to neutral, the monomers of acrylic acid and N-isopropylacrylamide are also polymerized. As a result, the acrylic acid monomer, which is an organic acid, disappears, and the etching function is lost (weakened).

[0277] The difference between the substrate processing in the third embodiment and the substrate processing in the first embodiment lies in the content of the etching acceleration process (step S4) and the etching mitigation process (step S5).

[0278] Figure 16A This is a schematic diagram illustrating an example of an etching acceleration process (step S4) in substrate processing based on substrate processing apparatus 1Q. Figure 16BThis is a schematic diagram illustrating an example of an etching mitigation process (step S5) in substrate processing based on substrate processing apparatus 1Q.

[0279] In the etching acceleration step (step S4) of the substrate processing in the third embodiment, the pH adjustment liquid valve 54 is opened when the third moving nozzle 11 is in the processing position. This supplies pH adjustment liquid from the third moving nozzle 11 toward the processing film 100 on the substrate W (pH adjustment liquid supply step, pH adjustment liquid ejection step). The supply of the pH adjustment liquid adjusts the pH of the liquid components in the processing film 100 on the substrate W to either acidic or alkaline. This causes the pH-responsive polymer in the processing film 100 to decompose and form monomeric organic acids, thereby promoting the etching of the surface portion of the substrate W (etching acceleration step).

[0280] Next, with the third moving nozzle 11 in the processing position, the pH adjustment liquid valve 54 is closed, and instead, the cleaning liquid valve 52 is opened. This stops the supply of pH adjustment liquid from the third moving nozzle 11 and begins the supply of cleaning liquid (neutralizing liquid) from the third moving nozzle 11 (neutralizing liquid supply process, neutralizing liquid ejection process). Through the supply of neutralizing liquid, the pH of the liquid components in the processing film 100 on the substrate W approaches neutral. As a result, the monomers in the processing film 100 polymerize and the monomeric organic acids disappear, thereby mitigating the etching of the surface layer of the substrate W (etch mitigation process).

[0281] Next, use Figures 17A to 17F This describes the state of the upper surface 151 of the substrate W during substrate processing. Figures 17A to 17F A schematic diagram illustrating the state near the upper surface 151 of substrate W during substrate processing.

[0282] like Figure 17A As shown, the processed film 100 formed in the processed film formation process (step S3) retains particles 103 attached to the surface portion 150 of the substrate W. Before the etching function demonstration process, the processed film 100 contains a pH-responsive polymer 114, a low-soluble component 111, and a high-soluble component 112. The pH-responsive polymer 114, the low-soluble component 111, and the high-soluble component 112 become solid by evaporation of at least a portion of the solvent contained in the processing solution.

[0283] pH-responsive polymer 114, low-soluble component 111, and high-soluble component 112 are mixed in the treatment membrane 100. Strictly speaking, the pH-responsive polymer 114, low-soluble component 111, and high-soluble component 112 are not uniformly distributed throughout the treatment membrane 100. There are regions in the treatment membrane 100 where pH-responsive polymer 114, low-soluble component 111, and high-soluble component 112 are concentrated.

[0284] Next, refer to Figure 17B The pH-responsive polymer 114 is decomposed through a pH adjustment treatment. Specifically, the pH-responsive polymer 114 is decomposed, thereby forming an organic acid 115 and a monomer 116 that is not an organic acid in the treated film 100. In the case where the pH-responsive polymer 114 is a second polymer, the monomer 116 is an N-isopropylacrylamide monomer, and the organic acid 115 is an acrylic acid monomer. The organic acid 115 in the treated film 100 increases, thereby promoting the etching of the surface portion 150 of the substrate W (etching promotion process). Through the formation of the organic acid 115, the etching of the surface portion 150 of the substrate W continues to progress. As etching continues to progress, the upper surface 151 of the substrate W recedes.

[0285] like Figure 17C As shown, by the retraction of the upper surface 151 of the substrate W (etching of the surface portion 150 of the substrate W), the particles 103 float from the upper surface 151 of the substrate W. Thereby, the particles 103 are more strongly held by the processing film 100 (especially the low-solubility component 111). Etching of the surface portion 150 of the substrate W forms etching residue 104. The processing film 100 (especially the low-solubility component 111) holds the etching residue 104 together with the particles 103 that were already attached to the upper surface 151 of the substrate W before the etching process.

