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 component forming step of performing an etching component forming process on the treatment film, thereby forming an etching component in the treatment film; an etching step of etching a surface layer portion of the substrate by the etching component formed in the etching component forming step; and a treatment film removing step of supplying a peeling liquid to a surface of the treatment film, thereby peeling the treatment film from the surface of the substrate to remove the treatment film from the surface of the substrate.

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing method for processing a substrate, a substrate processing apparatus, and a processing liquid used for the substrate processing method and the substrate processing apparatus. The substrate to be processed includes, for example, a semiconductor wafer, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and a substrate for a flat panel display (FPD) such as a liquid crystal display device, a plasma display, an organic EL (electroluminescence) display device, and the like. BACKGROUND

[0002] Hydrofluoric acid is used as an etching liquid for etching the surface of a substrate (see Patent Document 1 below). After the substrate is processed with the etching liquid, the surface of the substrate is rinsed with a rinse liquid such as DIW (deionized water).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: U.S. Patent Application Publication No. 2012 / 260949 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] In such an etching process, the amount of discharge of the etching liquid and the rinse liquid mixed with the etching liquid is large, and thus the environmental burden is large. Therefore, an object of the present application is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid that can reduce the amount of use of an etching component.

[0008] MEANS FOR SOLVING THE PROBLEMS

[0009] One of the embodiments of the present application is to provide a substrate processing method including: a treatment film forming step of supplying a treatment liquid to the 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 component forming step of performing an etching component forming process on the treatment film, thereby forming an etching component in the treatment film; an etching step of etching a surface layer portion of the substrate by the etching component formed in the etching component forming step; and a treatment film removing step of supplying a peeling liquid to the surface of the treatment film, thereby peeling the treatment film from the surface of the substrate and removing the treatment film from the surface of the substrate.

[0010] According to the substrate processing method, a processing film formed on a substrate is subjected to a treatment for forming an etching component by heating, light irradiation, water supply, or the like. Thus, an etching component is formed in the processing film, and the surface layer of the substrate is etched by the etching component.

[0011] Unlike the substrate processing method, in a method for etching the surface layer of a substrate while continuously supplying an etching liquid to the surface of the substrate, the etching component is continuously discharged toward the outside of the substrate. On the other hand, the etching component formed in the processing film does not escape to the outside of the substrate but reacts with the surface layer of the substrate. Thus, the consumption of the etching component can be reduced.

[0012] Further, in the processing film removal process, the processing film is not removed from the surface of the substrate by being dissolved in the peeling liquid but is removed from the surface of the substrate by being peeled. Thus, the removal target object such as a particle adhering to the surface of the substrate can be peeled and removed from the surface of the substrate.

[0013] Further, the surface of the substrate is recessed more than before the start of the etching process because the surface layer of the substrate is etched by the etching component. Thus, the removal target object can be floated from the surface of the substrate. Thus, the processing film can be peeled and removed by peeling after the etching based on the etching component in the processing film, and thus the removal target object can be peeled and removed favorably.

[0014] Further, the processing film need not be composed only of a solid component. The processing film can be composed of both a solid component and a liquid component as long as the entire processing film maintains a fixed shape.

[0015] In one of embodiments of the present application, the substrate processing method further includes a high-solubility component formation process of forming a first high-solubility component in the processing film by subjecting the processing film to a high-solubility component formation treatment after the etching component formation process and before the processing film removal process, the first high-solubility component having a higher solubility in the peeling liquid than other components in the processing film. Then, in the processing film removal process, the peeling liquid is supplied to the surface of the substrate, and thus the first high-solubility component in the processing film is dissolved.

[0016] According to the substrate processing method, the high-dissolubility component formation processing such as light irradiation is performed, and thus the first high-dissolubility component is formed in the processing film. The first high-dissolubility component formed in the processing film is dissolved by the peeling liquid supplied to the surface of the substrate later. The first high-dissolubility component in the processing film is selectively dissolved by the peeling liquid, and thus a gap (through-hole) is formed in the processing film. Therefore, the peeling liquid can rapidly reach the interface between the processing film and the substrate via the gap formed in the processing film. The peeling liquid reaches the interface between the substrate and the processing film, and thus the processing film is peeled from the surface of the substrate. Thus, the processing film can be rapidly peeled from the surface of the substrate after the etching based on the etching component is completed.

[0017] In one embodiment of the present application, in the aforementioned processing film formation step, the aforementioned processing film containing the first low-dissolubility component is formed, and the aforementioned first low-dissolubility component has a lower solubility in the aforementioned peeling liquid than the aforementioned first high-dissolubility component.

[0018] According to the substrate processing method, the solubility of the first low-dissolubility component in the peeling liquid is lower than the solubility of the first high-dissolubility component in the peeling liquid. Therefore, the first high-dissolubility component is dissolved by the peeling liquid, and on the other hand, the first low-dissolubility component is not dissolved by the peeling liquid but is maintained in the processing film in a solid state.

[0019] Therefore, the first high-dissolubility component can be dissolved in the peeling liquid while the first low-dissolubility component is maintained in the processing film without being dissolved in the peeling liquid. Therefore, the peeling liquid reaches the interface between the substrate and the processing film via the gap formed by the dissolution of the first high-dissolubility component.

[0020] As a result, the processing film can be rapidly peeled from the surface of the substrate after the etching based on the etching component is completed.

[0021] Since the first low-dissolubility component is maintained in a solid state, the removal target object can be held by the first low-dissolubility component even after the first high-dissolubility component is dissolved. Even when the processing film is removed from the surface of the substrate by the peeling liquid, the state of holding the removal target object can be maintained by the processing film.

[0022] In one embodiment of the present application, the aforementioned processing film containing the first reaction component is formed in the aforementioned processing film formation step. In the aforementioned etching component formation step, the aforementioned first reaction component is decomposed by the aforementioned etching component formation processing, and thus the second reaction component and the aforementioned etching component are formed in the aforementioned processing film. Subsequently, in the aforementioned high-dissolubility component formation step, the aforementioned second reaction component is decomposed by the aforementioned high-dissolubility component formation processing, and thus the aforementioned first high-dissolubility component is formed in the aforementioned processing film.

[0023] According to this substrate processing method, the first reaction component is decomposed by the etching component formation processing, thereby forming the etching component and the second reaction component. Since the etching component is formed by an external stimulus, it is easy to manage the timing of the start of etching compared to a case where the component in the processing film is naturally decomposed to form the etching component.

[0024] Next, the second reaction component is decomposed by the external stimulus of the high-solubility component formation processing and forms the first high-solubility component, which is dissolved by the peeling liquid supplied to the surface of the substrate thereafter. Therefore, the processing film is maintained on the substrate until the peeling liquid is supplied, and is peeled off promptly by the supply of the peeling liquid. Thus, it is possible to suppress the consumption of the etching component and to accurately manage the etching amount of the surface layer portion of the substrate.

[0025] In one embodiment of the present application, the aforementioned substrate processing method further includes a decomposition promotion liquid supply step of supplying a decomposition promotion liquid to the surface of the aforementioned substrate, the aforementioned decomposition promotion liquid being used to promote the decomposition of the aforementioned first reaction component in the aforementioned etching component formation step. According to this substrate processing method, the decomposition of the first reaction component is promoted by the decomposition promotion liquid. Thus, it is possible to promptly etch the surface layer portion of the substrate.

[0026] In one embodiment of the present application, the decomposition of the aforementioned second reaction component is promoted by the aforementioned decomposition promotion liquid supplied to the surface of the aforementioned substrate in the aforementioned decomposition promotion liquid supply step. According to this substrate processing method, the decomposition of the second reaction component is promoted by the decomposition promotion liquid. Thus, it is possible to promptly form the first high-solubility component.

[0027] In one embodiment of the present application, the aforementioned processing film containing the first reaction component is formed in the aforementioned processing film formation step. Next, the aforementioned processing film is subjected to the etching component formation processing, thereby decomposing the aforementioned first reaction component in the aforementioned processing film and forming the etching component.

[0028] According to this substrate processing method, the first reaction component is decomposed by the etching component formation processing, thereby forming the etching component. Since the etching component is formed by an external stimulus, it is easy to manage the timing of the start of etching compared to a case where the component in the processing film is naturally decomposed to form the etching component. Thus, it is possible to accurately manage the etching amount of the surface layer portion of the substrate.

[0029] In one embodiment of the present application, the aforementioned first reaction component is a carboxylic acid ester or a sulfonic acid ester. A carboxylic acid ester or a sulfonic acid ester, etc. can form an acid component such as a carboxylic acid or a sulfonic acid by hydrolysis, and the aforementioned acid component functions as the etching component.