[0286] Next, refer to Figure 17D Through neutralization treatment, a plurality of monomers containing organic acid 115 are polymerized to form a pH-responsive polymer 114. By reducing the organic acid 115 in the treated film 100, the acidity of the liquid component in the treated film 100 is weakened. This stops the etching of the surface portion 150 of the substrate W (etching stop process). With the cessation of etching, the retraction of the upper surface of the substrate W stops.

[0287] Next, refer to Figure 17E The highly soluble component 112 is selectively dissolved by the stripping and removal liquid. That is, the treated membrane 100 is locally dissolved (dissolution process, local dissolution process).

[0288] Taking the selective dissolution of the highly soluble component 112 as an opportunity, through holes 106 are formed in the portion of the treated membrane 100 where the highly soluble component 112 is concentrated (through hole formation process).

[0289] In areas where highly soluble component 112 is concentrated, less soluble component 111 is also present, rather than only highly soluble component 112. Since the stripping and removal liquid not only dissolves highly soluble component 112 but also dissolves the less soluble component 111 surrounding highly soluble component 112, through-holes 106 are formed.

[0290] In the case where a moderate amount of neutralizing liquid remains in the treated membrane 100, the stripping removal liquid dissolves into the neutralizing liquid remaining in the treated membrane 100 while partially dissolving the treated membrane 100. Specifically, the stripping removal liquid dissolves into the neutralizing liquid remaining in the treated membrane 100 while dissolving the highly soluble component 112 in the treated membrane 100, thereby forming through-holes 106. Therefore, the stripping removal liquid can easily enter the treated membrane 100 (dissolution entry process).

[0291] The stripping and removal liquid that has reached the upper surface 151 of the substrate W acts on the interface between the treatment film 100 and the substrate W and peels off the treatment film 100, thereby removing the peeled treatment film 100 from the upper surface 151 of the substrate W (stripping and removal process).

[0292] In detail, the low-soluble component 111 has low solubility in the stripping solution, and most of the low-soluble component 111 is maintained in a solid state. Therefore, only a small amount of the low-soluble component 111 near its surface is dissolved by the stripping solution. Thus, the stripping solution reaching the vicinity of the upper surface 151 of the substrate W via the through-hole 106 only partially dissolves the low-soluble component 111 near the upper surface 151 of the substrate W. Therefore, as... Figure 17E As shown in the enlarged view, the stripping removal liquid slowly dissolves the low-solubility component 111 in the solid state near the upper surface 151 of the substrate W and gradually enters the gap G between the treatment film 100 and the upper surface 151 of the substrate W (stripping removal liquid entry process).

[0293] Next, for example, cracks (cracks) are formed in the treated membrane 100 starting from the periphery of the through-hole 106. Therefore, the highly soluble component 112 is also referred to as the crack-inducing component. The treated membrane 100 splits through the formation of cracks and becomes a membrane sheet 108. For example... Figure 17F As shown, the membrane 108 of the processing membrane 100 is peeled off from the substrate W while holding the object to be removed 105 (processing membrane splitting process, processing membrane peeling process).

[0294] Next, a stripping and removing liquid is continuously supplied, thereby rinsing the treatment membrane 100, which becomes membrane 108, while holding the object to be removed 105. In other words, the membrane 108 holding the object to be removed 105 is pushed out of the substrate W and removed from the upper surface 151 of the substrate W (treatment membrane removal process, object to be removed process). As a result, the upper surface 151 of the substrate W can be cleaned well.

[0295] The low-soluble component 111 functions as a solid state maintenance component to maintain a solid state in the treatment membrane 100 from the formation of the treatment membrane 100 until it is supplied with the stripping and removal liquid.

[0296] According to the third embodiment, the following effects are achieved. Etching of the surface portion 150 of the substrate W based on the processing film 100 does not begin during the formation of the processing film 100, but is promoted by adjusting the pH of the processing film 100. Furthermore, instead of removing the processing film 100 to stop etching, the etching is mitigated by neutralizing the processing film 100 while it is held on the substrate W. Since the easing and promotion of etching are triggered by an active process such as changing the pH in the processing film 100, the timing of etching promotion and easing can be easily controlled. That is, the state of easing etching and the state of easing etching can be switched according to the treatment of the processing film 100. Therefore, the timing of easing etching and the timing of easing etching are easily controlled. Therefore, the controllability of etching of the surface portion 150 of the substrate W can be improved.

[0297] Since the acidity of the monomeric organic acid is higher than that of the organic acid that forms the building blocks of the pH-responsive polymer, it is able to etch the surface portion 150 of the substrate W. Therefore, the etching of the surface portion 150 of the substrate W can be accelerated or slowed down by processing the decomposition and formation of the pH-responsive polymer 114 in the film 100.

[0298] Furthermore, in the case where the etching process, which combines the etching mitigation step and the etching acceleration step as a single cycle, is repeatedly performed, the liquid component in the treatment film 100 is replaced with the pH adjustment solution or cleaning solution each time a pH adjustment solution or cleaning solution is supplied to the treatment film 100. Therefore, the etching residue 104 formed on the upper surface 151 of the substrate W by etching is removed with the flow of the pH adjustment solution or cleaning solution. This suppresses the reduction in etching rate caused by the formation of etching residue 104.

[0299] Furthermore, according to the third embodiment, in addition to the effects described above, the same effects as the first embodiment can be achieved, except for the effects related to temperature-responsive polymers.

[0300] [Detailed description of the components in the treatment solution]

[0301] The following describes the components (solvent, low-soluble component, high-soluble component) used in the processing liquid of the above embodiments.

[0302] The following, "C" x～y “C” x ~C y "and "C x The term "..." indicates the number of carbons in a molecule or substituent. For example, C... 1～6 Alkyl refers to an alkyl chain having 1 or more but less than 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0303] In polymers having a plurality of repeating units, these repeating units constitute copolymerization. Unless otherwise specified or mentioned, these copolymerizations can be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or any mixture of these copolymerizations. When polymers or resins are represented by structural formulas, the n, m, etc., marked in parentheses indicate the number of repetitions.

[0304] [Low-soluble components]

[0305] (A) The low-soluble component comprises at least one of phenolic varnish, polyhydroxystyrene, polystyrene, polyacrylic acid derivative, polymaleic acid derivative, polycarbonate, polyvinyl alcohol derivative, polymethylacrylic acid derivative, and copolymers thereof. Preferably, (A) may also comprise at least one of phenolic varnish, polyhydroxystyrene, polyacrylic acid derivative, polycarbonate, polymethylacrylic acid derivative, and copolymers thereof. More preferably, (A) may also comprise at least one of phenolic varnish, polyhydroxystyrene, polycarbonate, and copolymers thereof. The phenolic varnish may also be phenol novolac.

[0306] As a low-soluble component (A), the treatment solution may contain one suitable example as described above, or a combination of two or more suitable examples as described above. For example, the low-soluble component (A) may contain both phenolic varnish and polyhydroxystyrene.

[0307] (A) A preferred form of the low-soluble component is that it is dried to form a film, and the film formed is not mostly dissolved by the stripping solution, but is stripped by the stripping solution while still containing the object to be removed. Alternatively, it may be a form in which only a very small portion of the low-soluble component (A) is dissolved by the stripping solution.

[0308] Preferably, (A) the low-soluble component does not contain fluorine and / or silicon, more preferably (A) the low-soluble component does not contain either fluorine or silicon.

[0309] The copolymerization is preferably random copolymerization or block copolymerization.

[0310] Although not intended to limit the scope of the claims, the various compounds shown in Chemical Formulas 1 to 7 below can be cited as specific examples of (A) low-soluble components.

[0311] [Chemical Formula 1]

[0312]

[0313] [Chemical Formula 2]

[0314]

[0315] [Chemical Formula 3]

[0316]

[0317] (An asterisk * indicates a bond with an adjacent constituent unit.)

[0318] [Chemical Formula 4]

[0319]

[0320] (R represents C) 1～4 Alkyl groups and other substituents. An asterisk (*) indicates a bond with an adjacent constituent unit.

[0321] [Chemical Formula 5]

[0322]

[0323] [Chemical Formula 6]

[0324]

[0325] [Chemical Formula 7]

[0326]

[0327] (Me represents methyl. The asterisk * indicates a bond with an adjacent building block.)

[0328] (A) The weight-average molecular weight (Mw) of the low-soluble component is preferably from 150 to 500,000, more preferably from 300 to 300,000, even more preferably from 500 to 100,000, and even more preferably from 1,000 to 50,000.