[0030] In one embodiment of the present invention, a treatment film containing a second highly soluble component is formed in the aforementioned treatment film forming step. Then, the aforementioned second highly soluble component in the treatment film is dissolved using the aforementioned stripping solution supplied in the aforementioned treatment film removal step.

[0031] According to this substrate processing method, a processing film containing a second highly soluble component is formed during the processing film formation process. The second highly soluble component in the processing film is dissolved by a stripping liquid subsequently supplied to the surface of the substrate. The stripping liquid selectively dissolves the second highly soluble component in the processing film, thereby forming gaps (through holes) in the processing film. Therefore, the stripping liquid can rapidly reach the interface between the processing film and the substrate through the gaps formed in the processing film. The stripping liquid enters the interface between the substrate and the processing film, peeling the processing film from the surface of the substrate. Thus, after etching based on the etching component is completed, the processing film can be rapidly peeled from the surface of the substrate.

[0032] In one embodiment of the present invention, the aforementioned treatment film containing a second low-soluble component is formed in the aforementioned treatment film forming process, wherein the second low-soluble component has lower solubility in the aforementioned stripping solution than the second high-soluble component.

[0033] According to this substrate processing method, the second low-soluble component has lower solubility in the stripping solution than the second high-soluble component. Therefore, the second high-soluble component is dissolved by the stripping solution, while the second low-soluble component is not dissolved by the stripping solution but is maintained in a solid state in the processed film.

[0034] Therefore, the second highly soluble component can be dissolved in the stripping solution while the second less soluble component is kept in the treated film without dissolving in the stripping solution. Thus, the stripping solution reaches the interface between the substrate and the treated film through the gap created by the dissolution of the second highly soluble component.

[0035] As a result, the treatment film can be quickly peeled off from the surface of the substrate after the etching based on the etching components is completed.

[0036] Because the second least soluble component is maintained in a solid state, the target material can be retained by the second least soluble component even after the second most soluble component dissolves. Even after the stripping solution is supplied, the state of the target material can be maintained by the treatment membrane.

[0037] In one embodiment of the present invention, the surface layer of the substrate is etched in the aforementioned etching process, thereby forming etching residue. The etching residue is retained by the aforementioned processing film formed in the aforementioned processing film formation process. Furthermore, the aforementioned processing film removal process includes the following step: removing the etching residue together with the aforementioned processing film while the etching residue is retained by the aforementioned processing film.

[0038] According to this substrate processing method, the etching residue generated by etching the surface layer of the substrate is removed from the substrate surface together with the processing film during the processing film removal process. Therefore, after removing the processing film, there is no need to perform a separate process to remove the etching residue.

[0039] Another embodiment of the present invention provides 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 present on the surface of the substrate, thereby forming a processing film on the surface of the substrate; an etching component forming processing unit for performing an etching component forming process on the processing film; a stripping liquid supply unit for supplying stripping liquid toward the surface of the substrate for stripping the processing film from the surface of the substrate; and a controller for controlling the processing liquid supply unit, the processing film forming unit, the etching component forming processing unit, and the stripping liquid supply unit.

[0040] 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 supplied to 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 component formation process, performing the aforementioned etching component formation process by the aforementioned etching component formation processing unit, thereby forming etching components in the aforementioned processing film; an etching process, etching the surface portion of the aforementioned substrate by using the etching components formed in the aforementioned etching component formation process; and a processing film removal process, supplying stripping liquid from the aforementioned stripping liquid supply unit toward the surface of the aforementioned substrate, thereby peeling the aforementioned processing film off the surface of the aforementioned substrate and removing the aforementioned processing film from the surface of the aforementioned substrate.

[0041] According to this substrate processing apparatus, the same effect as the aforementioned substrate processing method is achieved.

[0042] In another embodiment of the present invention, a processing liquid is provided, which forms a processing film by curing or hardening, and the processing film can be peeled off from the surface of a substrate by a stripping liquid. The processing liquid comprises: a reactive component, which forms an etching component in the processing film by an etching component formation process, the etching component being used to etch the surface portion of the substrate; and a solid state maintaining component, which maintains a solid state in the processing film even after the etching component formation process.

[0043] Based on this configuration, a processing film is formed by solidifying or hardening a processing solution on the surface of a substrate. In this state, etching components are formed through processes such as heating, light irradiation, and water supply, thereby forming etching components within the processing film. On the other hand, the solid-state maintaining components remain in a solid state even after the etching component formation process. Therefore, the surface layer of the substrate can be etched using the etching components formed in the processing film. That is, the surface layer of the substrate can be etched without allowing etching components to escape to the outside of the substrate. Therefore, compared to etching solutions that are continuously supplied to the surface of the substrate to etch the surface layer, the consumption of etching components can be reduced.

[0044] 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

[0045] 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.

[0046] 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.

[0047] Figure 3A This is a schematic diagram illustrating an example of the decomposition reaction of the first reactive component in a processed film formed based on etching components.

[0048] Figure 3B This is a schematic diagram illustrating an example of the decomposition reaction of the second reactant in a treated membrane based on the formation of highly soluble components.

[0049] Figure 4A This is a schematic diagram illustrating another example of the decomposition reaction of the first reactive component in the treated film formed based on the aforementioned etching component formation process.

[0050] Figure 4B This is a schematic diagram illustrating another example of the decomposition reaction of the second reactive component in the treated membrane based on the aforementioned treatment of highly soluble components.

[0051] Figure 5 This is a block diagram showing the electrical configuration of the main parts of the aforementioned substrate processing apparatus.

[0052] Figure 6 This is a flowchart illustrating an example of substrate processing based on the aforementioned substrate processing apparatus.

[0053] Figure 7AThis is a schematic diagram illustrating the state of the processing solution supply process (step S2) for the aforementioned substrate processing.

[0054] Figure 7B This is a schematic diagram illustrating the state of the processing film formation process (step S3) of the aforementioned substrate processing.

[0055] Figure 7C This is a schematic diagram illustrating the state of the processing film formation process (step S3) of the aforementioned substrate processing.

[0056] Figure 7D This is a schematic diagram illustrating the state of the processing film heating process (step S4) of the aforementioned substrate processing.

[0057] Figure 7E This is a schematic diagram illustrating the state of the aforementioned substrate processing light irradiation process (step S6).

[0058] Figure 7F This is a schematic diagram illustrating the state of the aforementioned substrate processing film removal process (step S7).

[0059] Figure 7G This is a schematic diagram illustrating the state of the aforementioned substrate processing film removal process (step S7).

[0060] Figure 7H This is a schematic diagram illustrating the state of the cleaning process (step S8) of the aforementioned substrate treatment.

[0061] Figure 7I This is a schematic diagram illustrating the state of the aforementioned substrate processing residue removal process (step S9).

[0062] Figure 8A This is a schematic diagram illustrating the state of removing the treatment film from the surface of a substrate.

[0063] Figure 8B This is a schematic diagram illustrating the state of removing the treatment film from the surface of a substrate.

[0064] Figure 8C This is a schematic diagram illustrating the state of removing the treatment film from the surface of a substrate.

[0065] Figure 8D This is a schematic diagram illustrating the state of removing the treatment film from the surface of a substrate.

[0066] Figure 8E This is a schematic diagram illustrating the state of removing the treatment film from the surface of a substrate.

[0067] Figure 8F This is a schematic diagram illustrating the state of removing the treatment film from the surface of a substrate.

[0068] Figure 9A This is a flowchart illustrating the second example of the aforementioned substrate processing.

[0069] Figure 9B This is a flowchart illustrating the third example of the aforementioned substrate processing.

[0070] Figure 9C This is a flowchart illustrating the fourth example of the aforementioned substrate processing.

[0071] Figure 9D This is a flowchart illustrating the fifth example of the aforementioned substrate processing.

[0072] Figure 10 This is a schematic diagram illustrating an example of the decomposition reaction of the first reactive component in the processed film formed based on the aforementioned etching component formation process during substrate processing in the second embodiment.

[0073] Figure 11 This is a schematic diagram illustrating another example of the decomposition reaction of the first reactive component in the processed film formed based on the aforementioned etching component formation process in the substrate processing of the second embodiment.

[0074] Figure 12 This is a flowchart illustrating an example of substrate processing based on the substrate processing apparatus of the second embodiment.

[0075] 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.

[0076] Figure 13B 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.

[0077] Figure 13C 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.

[0078] Figure 13D 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.

[0079] Figure 13E 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.

[0080] Figure 14A This is a flowchart illustrating the second example of the aforementioned substrate processing.

[0081] Figure 14B This is a flowchart illustrating the third example of the aforementioned substrate processing.