[0329] (A) The low-soluble component can be obtained through synthesis. Alternatively, it can be obtained through procurement. In the case of procurement, the following supply sources can be cited as examples. These supply sources can also synthesize (A) polymers.

[0330] Phenolic varnishes: SHOUWA KASEI Co., Ltd., ASAHI YUKIZAI CORPORATION, Gun Ei Chemical Industry Co., Ltd., and Sumitomo Bakelite Co., Ltd. (Japan).

[0331] Polyhydroxystyrene: NIPPON SODA Co., Ltd., Maruzen Petrochemical Co., Ltd., TOHO Chemical Industry Co., Ltd.

[0332] Polyacrylic acid derivatives: Nippon Shokubai Co., Ltd.

[0333] Polycarbonate: Sigma-Aldrich Co., LLC.

[0334] Polymethacrylic acid derivatives: Sigma-Aldrich Co. LLC.

[0335] [Highly soluble ingredients]

[0336] (B) The highly soluble component is (B') the crack-promoting component. (B') The crack-promoting component comprises a hydrocarbon, and further comprises a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). In the case where (B') the crack-promoting component is a polymer, one of the constituent units comprises a hydrocarbon in each unit, and further comprises a hydroxyl group and / or a carbonyl group. Examples of carbonyl groups include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, with carboxylic acids being preferred.

[0337] While not intended to limit the scope of the claims and not to be theoretically bound, consider the following: when a treatment film is formed on a substrate where the treatment solution has dried, and the treatment film is peeled off with a stripping solution, the highly soluble component (B) becomes the catalyst for the peeling of the treatment film. Therefore, it is preferable that the highly soluble component (B) is a component whose solubility in the stripping solution is higher than that of the less soluble component (A). The crack-promoting component (B') may contain a ketone in the form of a carbonyl group, and cyclic hydroxyl groups are examples. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0338] In a more specific form, (B) the highly soluble component is represented by at least one of (B-1), (B-2) and (B-3) below.

[0339] (B-1) is a compound comprising one to six (preferably one to four) units of the following chemical formula 8 as building blocks, each building block being bonded by a linker (linker L1). Here, the linker L1 can be a single bond or a C bond. 1～6 Alkylene. The above C 1～6 Alkyl groups serve as linkers to form structural units, and are not limited to divalent groups. Divalent to tetravalent groups are preferred. The above C 1～6 Alkylenes can be either straight-chain or branched.

[0340] [Chemical Formula 8]

[0341]

[0342] C y1 C 5～30 The hydrocarbon ring is preferably phenyl, cyclohexane, or naphthyl, more preferably phenyl. As a preferred embodiment, the linker L1 connects to a plurality of C atoms. y1 .

[0343] R1 is independently C 1～5 Alkyl groups, preferably methyl, ethyl, propyl, or butyl. The above C 1～5 Alkyl groups can be either straight-chain or branched.

[0344] n b1 It can be 1, 2, or 3, preferably 1 or 2, and more preferably 1. b1’ The value can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0345] The following chemical formula 9 is used to represent the constituent unit described in chemical formula 8. Linker L9 is preferably a single bond, methylene, ethylene, or propylene.

[0346] [Chemical Formula 9]

[0347]

[0348] Although not intended to limit the scope of the claims, examples of preferred embodiments of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These can also be obtained through polymerization or condensation.

[0349] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, represented by chemical formula 10 below, is selected for illustration. The same compound in (B-1) has three constituent units of chemical formula 8, which are linked by linker L1 (methylene). b1 =n b1’ =1, R1 is a methyl group.

[0350] [Chemical Formula 10]

[0351]

[0352] (B-2) is represented by the following chemical formula 11.

[0353] [Chemical Formula 11]

[0354]

[0355] R 21 R 22 R 23 and R 24 Each can be independently hydrogen or C. 1～5 Alkyl groups are preferably hydrogen, methyl, ethyl, tert-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

[0356] Connector L 21 and connector L 22 C, each independently1～20 alkylene, C 1～20 Cycloalkylene, C 2～4 alkenylene, C 2～4 Alkyne or C 6～20 arylene groups. These groups can also be converted by C. 1～5 Alkyl or hydroxyl groups are used for substitution. Here, "alkenyl" refers to a divalent hydrocarbon group having one or more double bonds, and "alkynyl" refers to a divalent hydrocarbon group having one or more triple bonds. Linker L 21 and connector L 22 C is preferred 2～4 Alkylene, acetylene (C2 acetylide), or phenylene, more preferably C2 acetylide. 2～4 Alkylene or acetylene, more preferably acetylene.

[0357] n b2 It can be 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0358] Although not intended to limit the scope of the claims, 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol are examples of preferred embodiments of (B-2). As another approach, and as a preferred example of (B-2), examples include 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-benzenediol.

[0359] (B-3) A polymer comprising constituent units represented by the following chemical formula 12, and having a weight-average molecular weight (Mw) of 500 to 10,000. The weight-average molecular weight is preferably 600 to 5,000, more preferably 700 to 3,000.

[0360] [Chemical Formula 12]

[0361]

[0362] Here, R25 The constituent units are -H, -CH3, or -COOH, preferably -H or -COOH. A (B-3) polymer may also contain two or more constituent units represented by chemical formula 12.

[0363] While not intended to limit the scope of the claims, polymers of acrylic acid, maleic acid, or combinations thereof are cited as preferred examples of polymers (B-3). Polyacrylic acid and maleic acid-acrylic acid copolymers are more preferred examples.

[0364] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0365] As an example, consider the maleic acid-acrylic acid copolymer shown in Chemical Formula 13 below. The maleic acid-acrylic acid copolymer comprises (B-3) and has two constituent units represented by Chemical Formula 12, wherein R in one constituent unit... 25 For -H, R is in other constituent units. 25 It is -COOH.

[0366] [Chemical Formula 13]

[0367]

[0368] Needless to say, the treatment solution may also contain one or more of the above-mentioned preferred examples as (B) the highly soluble component. For example, (B) the highly soluble component may also contain 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0369] (B) The molecular weight of the highly soluble component may also be 80 to 10,000. (B) The molecular weight of the highly soluble component is preferably 90 to 5,000, more preferably 100 to 3,000. In the case where the highly soluble component in (B) is a resin, copolymer, or polymer, the molecular weight is expressed as weight-average molecular weight (Mw).

[0370] (B) Highly soluble components can be obtained through synthesis or procurement. Examples of suppliers include Sigma-Aldrich Co., LLC., Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai Co., Ltd.

[0371] [solvent]

[0372] (C) The solvent is preferably an organic solvent. (C) The solvent may also be volatile. Volatility means that its volatility is higher than that of water. For example, the boiling point of solvent (C) under one atmosphere of pressure is preferably 50°C to 250°C. The boiling point of solvent under one atmosphere of pressure is more preferably 50°C to 200°C, and even more preferably 60°C to 170°C. The boiling point of solvent under one atmosphere of pressure is even more preferably 70°C to 150°C. In the case where the functional component is a temperature-responsive polymer, the solvent preferably contains pure water. Pure water is preferably DIW. In the case where the functional component is a pH-responsive polymer, the solvent may not contain pure water as long as it is miscible with a pH-adjusting solution.

[0373] Examples of organic solvents include: alcohols such as isopropanol (IPA); ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as PGME (propylene glycol monomethyl ether) and PGEE (propylene glycol monoethyl ether); propylene glycol monoalkyl ether acetates such as PGMEA (propylene glycol monomethyl ether acetate) and propylene glycol monoethyl ether acetate; and methyl lactate and ethyl lactate. Lactic acid esters such as lactate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone; amides such as N,N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. These organic solvents can be used alone or in mixtures of two or more.

[0374] [Other Implementation Methods]

[0375] The present invention is not limited to the embodiments described above, and may be further implemented in other ways.

[0376] For example, the self-rotating clamp 5 is not limited to a clamping type clamp, but can also be a vacuum type clamp; the clamping type clamp causes a plurality of clamping pins 20 to contact the peripheral end face of the substrate W, and the vacuum type clamp causes the lower surface of the substrate W to be adsorbed onto the upper surface of the self-rotating base 21, thereby holding the substrate W horizontally.

[0377] Furthermore, in the above embodiment, the heating of the processing film 100 is performed by the heater unit 6, which heats the processing film 100 via the substrate W. The heating of the processing film 100 can also be performed by a heater used to directly heat the processing film 100 from above.