[0082] Figure 14C This is a flowchart illustrating the fourth example of the aforementioned substrate processing.

[0083] Figure 14D This is a flowchart illustrating the fifth example of the aforementioned substrate processing.

[0084] Figure 15 This is a schematic diagram illustrating a variation of the heater unit included in the aforementioned substrate processing apparatus.

[0085] Figure 16 This is a schematic diagram illustrating a first variation of the light irradiation unit provided in the aforementioned substrate processing apparatus.

[0086] Figure 17 This is a schematic diagram illustrating a second variation of the light irradiation unit provided in the aforementioned substrate processing apparatus. Detailed Implementation

[0087] [First Implementation Method]

[0088] 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.

[0089] 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 substrate. As the substrate W, a substrate with etchable components exposed on its surface can be used.

[0090] As the substrate W, it is preferable to use a substrate whose surface exposes at least one of SiO2 (silicon oxide), TiN (titanium nitride), Cu (copper), and Ru (ruthenium). Only one of the above substances may be exposed on the surface of the substrate W, or multiple of the above substances may be exposed. Alternatively, an etchable substance other than the above substances may be exposed on the surface of the substrate W.

[0091] 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.

[0092] 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 contains a processing liquid, a stripping liquid, a cleaning liquid (decomposition promoting liquid), a residue removal liquid, etc.

[0093] 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.

[0094] Figure 2 This is a schematic diagram illustrating an example of the configuration of the processing unit 2. The processing unit 2 further includes a spin chuck 5, a heater unit 6, a light irradiation unit 8, a first moving nozzle 9, a second moving nozzle 10, a third moving nozzle 11, and a fourth moving nozzle 12.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] The first cover 72A and the second cover 72B each have an annular groove that opens upwards.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] The light irradiation unit 8 is, for example, installed on the upper wall 4a of the chamber 4. The light irradiation unit 8 irradiates light toward the upper surface of the substrate W through a slit 4b provided in the upper wall 4a of the chamber 4.

[0116] The light irradiation unit 8 includes: a lamp 80 that emits light; a lamp housing 81 that houses the lamp 80; and a shutter 82 that blocks the light emitted from the lamp 80. The lamp 80 includes, for example, a filament and a quartz tube for housing the filament. The light emitted from the lamp 80 can be, for example, infrared, ultraviolet, or visible light.

[0117] The processing unit 2 further includes: a lamp energizing unit 85 configured to energize the lamp 80 and stop energizing the lamp 80; and a gate opening / closing unit 86 for opening and closing the gate 82. The lamp 80 emits light by being energized. The gate 82 moves between a closed position (blocking position) and an open position (illumination position), the closed position being the position that blocks the light emitted by the lamp 80, and the open position being the position that allows the light emitted by the lamp 80 to pass through.

[0118] The lamp power supply unit 85 is, for example, a power source; the door opening and closing unit 86 is, for example, a motor.

[0119] The first moving nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) used to supply (eject) processing liquid toward the upper surface of the substrate W held by the rotating clamp 5.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] The rotation shaft drive unit causes the rotation shaft to rotate about a vertical axis of rotation, 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 move up and down. Based on the swinging and lifting of the arm, the first moving nozzle 9 moves in both the horizontal and vertical directions. The rotation shaft drive unit includes: a motor to rotate the rotation shaft; and a ball screw mechanism to move the rotation shaft up and down.

[0124] 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.

[0125] 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 particles or other objects to be removed from the substrate W. Examples of objects to be removed include foreign matter adhering to the surface of the substrate W.

[0126] 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.

[0127] Furthermore, the treatment membrane does not necessarily need to be composed solely of solid components. As long as the membrane is non-flowing and maintains a fixed overall shape, it can also be 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.

[0128] The processing solution contains a primary reactive component (reactive component) and a low-soluble component as a solute. The primary reactive component is the component that exhibits etching function through external stimuli. External stimuli include, for example, heating, light irradiation, and the supply of liquids such as water.

[0129] These external stimuli induce a decomposition reaction that causes the first reactive component to decompose. This results in the formation of an etching component and a second reactive component. The etching component is a component capable of etching the surface layer of the substrate W.

[0130] The second reactant component decomposes upon exposure to light. In other words, light exposure induces a decomposition reaction that decomposes the second reactant component. This decomposition of the second reactant component forms a first highly soluble component. The first highly soluble component is a component with high solubility in the stripping solution described later (compared to other components in the treated film). The etching component and the first highly soluble component are, for example, organic acids. The first highly soluble component does not need to have the acidity required to etch the surface layer of the substrate W; it only needs to have the polarity required to dissolve in the stripping solution described later.

[0131] As the first reactant, carboxylic acid esters or sulfonate esters can be used, for example. Examples of carboxylic acid esters include polyethylene terephthalate, polylactic acid, polybutylene terephthalate, and polyethylene naphthalate.

[0132] Carboxylic esters that can be used as the first reactant do not necessarily have to be polymers. Examples of non-polymer carboxylic esters include diethoxyethyl succinate, di(2-ethylhexyl)adipate, di(2-ethylhexyl)sebacic acid, 4,5-epoxycyclohexane-1,2-di(2-ethylhexyl)dicarboxylic acid, and 4-cyclohexene-1,2-dicarboxylic acid. Bis(2-ethylhexyl) phthalate, diisoamyl phthalate, naphthalene dicarboxylic acid(2-ethylhexyl) phthalate, etc.

[0133] The first reactant may also include one or more carboxylic acid esters selected from these carboxylic acid esters.

[0134] Examples of sulfonate esters include N-(tert-butoxycarbonyl)-p-toluenesulfonamide, sodium dimethyl 5-sulphonatoisophthalate, 1-methoxycarbonylpentadecane-5-sulfonic acid, tert-butyl 4-[3-(methoxycarbonyl)phenylsulfonamido]piperidine-1-carboxylate, and 2-tert-butoxycarbonylmethoxyphenyldiphenylsulfoniumnonafluoro-n-butane sulfonate.

[0135] The first reactant may also include one or more sulfonates selected from these sulfonates.

[0136] like Figure 3A As shown, in the case where the first reactant is a carboxylic acid ester, the first reactant is hydrolyzed in the presence of water and under heating conditions (e.g., above 50°C and below 80°C). The carboxylic acid generated by hydrolysis is the etching component, and the alcohol generated together with the carboxylic acid during hydrolysis is the second reactant.

[0137] exist Figure 3A In this context, R1 is, for example, a hydrocarbon group, and R2 is, for example, a functional group possessing an ester group. Figure 3B As shown, R2 is R3-CO2-R4. R3 and R4 are, for example, hydrocarbon groups.

[0138] R1 can also be a functional group in which the hydrogen atom in the hydrocarbon group has been replaced by a fluorine or chlorine atom. Compared to the case where R1 is a functional group in the hydrocarbon group that does not contain fluorine or chlorine atoms, the acidity of the etching component is higher when R1 is a functional group in the hydrocarbon group in which the hydrogen atom has been replaced by a fluorine or chlorine atom. Therefore, the surface layer of the substrate W can be etched quickly.

[0139] In the case where the first reactant is a carboxylic acid ester, such as Figure 3B As shown, in the presence of water and under heating conditions (e.g., above 50°C and below 80°C), light is irradiated, thereby hydrolyzing the second reactant. The carboxylic acid generated by the hydrolysis of the second reactant is the first highly soluble component. Figure 3BR3 and R4 are hydrocarbon groups, etc. The carboxylic acid, which acts as the first highly soluble component, does not have the acidity required to etch the surface layer of the substrate W, but only the polarity required to be dissolved by the stripping solution described later.

[0140] like Figure 4A As shown, in the case where the first reactant is a sulfonate ester, the first reactant is hydrolyzed in the presence of water under heating conditions (e.g., above 50°C and below 80°C). The sulfonic acid generated by the hydrolysis of the first reactant is the etching component, and the alcohol generated together with the sulfonic acid during hydrolysis is the second reactant. Figure 4A In the middle, R 11 For example, a hydrocarbon group, R 12 For example, some of the functional groups have ester groups. Figure 4B As shown, R 12 For R 13 -SO3-R 14 R 13 and R 14 For example, a hydrocarbon group.

[0141] R 11 It can also be a functional group in which the hydrogen atom in a hydrocarbon group has been replaced by a fluorine or chlorine atom. (Similar to R) 11 Compared to the case where the hydrocarbon group does not contain functional groups with fluorine or chlorine atoms, in R 11 In cases where hydrogen atoms in hydrocarbon groups have been replaced by fluorine or chlorine functional groups, the acidity of the etching component is high. Therefore, the surface layer of substrate W can be etched rapidly.

[0142] In the case where the first reactant is a sulfonate ester, such as Figure 4B As shown, in the presence of water and under heating conditions (e.g., above 50°C and below 80°C), light is irradiated, thereby hydrolyzing the second reactant. The sulfonic acid generated by the hydrolysis of the second reactant is the first highly soluble component. Figure 4B In the middle, R 13 and R 14 For example, a hydrocarbon group. The sulfonic acid, which acts as the first highly soluble component, does not have the acidity required to etch the surface layer of the substrate W, but only the polarity required to be dissolved by the stripping solution described later.

[0143] In the case where the first reactant is a carboxylic acid, the etching component is a molecule with a carboxyl group as a functional group at the end. In the case where the first reactant is a sulfonic acid, the etching component is a molecule with a sulfonic acid group as a functional group at the end. In the case where the first reactant is a carboxylic acid, the second reactant is a molecule with a carboxylic ester bond within the molecule and a hydroxyl group (hydroxyl group) at the end. In the case where the first reactant is a sulfonic acid, the second reactant is a molecule with a sulfonate ester bond within the molecule and a hydroxyl group (hydroxyl group) at the end.

[0144] As a low-soluble component, it is a substance with lower solubility in the stripping solution described later than the first high-soluble component. The low-soluble component remains in a solid state even after etching component formation treatment. An example of a low-soluble component is phenolic varnish (novolac). This low-soluble component is an example of the first low-soluble component and also an example of a component that maintains a solid state.

[0145] The solvent contained in the treatment solution need only be a liquid used to dissolve the poorly soluble components and the first reaction components. Preferably, the solvent contained in the treatment solution is a liquid with miscibility (miscibility) with the stripping 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).

[0146] The treatment membrane is mainly composed of a low-soluble component in a solid state (low-soluble component solid) and a first reaction component in a solid state (first reaction component solid).

[0147] The term "solid state" can also refer to a state consisting solely of solid components without any liquid components. A solid state can also be a semi-solid state containing liquid components or a gel state. Solvent residues may also remain in the treated membrane.

[0148] A detailed description of the solvents and low-soluble components contained in the treatment solution is provided below.

[0149] The second moving nozzle 10 is an example of a stripping fluid nozzle (stripping fluid supply unit), used to continuously supply (spray) stripping fluid such as ammonia towards the upper surface of the substrate W held by the rotating clamp 5. The stripping fluid is a liquid used to peel off the treatment film formed on the substrate W from the upper surface of the substrate W.

[0150] 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).

[0151] 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.

[0152] 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.

[0153] The second movable nozzle 10 is connected to the stripping fluid pipe 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 pipe 41, is opened, the stripping fluid is also 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 stripping fluid valve 51 is open, the stripping fluid is supplied to the central region of the upper surface of the substrate W.

[0154] The stripping fluid sprayed from the second movable nozzle 10 is a liquid that makes the first highly soluble component more easily soluble than the less soluble component. The stripping fluid 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 solution (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. The stripping fluid is not limited to alkaline liquids and may also be pure water (preferably DIW) or an aqueous solution of either neutral or acidic conditions (non-alkaline aqueous solution).

[0155] 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.

[0156] 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).

[0157] 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.

[0158] 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.

[0159] 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 flows continuously from the nozzle outlet of the third movable nozzle 11 and is sprayed downwards. 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.

[0160] Examples of cleaning solutions include pure water (such as DIW), carbonated water, electrolyzed ionized water, hydrochloric acid with a dilution concentration (e.g., approximately 1 ppm to 100 ppm), ammonia with a dilution concentration (e.g., approximately 1 ppm to 100 ppm), and reduced water (hydrogen water). Liquids that can be used as cleaning solutions contain water. Therefore, the cleaning solution can be used as an external stimulus to induce the etching function of the first reaction component. Specifically, the cleaning solution can be used as a decomposition accelerating solution for the decomposition (hydrolysis) of the first reaction component. The third moving nozzle 11 can also be a decomposition accelerating solution nozzle (decomposition accelerating solution supply unit).

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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 downwards 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.

[0166] The residue removal solution is a liquid that, after the stripping liquid is 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, it is preferable that the residue removal solution has compatibility with the stripping liquid. After being peeled off from the upper surface of the substrate W by the stripping liquid 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.

[0167] 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.

[0168] Organic solvents that function as residue removal liquids and low surface tension liquids include, for example, liquids containing at least one of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (Propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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, lamp energizing unit 85, gate opening / closing unit 86, processing fluid valve 50, stripping 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.

[0173] Figure 6 This is a flowchart illustrating a first 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-7I This is a schematic diagram used to illustrate the state of each step in the substrate processing.

[0174] like Figure 6As 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), processing film heating process (step S4), decomposition promoting liquid supply process (step S5), light irradiation process (step S6), processing film removal process (step S7), cleaning process (step S8), residue removal process (step S9), spin drying process (step S10), and substrate unloading process (step S11).

[0175] The following mainly refers to Figure 2 as well as Figure 6 Appropriate reference Figures 7A-7I .

[0176] 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).

[0177] When the substrate W is being moved in, the heater unit 6 is positioned in a non-heating position with the heater 62 energized. The non-heating position is one where the substrate W is not heated. For example, the lower position is a non-heating position. The non-heating position simply requires that the substrate W be moved away from it at a level where its temperature will not rise. When the substrate W is being moved in, the light irradiation unit 8 has its barrier 82 positioned in a closed position with the lamp energized.

[0178] The substrate W held by the rotating clamp 5 continues until the spin-drying process (step S10) ends. During the period from the start of the substrate holding process until the end of the spin-drying process (step S10), 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).

[0179] 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.

[0180] With the first moving nozzle 9 in the processing position, the processing fluid valve 50 is opened. Thus, as... Figure 7AAs 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 upper surface of the substrate W by centrifugal force and is coated on the entire upper surface of the substrate W. As a result, a liquid film 101 of the processing liquid is formed on the substrate W (processing liquid film formation process).

[0181] 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.

[0182] Next, execute Figure 7B as well as Figure 7C The processing film formation process shown is step S3. In this process, the processing liquid on the substrate W is cured or hardened to form a processing film 100 on the upper surface of the substrate W (see reference). Figure 7C ).

[0183] 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.

[0184] 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.

[0185] 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 is formed from the center side of substrate W towards the periphery. Through this airflow, the gaseous solvent 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 membrane 100 is shown to be formed. In the treatment membrane formation process, the rotating motor 23 functions as a treatment membrane formation unit. The rotating motor 23 also functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the treatment liquid.

[0186] In the membrane formation process, the removal of the treatment liquid based on centrifugal force may not be necessary, and the treatment membrane 100 may be formed solely by solvent evaporation. In this case, the consumption of the treatment liquid can be suppressed.

[0187] 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.

[0188] Next, the following steps are performed: a film heating process (step S4) to heat the film 100; and a decomposition accelerator supply process (step S5) to supply a cleaning solution as a decomposition accelerator to the upper surface of the substrate W.

[0189] Specifically, the third nozzle moving unit 37 moves the third moving nozzle 11 to the processing position. The processing position of the third moving nozzle 11 is, for example, the central position. Then, with the third moving nozzle 11 in the processing position, the cleaning fluid valve 52 is opened. Thus, as... Figure 7D As shown, a cleaning solution, which serves as a decomposition accelerator, is supplied (ejected) from the third moving nozzle 11 toward the central region of the upper surface of the rotating substrate W (decomposition accelerator supply process, decomposition accelerator ejection process). The cleaning solution supplied to the upper surface of the substrate W expands to the entire upper surface of the substrate W by centrifugal force. As a result, the treatment film 100 on the substrate W expands due to the cleaning solution.

[0190] Next, 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 separated 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.

[0191] Either the membrane heating process (step S4) or the decomposition accelerator supply process (step S5) can be started first.

[0192] By heating the treatment film 100 and supplying a cleaning solution, the first reactive component in the treatment film 100 is decomposed to generate an etching component and a second reactive component. In the case where the first reactive component is a carboxylic acid ester or a sulfonate ester, the first reactive component is hydrolyzed. Thus, an etching component formation process is performed, in which etching components are formed in the treatment film 100 through etching component formation treatment of the treatment film 100 (heating and supply of cleaning solution). The substrate W is etched using the etching components formed in the treatment film 100 (etching process). The heater unit 6 and the third moving nozzle 11 function as an etching component formation processing unit.

[0193] The supply of cleaning solution and the heating of substrate W are continued for a predetermined time, for example, for 30 seconds. In the film heating process (step S4) and the decomposition accelerator supply process (step S5), substrate W is rotated at a predetermined etching composition rotation speed, for example, at 800 rpm.