[0378] Furthermore, a heating fluid such as warm water can be supplied to the lower surface of the substrate W to enhance the heating of the processing film 100. Alternatively, the supply of the heating fluid can be stopped to reduce the heating of the processing film 100. The heating of the processing film 100 can also be reduced by a cooling fluid such as cooling water.

[0379] Furthermore, unlike the embodiments described above, the etching function demonstration process may also include heat enhancement treatment and pH adjustment treatment. That is, the pH of the liquid component in the treatment film may be set to acidic or alkaline while the treatment film is heated, thereby promoting the etching of the surface layer of the substrate W. In this case, at least one of the heat weakening treatment and neutralization treatment is performed on the treatment film, thereby mitigating the etching of the surface layer of the substrate W.

[0380] Furthermore, the second and third embodiments described above can also be combined. Specifically, in the third embodiment, a treatment solution containing a low-soluble component as a solute and a pH-responsive polymer is used, and a dissolving and removing solution can be used instead of a stripping and removing solution.

[0381] In this specification, when "to" (i.e., "~" or "-") is used to indicate a numerical range, unless otherwise specified, it includes both endpoints and the unit is common. Although embodiments of the invention have been described in detail, these embodiments are merely specific examples used to clarify the technical content of the invention, and the invention should not be construed as limited to these specific examples. The invention is defined only by the appended claims.

[0382] This application corresponds to Japanese Patent Application No. 2020-126875, filed with the Japan Patent Office on July 27, 2020, and all contents of Japanese Patent Application No. 2020-126875 are incorporated herein by reference.

[0383] Explanation of reference numerals in the attached figures

[0384] 1: Substrate processing device

[0385] 1P: Substrate processing apparatus

[0386] 1Q: Substrate processing apparatus

[0387] 3: Controller

[0388] 6: Heater Unit (Processing Membrane Heating Unit)

[0389] 9: First moving nozzle (processing fluid supply unit)

[0390] 11: Third moving nozzle (pH adjustment solution supply unit, neutralization solution supply unit)

[0391] 23: Rotating motor (processing membrane forming unit)

[0392] 65: Heater lifting unit (heater adjustment unit)

[0393] 110: Temperature-responsive polymers

[0394] 111: Low-soluble components

[0395] 112: Highly soluble components

[0396] 113: Proton

[0397] 114: pH-responsive polymers

[0398] 115: Organic acids

[0399] 150: Surface layer

[0400] 151: Top surface (surface of the substrate)

[0401] 152: Trench

[0402] 153:Bottom wall

[0403] 154: Sidewall

[0404] 154a: Opening side

[0405] 154b: Bottom wall side

[0406] 155: Opening

[0407] W: substrate.

Claims

1. A substrate processing method, wherein, include: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate and the treatment liquid on the surface of the substrate is cured or hardened, thereby forming a treatment film on the surface of the substrate. The etching promotion process involves etching the processing film to reveal its etching function, thereby promoting the etching of the surface portion of the substrate based on the processing film. as well as The etching mitigation process involves removing the etching function of the treatment film, thereby mitigating the etching of the surface portion of the substrate based on the treatment film while the treatment film is maintained on the substrate. The etching process includes a pH adjustment process, in which a pH adjustment solution is supplied to the treatment film on the substrate to adjust the pH of the treatment film to either acidic or alkaline. The etching function disappearance process includes: neutralization treatment, supplying a neutralizing solution toward the treatment film on the substrate, so that the pH of the treatment film is closer to neutral than the pH of the treatment film after the pH adjustment treatment.

2. The substrate processing method as described in claim 1, wherein, The etching function enhancement process includes: a heat strengthening process to enhance the heating of the treatment film; the etching function disappearance process includes: a heat weakening process to reduce the heating of the treatment film.

3. The substrate processing method as described in claim 1, wherein, In the processing film forming process, a processing film containing functional display components is formed, and the functional display components exhibit etching function through the etching functional display treatment.

4. The substrate processing method as described in claim 3, wherein, The functional component is a polymer that releases protons into the treated membrane through the etching functional process and then removes protons from the treated membrane through the etching functional process. The etching acceleration process includes the following steps: the polymer releases protons through the etching functional enhancement treatment, thereby promoting the etching of the surface portion of the substrate. The etching mitigation process includes the following steps: imparting protons to the polymer through the etching function disappearance treatment, thereby mitigating the etching of the surface portion of the substrate.