[0194] Next, a light irradiation process (step S6) is performed, in which light is irradiated onto the processing film 100 on the substrate W.

[0195] Specifically, the cleaning fluid valve 52 is closed, and the third nozzle moving unit 37 moves the third moving nozzle 11 to the retracted position. By closing the cleaning fluid valve 52, the supply of cleaning fluid to the upper surface of the substrate W is stopped. This removes the liquid film of cleaning fluid from the substrate W.

[0196] Next, the heater lifting unit 65 moves the heater unit 6 to a non-heating position. Then, the gate opening / closing unit 86 moves the gate 82 to the open position. Thus, as... Figure 7E As shown, light is irradiated from the light irradiation unit 8 toward the processing membrane 100 (light irradiation process).

[0197] By irradiating the treatment membrane 100 with light, the second reactant in the treatment membrane 100 is decomposed to generate a first highly soluble component. In the case where the first reactant is a carboxylic acid ester or a sulfonate ester, the second reactant is hydrolyzed. Thus, a highly soluble component formation process is performed, in which the first highly soluble component is formed in the treatment membrane 100 through a highly soluble component formation treatment (light irradiation). The light irradiation unit 8 functions as a highly soluble component formation treatment unit.

[0198] Preferably, the cleaning solution supplied in the above-mentioned decomposition promoting solution supply step remains in the treatment membrane 100, and preferably, the heat supplied in the above-mentioned treatment membrane heating step also remains in the treatment membrane 100. This promotes the decomposition of the second reaction component based on light irradiation. In particular, when the first reaction component is a carboxylic acid ester or a sulfonate ester, hydrolysis caused by the retention of the cleaning solution and the heat is significantly promoted.

[0199] In the light irradiation process (step S6), the substrate W is rotated at a predetermined high-solubility component rotation speed, for example, at 800 rpm.

[0200] Next, a processing film removal process (step S7) is performed, in which the processing film 100 is peeled off and removed from the upper surface of the substrate W by supplying a stripping liquid to the upper surface of the substrate W.

[0201] Specifically, the gate opening / closing unit 86 moves the gate 82 to the closed position, thereby stopping the illumination of light onto the treatment membrane 100. Next, the second nozzle moving unit 36 ​​moves the second moving nozzle 10 to the treatment position. The treatment position of the second moving nozzle 10 is, for example, the central position.

[0202] With the second moving nozzle 10 in the processing position, the stripping fluid valve 51 is opened. Thus, as... Figure 7F As shown, a stripping fluid is supplied (ejected) from the second moving nozzle 10 toward the central region of the upper surface of the rotating substrate W (stripping fluid supply process, stripping fluid ejection process). The stripping fluid supplied to the upper surface of the substrate W is spread to the entire substrate W by centrifugal force. The stripping fluid supplied to the upper surface of the substrate W dissolves the first highly soluble component 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 solution is continuously supplied, thereby peeling and removing the treatment film 100 from the upper surface of the substrate W (treatment film removal process).

[0203] In the film removal process (step S7), the substrate W rotates at a predetermined removal rotation speed, for example, at 800 rpm.

[0204] Next, a cleaning process (step S8) is performed, in which the stripping fluid 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.

[0205] 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 stripping 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 fluid process, stripping fluid discharge process).

[0206] Cleaning fluid is supplied to the upper and lower surfaces of substrate W for a predetermined time, for example, 30 seconds. In the cleaning process (step S8), substrate W is rotated at a predetermined stripping fluid removal rotation speed, for example, 800 rpm.

[0207] Next, a residue removal process (step S9) 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.

[0208] 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.

[0209] 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).

[0210] The residue removal liquid supplied to the upper surface of the substrate W from the fourth moving nozzle 12 is subjected to centrifugal force and expands radially to cover the entire upper surface of the substrate W. A problem arises: even after the treatment film is peeled off from the substrate W and removed from the substrate W by the stripping liquid, residue from the treatment film remains on the upper surface of the substrate W. The residue removal liquid supplied to the upper surface of the substrate W also dissolves this residue from the treatment film. Through centrifugal force, the residue removal liquid, having dissolved the residue from the treatment film, is also discharged from the periphery of the upper surface of the substrate W. Thus, the residue from the treatment film on the substrate W is removed (residue removal process).

[0211] 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 S9), the substrate W rotates at a predetermined residue removal rotation speed, for example, 300 rpm.

[0212] Next, a spin-drying process (step S10) is performed, in which the substrate W is rotated at high speed to dry the upper surface of the substrate W. Specifically, the residue removal liquid valve 53 is closed. This stops the supply of residue removal liquid to the upper surface of the substrate W.

[0213] 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.

[0214] 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.

[0215] 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 S11). The substrate W is transferred from the transport robot CR to the transport robot IR, and is received by the transport robot IR into the carrier C.

[0216] Next, use Figures 8A-8F The state of the peeling treatment film 100 from the substrate W is described in detail. Figures 8A-8F This is a schematic diagram illustrating the state of the treatment film 100 being peeled off from the substrate W.

[0217] 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 of the substrate W. Before the etching component formation process, the processed film 100 contains a first reactive component 110 in a solid state and a low-solubility component 111 in a solid state. The first reactive component 110 and the low-solubility component 111 are solidified or hardened by the evaporation of at least a portion of the solvent contained in the processing liquid.

[0218] Next, refer to Figure 8B The first reactive component 110 is decomposed through an etching component formation process (heating and supply of a decomposition-promoting solution such as water). Specifically, in the decomposition-promoting solution supply step (step S4), a cleaning solution, serving as the decomposition-promoting solution, is supplied to the processed film 100, causing the processed film 100 to expand. When the substrate W is heated in the presence of the cleaning solution (processed film heating step), the first reactive component 110 is decomposed. The decomposition of the first reactive component 110 forms an etching component 112 and a second reactive component 113 in the processed film 100 (etching component formation step, second reactive component formation step). Figure 8CAs shown, the surface portion 150 of the substrate W is etched by etching components 112 formed in the processing film 100 (etching process). The surface portion 150 of the substrate W refers to the portion near the upper surface 151 of the substrate W.

[0219] The etched component 112 is dissolved by the cleaning solution used as a decomposition-promoting liquid. The etched component 112 that contacted the upper surface 151 of the substrate W is removed by etching the surface layer 150 of the substrate W. Therefore, as Figure 8C As shown, the etching component 112 in the processing film 100 moves to the upper surface 151 side of the substrate W in such a way that the concentration of the etching component 112 in contact with the upper surface 151 of the substrate W does not decrease within the processing film 100. Because the processing film 100 expands due to the cleaning solution, the etching component 112 easily moves within the processing film 100. Etching of the surface portion 150 of the substrate W progresses slowly and continuously, with the upper surface 151 of the substrate W receding towards the lower surface side.

[0220] As the upper surface 151 of the substrate W is retracted (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 encapsulated by the processing film 100 (especially the low-solidity component 111 in a solid state) and thus held more firmly. Etching of the surface portion 150 of the substrate W forms etching residue 104. The processing film 100 (especially the low-solidity component 111 in a solid state) 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. The particles 103 and the etching residue 104 are collectively referred to as the object to be removed 105.

[0221] Next, the second reactive component 113 is decomposed through a highly soluble component formation treatment (light irradiation). Specifically, in the light irradiation step (step S6), the treated membrane 100 is irradiated with light, thereby decomposing the second reactive component 113. For example... Figure 8D As shown, a first highly soluble component 114 is formed in the treatment membrane 100 by decomposing the second reactive component 113 (first highly soluble component formation step). As described above, light irradiation is performed while the treatment membrane 100 has residual cleaning liquid and is sufficiently heated, thereby promoting the decomposition of the second reactive component 113.

[0222] Next, refer to Figure 8E The first highly soluble component 114 is selectively dissolved by the stripping solution. That is, the treated membrane 100 is locally dissolved (dissolution process, local dissolution process).

[0223] The phrase "the first highly soluble component 114 in the solid state is selectively dissolved" does not mean that only the first highly soluble component 114 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 first highly soluble component 114 in the solid state is dissolved.

[0224] Taking the selective dissolution of the first highly soluble component 114 as an opportunity, through holes 106 are formed in the portion of the treated membrane 100 where the first highly soluble component 114 is concentrated (through hole formation process).

[0225] The portion where the first highly soluble component 114 is concentrated also contains the low-soluble component 111, rather than only containing the first highly soluble component 114. Since the stripping fluid not only dissolves the first highly soluble component 114 but also dissolves the low-soluble component 111 surrounding the first highly soluble component 114, it promotes the formation of the through-hole 106.

[0226] When viewed from above, the through-hole 106 is, for example, a few nanometers in diameter. The through-hole 106 does not need to be clearly defined to the extent that it can be observed. That is, the through-hole 106 only needs to form a path in the processing film 100 for the stripping 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.

[0227] Here, when solvent and cleaning solution remain moderately in the treated membrane 100, the stripping liquid partially dissolves the treated membrane 100 while dissolving into the solvent and cleaning solution remaining in the treated membrane 100. Specifically, the stripping liquid dissolves the first highly soluble component 114 in the treated membrane 100 while dissolving into the solvent and cleaning solution remaining in the treated membrane 100, thereby forming through-holes 106. Therefore, the stripping liquid easily enters into the treated membrane 100 (dissolution entry process).

[0228] The stripping 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 (peeling removal process).

[0229] 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, the stripping solution reaching the vicinity of the upper surface 151 of the substrate W via the through-hole 106 only dissolves a portion of the low-soluble component 111 in the vicinity of the upper surface 151 of the substrate W. Thus, as Figure 8EAs shown in the enlarged view, the stripping liquid slowly dissolves the low-solubility component 111 in the solid state near the upper surface 151 of the substrate W while gradually entering the gap G between the processing film 100 and the upper surface 151 of the substrate W (stripping liquid entry process).

[0230] Next, for example, cracks are formed in the treated membrane 100 starting from the periphery of the through-hole 106. Therefore, the first highly soluble component 114 is referred to as the crack-inducing component. The treated membrane 100 splits through the formation of cracks and becomes a membrane sheet 108. As... 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).

[0231] Next, a stripping solution is continuously supplied, thereby rinsing the treatment membrane 100 (diaphragm 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 removal process). As a result, the upper surface 151 of the substrate W can be thoroughly cleaned.

[0232] According to the first embodiment, the following effects are achieved.

[0233] According to the first embodiment, the processing film 100 formed on the substrate W is subjected to etching component formation processes such as heating, light irradiation, and water supply. As a result, etching components 112 are formed in the processing film 100, and the surface layer 150 of the substrate W is etched by the etching components 112.

[0234] Unlike this method, in the method of etching the surface layer 150 of the substrate W while continuously supplying etchant to the upper surface 151 of the substrate W, the etching component 112 is continuously discharged outward from the substrate W. On the other hand, the etching component 112 formed in the processing film 100 is not discharged to the outside of the substrate W but reacts with the surface layer 150 of the substrate W. Therefore, the consumption of etching component 112 can be reduced.

[0235] Furthermore, in the processing film removal process, the processing film 100 is peeled off and removed from the upper surface 151 of the substrate W, rather than being dissolved by the stripping liquid and removed from the upper surface 151 of the substrate W. Therefore, particles 103 and other objects to be removed that are attached to the upper surface 151 of the substrate W can be peeled off and removed from the upper surface 151 of the substrate W.

[0236] Furthermore, the surface portion 150 of the substrate W is etched by the etching component 112, thereby causing the upper surface 151 of the substrate W to recede to the lower surface side of the substrate W compared to before the etching process began. Therefore, the object to be removed 150 can be lifted from the upper surface 151 of the substrate W. Thus, after etching based on the etching component 112 in the treatment film 100, the object to be removed 105 can be effectively removed by peeling off the treatment film 100.

[0237] Furthermore, according to the first embodiment, after the etching component formation step and before the processing film removal step, the processing film 100 is subjected to a high-solubility component formation treatment such as light irradiation, thereby forming a first high-solubility component 114 in the processing film 100. In the subsequent processing film removal step, a stripping solution is supplied to the upper surface 151 of the substrate W, thereby dissolving the first high-solubility component 114 in the processing film 100. The dissolution of the first high-solubility component 114 in the processing film 100 by the stripping solution forms a through-hole 106 in the processing film 100. Therefore, the stripping solution can quickly reach the interface between the processing film 100 and the substrate W through the through-hole 106 formed in the processing film 100. The stripping solution enters the interface between the substrate W and the processing film 100 and peels the processing film 100 from the upper surface 151 of the substrate W. Thus, after the etching based on the etching component 112 is completed, the processing film 100 can be quickly peeled from the upper surface 151 of the substrate W.

[0238] According to the first embodiment, in the process of forming a processing membrane, a processing membrane 100 containing a low-soluble component 111 is formed, wherein the low-soluble component 111 has a lower solubility in the stripping solution than the first high-soluble component 114.

[0239] According to this method, the solubility of the low-soluble component 111 in the stripping solution is lower than that of the first highly soluble component 114 in the stripping solution. Therefore, the first highly soluble component 114 is dissolved by the stripping solution, while the low-soluble component 111 is not dissolved by the stripping solution but is maintained in a solid state in the treated membrane 100.

[0240] Therefore, the first highly soluble component 114 can be dissolved in the stripping liquid while the less soluble component 111 is not dissolved in the stripping liquid, thus maintaining it in the processed film 100. Therefore, the stripping liquid reaches the interface between the substrate W and the processed film 100 through the through-holes 106 formed by the dissolution of the first highly soluble component 114.

[0241] As a result, after etching based on etch component 112 is completed, the treatment film 100 can be quickly peeled off from the upper surface 151 of the substrate W.

[0242] 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 first high-soluble component 114 has dissolved. Even when the treatment film 100 is removed from the surface of the substrate W by the stripping liquid, the object to be removed 105 can be maintained by the treatment film 100. Therefore, compared to 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 liquid can be increased. As a result, the object to be removed 105 can be effectively removed from the upper surface of the substrate W by the stripping liquid.

[0243] Furthermore, according to the first embodiment, a treatment film 100 containing a first reactive component 110 is formed in the treatment film formation step. In the etching component formation step, the first reactive component 110 is decomposed by an etching component formation treatment, thereby forming a second reactive component 113 and an etching component 112 in the treatment film 100. Next, in the high-solubility component formation step, the second reactive component 113 is decomposed by a high-solubility component formation treatment, thereby forming a first high-solubility component 114 in the treatment film 100.

[0244] According to this method, the first reaction component 110 is also decomposed through the etching component formation process to form the etching component 112. Since the etching component 112 is formed by external stimulation, it is easier to manage the timing of etching initiation compared to the case where the components in the treatment film 100 decompose naturally to form the etching component 112.

[0245] Next, the second reaction component 113 decomposes and forms a first highly soluble component 114 based on the external stimulus of the highly soluble component formation treatment. The first highly soluble component 114 is then dissolved by the stripping liquid supplied to the upper surface 151 of the substrate W. Therefore, the treated film 100 remains on the substrate W before the stripping liquid is supplied and is rapidly peeled off by the supply of the stripping liquid. Therefore, the consumption of the etching component 112 can be suppressed and the etching amount of the surface layer 150 of the substrate W can be precisely managed.

[0246] Furthermore, according to the first embodiment, a decomposition accelerating liquid is supplied to the upper surface 151 of the substrate W to promote the decomposition of the first reactive component 110 in the etching component formation process. Since the decomposition of the first reactive component 110 is promoted by the decomposition accelerating liquid, the surface layer 150 of the substrate W can be etched quickly.

[0247] Furthermore, according to the first embodiment, the decomposition of the second reactive component 113 is promoted by the decomposition promoting liquid supplied to the upper surface 151 of the substrate W during the decomposition promoting liquid supply process. According to this method, the decomposition of the second reactive component 113 is promoted by the decomposition promoting liquid. As a result, the first highly soluble component 114 can be rapidly formed.

[0248] Furthermore, according to the first embodiment, the first reaction component 110 is a carboxylic acid ester or a sulfonate ester. The carboxylic acid ester or sulfonate ester can be hydrolyzed to form an acid component (organic acid) such as a carboxylic acid or sulfonic acid, which functions as the etching component 112.

[0249] Furthermore, according to the first embodiment, the surface layer 150 of the substrate W is etched in the etching process, thereby forming etching residue 104. The etching residue 104 is retained by the processing film 100 formed in the processing film formation process. In addition, the processing film removal process includes the following steps: while the etching residue 104 is retained by the processing film 100, the etching residue 104 is removed together with the processing film 100.

[0250] According to this method, the etching residue 104 generated by etching the surface portion 150 of the substrate W is removed from the upper surface 151 of the substrate W together with the treatment film 100 during the treatment film removal process. Therefore, after removing the treatment film 100, there is no need to perform a separate process to remove the etching residue 104.

[0251] Next, other examples of substrate processing according to the first embodiment will be described.