5. The substrate processing method as described in claim 4, wherein, The polymer is a copolymer of N-isopropylacrylamide and N,N'-methylenebisacrylamide and acrylic acid.

6. The substrate processing method as described in claim 3, wherein, The functional component is a polymer having a plurality of constituent units, including an organic acid as one of the constituent units. The etching acceleration process includes the following steps: decomposing the polymer and forming a plurality of monomers, including monomeric organic acids, through the etching functional manifestation treatment, thereby promoting the etching of the surface portion of the substrate. The etching mitigation process includes the following steps: polymerizing a plurality of monomers in the treated film and forming the polymer by means of the etching function disappearance treatment, thereby mitigating the etching of the surface portion of the substrate.

7. The substrate processing method as described in claim 6, wherein, The polymer is a copolymer of N-isopropylacrylamide and acrylic acid. The organic acid is acrylic acid.

8. A substrate processing method, wherein, include: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate and the treatment liquid on the surface of the substrate is cured or hardened, thereby forming a treatment film on the surface of the substrate. The etching promotion process involves etching the processing film to reveal its etching function, thereby promoting the etching of the surface portion of the substrate based on the processing film. as well as The etching mitigation process involves removing the etching function of the treatment film, thereby mitigating the etching of the surface portion of the substrate based on the treatment film while the treatment film is maintained on the substrate. In the processing film formation step, a processing film containing functional display components is formed, and the functional display components exhibit etching functionality through the etching functional display treatment. The functional component is a polymer that releases protons into the treated membrane through the etching functional process and then removes protons from the treated membrane through the etching functional process. The etching acceleration process includes the following steps: the polymer releases protons through the etching functional enhancement treatment, thereby promoting the etching of the surface portion of the substrate. The etching mitigation process includes the following steps: imparting protons to the polymer through the etching function disappearance treatment, thereby mitigating the etching of the surface portion of the substrate.

9. The substrate processing method as described in claim 8, wherein, The polymer is a copolymer of N-isopropylacrylamide and N,N'-methylenebisacrylamide and acrylic acid.

10. A substrate processing method, wherein, include: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate and the treatment liquid on the surface of the substrate is cured or hardened, thereby forming a treatment film on the surface of the substrate. The etching promotion process involves etching the processing film to reveal its etching function, thereby promoting the etching of the surface portion of the substrate based on the processing film. as well as The etching mitigation process involves removing the etching function of the treatment film, thereby mitigating the etching of the surface portion of the substrate based on the treatment film while the treatment film is maintained on the substrate. In the processing film formation step, a processing film containing functional display components is formed, and the functional display components exhibit etching functionality through the etching functional display treatment. The functional component is a polymer having a plurality of constituent units, including an organic acid as one of the constituent units. The etching acceleration process includes the following steps: decomposing the polymer and forming a plurality of monomers, including monomeric organic acids, through the etching functional manifestation treatment, thereby promoting the etching of the surface portion of the substrate. The etching mitigation process includes the following steps: polymerizing a plurality of monomers in the treated film and forming the polymer by means of the etching function disappearance treatment, thereby mitigating the etching of the surface portion of the substrate.

11. The substrate processing method as described in claim 10, wherein, The polymer is a copolymer of N-isopropylacrylamide and acrylic acid. The organic acid is acrylic acid.

12. The substrate processing method according to any one of claims 1 to 11, wherein, The etching process is performed repeatedly, with the etching acceleration process and the etching mitigation process forming a cycle.

13. The substrate processing method according to any one of claims 1 to 11, wherein, Further includes: In the process of removing the treatment film, a removal liquid is supplied to the surface of the treatment film, thereby removing the treatment film from the surface of the substrate.

14. The substrate processing method as described in claim 13, wherein, The process for removing the treatment film includes a dissolution process in which the removal solution dissolves the treatment film, thereby removing the treatment film from the surface of the substrate.

15. The substrate processing method as described in claim 13, wherein, The processing film removal process includes a peeling removal process, in which the processing film is peeled off from the surface of the substrate using the removal liquid, thereby removing the processing film from the surface of the substrate.

16. The substrate processing method as described in claim 15, wherein, The surface layer of the substrate is etched, thereby forming etching residue that is retained by the treatment film. The process of removing the treatment film includes the following steps: removing the etching residue together with the treatment film while the etching residue is held by the treatment film.

17. A substrate processing method, wherein, include: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate and the treatment liquid on the surface of the substrate is cured or hardened, thereby forming a treatment film on the surface of the substrate. The etching promotion process involves etching the processing film to reveal its etching function, thereby promoting the etching of the surface portion of the substrate based on the processing film. The etching mitigation process involves removing the etching function of the treatment film, thereby mitigating the etching of the surface portion of the substrate based on the treatment film while the treatment film is maintained on the substrate. as well as In the film removal process, a removal solution is supplied to the surface of the treated film, thereby removing the treated film from the surface of the substrate. The processing film removal process includes a peeling removal process, in which the processing film is peeled off from the surface of the substrate using the removal liquid, thereby removing the processing film from the surface of the substrate. In the membrane formation process, a membrane is formed comprising a low-soluble component in a solid state and a high-soluble component in a solid state. The high-soluble component in the solid state has a higher solubility in the removal liquid than the low-soluble component. The stripping and removal process includes the following steps: while maintaining the low-soluble component in a solid state, selectively dissolving the high-soluble component in the removal liquid, thereby stripping the treatment film from the surface of the substrate.

18. A substrate processing method, wherein, include: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate and the treatment liquid on the surface of the substrate is cured or hardened, thereby forming a treatment film on the surface of the substrate. The etching promotion process involves etching the processing film to reveal its etching function, thereby promoting the etching of the surface portion of the substrate based on the processing film. as well as The etching mitigation process involves removing the etching function of the treatment film, thereby mitigating the etching of the surface portion of the substrate based on the treatment film while the treatment film is maintained on the substrate. The substrate has grooves that are circular when viewed from above, and these grooves cause the surface of the substrate to be recessed. The trench has a bottom wall and side walls, the side walls being connected to the bottom wall and extending in the depth direction of the trench. The sidewall has: The side portion of the bottom wall is connected to the bottom wall; as well as The opening on the side of the opening divides the groove. The process of forming the treatment membrane includes the following steps: forming the treatment membrane covering the bottom wall side portion of the sidewall and the bottom wall.

19. A substrate processing apparatus, wherein, include: The processing liquid supply unit supplies processing liquid toward the surface of the substrate; The processing film forming unit solidifies or hardens the processing liquid on the surface of the substrate, thereby forming a processing film on the surface of the substrate; A pH adjustment solution supply unit supplies pH adjustment solution toward the surface of the substrate, wherein the pH adjustment solution adjusts the pH of the treated membrane to be acidic or alkaline. A neutralization solution supply unit supplies a neutralization solution toward the surface of the substrate, the neutralization solution making the pH of the treated membrane close to neutral; as well as The controller controls the processing solution supply unit, the processing membrane formation unit, the pH adjustment solution supply unit, and the neutralization solution supply unit. The controller is programmed to execute: In the process of forming a treatment film, a treatment liquid is supplied from the treatment liquid supply unit toward the surface of the substrate, and the treatment liquid on the surface of the substrate is solidified or hardened by the treatment film forming unit, thereby forming a treatment film on the surface of the substrate. In the etching promotion process, the pH adjustment liquid is supplied from the pH adjustment liquid supply unit toward the surface of the substrate and the pH in the treatment film is adjusted to be acidic or alkaline, thereby promoting the etching of the surface portion of the substrate based on the treatment film. as well as In the etching mitigation process, the neutralizing solution is supplied from the neutralizing solution supply unit toward the surface of the substrate, so that the pH of the treated film is closer to neutral than the pH of the treated film after adjustment by the pH adjusting solution, thereby mitigating the etching of the surface portion of the substrate while the treated film is maintained on the substrate.

20. A treatment liquid, wherein, It forms a treatment film by curing or hardening it onto the surface of a substrate. The processing liquid contains a polymer that promotes etching of the surface portion of the substrate based on the processing film through an etching process, and mitigates etching of the surface portion of the substrate based on the processing film through an etching process that removes the etching. The etching process includes a pH adjustment process, in which a pH adjustment solution is supplied to the treatment film on the substrate to adjust the pH of the treatment film to either acidic or alkaline. The etching function disappearance process includes: neutralization treatment, supplying a neutralizing solution toward the treatment film on the substrate, so that the pH of the treatment film is closer to neutral than the pH of the treatment film after the pH adjustment treatment.

Images