[0252] Figure 9A This is a flowchart illustrating a second example of substrate processing according to the first embodiment. The second example of substrate processing and... Figure 6 The difference in substrate processing lies in omitting the decomposition accelerator supply step (step S5). That is, in the second example of substrate processing, the etching component formation process is heating the processed film, and the high-solubility component formation process is irradiating the processed film with light. In the second example of substrate processing, the heater unit 6 functions as the etching component formation processing unit, and the light irradiation unit 8 functions as the high-solubility component formation processing unit.

[0253] The first reactant is decomposed by heating. Moisture in the treatment membrane or atmosphere can also be used to promote the decomposition of the first reactant. The second reactant is decomposed by irradiating the treatment membrane with light. The decomposition of the second reactant is promoted by the heat remaining in the treatment membrane.

[0254] Figure 9B This is a flowchart illustrating a third example of substrate processing according to the first embodiment. The third example of substrate processing and... Figure 6The difference in substrate processing lies in omitting the heating step of the processing film (step S4). That is, in the third example of substrate processing, the etching component formation process is the supply of a decomposition promoting solution, and the highly soluble component formation process is the irradiation of the processing film with light. The first reactive component is decomposed at room temperature in the presence of the decomposition promoting solution. Room temperature is, for example, a temperature above 5°C and below 25°C. The second reactive component is decomposed by irradiating the processing film with light.

[0255] In the third example of substrate processing, the third moving nozzle 11 functions as an etching component formation processing unit, and the light irradiation unit 8 functions as a highly soluble component formation processing unit.

[0256] Figure 9C This is a flowchart illustrating a fourth example of substrate processing in the first embodiment. Although the fourth example of substrate processing is similar to... Figure 9B The third example of substrate processing is the same; however, in the fourth example of substrate processing, the etching component formation process involves supplying a decomposition-promoting solution and irradiating the processed film with light, while the highly soluble component formation process involves irradiating the processed film with light. The first and second reactive components are decomposed by the energy of light in the presence of the decomposition-promoting solution.

[0257] In the fourth example of substrate processing, the light irradiation unit 8 and the third moving nozzle 11 function as an etching component formation processing unit, and the light irradiation unit 8 functions as a highly soluble component formation processing unit.

[0258] Figure 9D This is a flowchart illustrating a fifth example of substrate processing according to the first embodiment. The fifth example of substrate processing and... Figure 6 The difference in substrate processing lies in omitting the processing film heating step (step S4) and the decomposition accelerator supply step (step S5). That is, in the fifth example of substrate processing, both the etching component formation process and the highly soluble component formation process involve irradiating the processing film with light. In this case, the decomposition of the first reactive component and the decomposition of the second reactive component occur simultaneously. In the case where the decomposition reaction of the first reactive component is hydrolysis, light is irradiated using the processing film 100 or moisture in the atmosphere at room temperature, thereby decomposing the first reactive component and the second reactive component.

[0259] In the fifth example of substrate processing, the light irradiation unit 8 functions as both an etching component formation processing unit and a highly soluble component formation processing unit.

[0260] In addition, although not illustrated, the decomposition accelerator supply process (step S5) and the light irradiation process (step S6) can be omitted, and the etching component formation process and the highly soluble component formation process can be performed in the film heating process (step S4).

[0261] [Second Implementation]

[0262] The substrate processing apparatus 1P of the second embodiment has the same configuration as the substrate processing apparatus 1 of the first embodiment (see reference). Figure 2 The main difference between the substrate processing apparatus 1P and the substrate processing apparatus 1 of the first embodiment is that the processing liquid contains, in addition to the first reactive component and the low-soluble component, a second highly soluble component as a solute.

[0263] As the first reactant, an ingredient that forms only the etching component can be used, instead of an ingredient that forms both the etching component and the second reactant through the etching component formation process. As the first reactant, the same carboxylic acid ester or sulfonate ester as in the first embodiment can also be used.

[0264] like Figure 10 As shown, in the case where the first reactant is a carboxylic acid ester, the first reactant is hydrolyzed in the presence of water and under heating conditions (e.g., above 50°C and below 80°C). The carboxylic acid generated by hydrolysis is the etching component.

[0265] exist Figure 10 In the middle, R 21 For example, a hydrocarbon group, R 22 For example, some functional groups have carboxylic acid ester groups. R 21 It can also be a functional group in which the hydrogen atom in a hydrocarbon group has been replaced by a fluorine or chlorine atom. (Similar to R) 21 Compared to the case where the hydrocarbon group does not contain functional groups with fluorine or chlorine atoms, in R 21 When the hydrogen atom in the hydrocarbon group has been replaced by a fluorine or chlorine atom functional group, the acidity of the etching component is high.

[0266] In the case where the first reactant is a sulfonate ester, such as Figure 11 As shown, the first reaction component is hydrolyzed in the presence of water and under heating conditions (e.g., above 50°C and below 80°C). The sulfonic acid generated by the hydrolysis of the first reaction component is the etching component.

[0267] exist Figure 11 In the middle, R 31 For example, a hydrocarbon group, R 32 For example, some functional groups have sulfonate groups. R 31 It can also be a functional group in which the hydrogen atom in a hydrocarbon group has been replaced by a fluorine or chlorine atom. (Similar to R) 31 Compared to the case where the hydrocarbon group does not contain functional groups with fluorine or chlorine atoms, in R 31When the hydrogen atoms in the hydrocarbon group have been replaced by functional groups containing fluorine or chlorine atoms, the acidity of the etching component is high. Therefore, the surface layer of the substrate W can be etched rapidly.

[0268] The second highly soluble component is one that has high solubility in the stripping solution. An example of a second highly soluble component is 2,2-bis(4-hydroxyphenyl)propane. As a low-soluble component, a substance with lower solubility in the stripping solution than the second highly soluble component can be used. An example of a low-soluble component is phenolic varnish. This is an example of a first low-soluble component and also an example of a second low-soluble component.

[0269] The solvent contained in the treatment solution need only be a liquid used to dissolve the low-soluble component, the first reactive component, and the second highly soluble component. Preferably, the solvent contained in the treatment solution is a liquid that is miscible with the stripping liquid. The same solvent as that contained in the treatment solution of the first embodiment can be used as the solvent contained in the treatment solution.

[0270] The treatment membrane is mainly composed of a low-soluble component in a solid state (low-soluble component solid), a first reactant component in a solid state (first reactant solid), and a second highly soluble component in a solid state (second highly soluble component solid). Solvent residues may also remain in the treatment membrane. Detailed descriptions of the solvents, low-soluble components, and second highly soluble components contained in the treatment solution are provided below.

[0271] Next, an example of substrate processing based on the substrate processing apparatus 1P of the second embodiment will be described. Figure 12 This is a flowchart illustrating a first example of substrate processing based on the substrate processing apparatus 1P according to the second embodiment.

[0272] like Figure 12 As shown, in substrate processing based on substrate processing apparatus 1P, for example, the following steps are performed sequentially: substrate loading step (step S1), processing liquid supply step (step S2), processing film formation step (step S3), processing film heating step (step S4), decomposition promoting liquid supply step (step S5), processing film removal step (step S7), cleaning step (step S8), residue removal step (step S9), spin drying step (step S10), and substrate unloading step (step S11). That is, with... Figure 6 The substrate processing shown is different, and the light irradiation process (step S6) is omitted.

[0273] Next, use Figures 13A-13E The state of the peeling treatment film 100 from the substrate W is described in detail. Figures 13A-13EThis is a schematic diagram illustrating the state of the treatment film 100 being peeled off from the substrate W.

[0274] 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 component formation process, the processed film 100 contains a first reactive component 110, a low-solubility component 111, and a second highly soluble component 116. The first reactive component 110, the low-solubility component 111, and the second highly soluble component 116 are solidified or hardened by the evaporation of at least a portion of the solvent contained in the processing liquid.

[0275] Next, refer to Figure 13B The first reactive component 110 is decomposed through an etching component formation process (heating and supply of a decomposition accelerator). Specifically, in the decomposition accelerator supply step (step S4), a cleaning solution, serving as the decomposition accelerator, is supplied to the processed film 100, causing the processed film 100 to expand. When the substrate W is heated in the presence of the cleaning solution (processed film heating step), the first reactive component 110 is decomposed. The decomposition of the first reactive component 110 forms an etching component 112 in the processed film 100 (etching component formation step). Figure 13C As shown, the surface layer 150 of the substrate W is etched by etching components 112 formed in the processing film 100 (etching process). The heater unit 6 and the third moving nozzle 11 function as etching component formation processing units.

[0276] The etching component 112 is dissolved in the cleaning solution used as a decomposition promoting solution. The portion of the etching component 112 that contacts the upper surface 151 of the substrate W in the treated film 100 is removed by etching the surface portion 150 of the substrate W. Therefore, as... Figure 13C As shown, the etching component 112 in the processing film 100 moves to the upper surface 151 side of the substrate W in such a way that the concentration of the etching component 112 in the portion of the processing film 100 that contacts the upper surface 151 of the substrate W does not decrease. In this way, the etching of the surface portion 150 of the substrate W continues to progress slowly, and the upper surface 151 of the substrate W recedes toward the lower surface side.

[0277] As the upper surface 151 of the substrate W is retracted (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 encapsulated by the processing film 100 (especially the low-solidity component 111 in a solid state) and thus held more firmly. Etching of the surface portion 150 of the substrate W forms etching residue 104. The processing film 100 (especially the low-solidity component 111 in a solid state) 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.

[0278] Next, refer to Figure 13D The second highly soluble component 116 is dissolved by the stripping solution. That is, the treated membrane 100 is locally dissolved (dissolution process, partial dissolution process). The second highly soluble component 116 is dissolved, thereby forming through holes 106 in the portion of the treated membrane 100 where the second highly soluble component 116 is concentrated (through hole formation process).

[0279] The portion containing the second most soluble component 116 also contains the least soluble component 111, rather than only containing the second most soluble component 116. Since the stripping fluid not only dissolves the second most soluble component 116 but also dissolves the least soluble component 111 surrounding the second most soluble component 116, it promotes the formation of the through-hole 106.

[0280] Here, when solvent and cleaning solution remain moderately in the treated membrane 100, the stripping liquid partially dissolves the treated membrane 100 while dissolving into the solvent and cleaning solution remaining in the treated membrane 100. Specifically, the stripping liquid dissolves the first highly soluble component 114 in the treated membrane 100 while dissolving into the solvent and cleaning solution remaining in the treated membrane 100, thereby forming through-holes 106. Therefore, the stripping liquid easily enters into the treated membrane 100 (dissolution entry process).

[0281] The stripping liquid that has reached the upper surface 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 (peeling and removal process).

[0282] 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, the stripping solution reaching the vicinity of the upper surface of the substrate W through the through-hole 106 only slightly dissolves a portion of the low-soluble component 111 near the upper surface of the substrate W. Thus, as... Figure 13D As shown in the enlarged view, the stripping liquid slowly dissolves the low-solubility component 111 in the solid state near the upper surface of the substrate W while gradually entering the gap G between the treatment film 100 and the upper surface of the substrate W (stripping liquid entry process).

[0283] Next, for example, cracks (cracks) are formed in the treated film 100 starting from the periphery of the through-hole 106. Therefore, the second highly soluble component 116 is referred to as the crack-inducing component. The treated film 100 splits through the formation of cracks and becomes a film sheet 108. For example... Figure 13E 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).

[0284] Next, a stripping solution is continuously supplied, thereby rinsing the treatment membrane 100 (diaphragm 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 of the substrate W (treatment membrane removal process, object to be removed removal process). As a result, the upper surface of the substrate W can be effectively cleaned.

[0285] According to the second embodiment, the same effects as those of the first embodiment are achieved. The surface portion 150 of the substrate W is etched by the etching components formed in the processing film 100, thereby reducing the consumption of the etching components 112. Furthermore, in the processing film removal process, since the processing film 100 is peeled off and removed from the upper surface 151 of the substrate W by the stripping liquid, the object to be removed 105 attached to the upper surface 151 of the substrate W can be peeled off and removed. Furthermore, since the object to be removed 105 can be lifted from the upper surface 151 of the substrate W by the retraction of the upper surface 51 of the substrate W caused by etching, the object to be removed 105 can be effectively peeled off during the peeling of the processing film 100.

[0286] Furthermore, the following effects can also be achieved according to the second embodiment. In the processing membrane formation step, a processing membrane 100 containing the second highly soluble component 116 is formed. Then, the second highly soluble component 116 in the processing membrane 100 is dissolved by the stripping liquid supplied in the processing membrane removal step.

[0287] According to this method, a treatment film 100 containing a second highly soluble component 116 is formed in the treatment film formation process. In the treatment film 100, the second highly soluble component 116 is subsequently dissolved by a stripping liquid supplied to the upper surface 151 of the substrate W. The stripping liquid dissolves the second highly soluble component 116 in the treatment film 100, thereby forming through-holes 106 in the treatment film 100. Therefore, the stripping liquid can rapidly reach the interface between the treatment film 100 and the substrate W through the through-holes 106 formed in the treatment film 100. The stripping liquid enters the interface between the substrate W and the treatment film 100, peeling the treatment film 100 from the upper surface 151 of the substrate W. Thus, after etching based on the etching component 112 is completed, the treatment film 100 can be rapidly peeled from the upper surface 151 of the substrate W.

[0288] Furthermore, according to the second embodiment, the solubility of the low-soluble component 111 in the stripping solution is lower than that of the second highly soluble component 116 in the stripping solution. Therefore, the second highly soluble component 116 is dissolved by the stripping solution, while the low-soluble component 111 is not dissolved by the stripping solution but is maintained in a solid state in the treatment membrane 100.

[0289] Therefore, the second highly soluble component 116 can be dissolved in the stripping liquid while the less soluble component 111 is not dissolved in the stripping liquid, thus maintaining it in the treated film 100. Therefore, the stripping liquid reaches the interface between the substrate W and the treated film 100 through the through-holes 106 formed by the dissolution of the second highly soluble component 116.

[0290] As a result, after the etching based on the etching components is completed, the treatment film 100 can be quickly peeled off from the upper surface 151 of the substrate W.

[0291] 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 second high-soluble component 116 has dissolved. Even after the stripping liquid is supplied, the object to be removed 105 can be maintained in a state by the treatment membrane 100. Therefore, compared to 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 liquid can be increased.

[0292] Next, other examples of substrate processing in the second embodiment will be described.

[0293] Figure 14A This is a flowchart illustrating a second example of substrate processing according to the second embodiment. The second example of substrate processing and... Figure 12 The difference in substrate processing lies in omitting the decomposition accelerator supply step (step S5). That is, in the second example of substrate processing in the second embodiment, the etching component formation process is the heating of the treatment film 100. The first reactive component decomposes by heating. The decomposition of the first reactive component can also be promoted by moisture in the treatment film or the atmosphere. In the second example of substrate processing, the heater unit 6 functions as an etching component formation processing unit.

[0294] Figure 14B This is a flowchart illustrating a third example of substrate processing according to the second embodiment. The third example of substrate processing according to the second embodiment is... Figure 12 The difference in substrate processing lies in omitting the film heating step (step S4). That is, in the third example of substrate processing, the etching component formation process is the supply of a decomposition promoting solution. The first reaction component is decomposed at room temperature in the presence of the decomposition promoting solution. In the third example of substrate processing, the third moving nozzle 11 functions as an etching component formation processing unit.

[0295] Figure 14C This is a flowchart illustrating a fourth example of substrate processing in the second embodiment. The fourth example of substrate processing and... Figure 12The difference in substrate processing lies in omitting the film heating process (step S4) and the decomposition accelerator supply process (step S5), replacing them with a light irradiation process (step S6). That is, in the fourth example of substrate processing, the etching component formation process is light irradiation. The first reaction component is decomposed by the energy of the light. The decomposition of the first reaction component can also be promoted by moisture in the film or the atmosphere. In the fourth example of substrate processing, the light irradiation unit 8 functions as an etching component formation processing unit.

[0296] Figure 14D This is a flowchart illustrating a fifth example of substrate processing in the second embodiment. The fifth example of substrate processing and... Figure 12 The difference in substrate processing lies in replacing the film heating process (step S4) with a light irradiation process (step S6). That is, in the fifth example of substrate processing, the etching component formation process involves light irradiation and the supply of a decomposition accelerating solution. The first reactive component is decomposed by irradiating light at room temperature in the presence of the decomposition accelerating solution. In the fifth example of substrate processing, the third moving nozzle 11 and the light irradiation unit 8 function as the etching component formation processing unit.

[0297] [Detailed description of the components in the treatment solution]

[0298] The following describes the components (solvent, low-soluble component, and second highly soluble component) used in the processing liquid of the above embodiments.

[0299] 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.).

[0300] 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.

[0301] [Low-soluble components]

[0302] (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.

[0303] As a low-soluble component (A), the treatment solution may also 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 also contain both phenolic varnish and polyhydroxystyrene.

[0304] (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 liquid, but is stripped by the stripping liquid while still retaining 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 liquid.

[0305] 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.

[0306] The copolymerization is preferably random copolymerization or block copolymerization.

[0307] 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.

[0308] [Chemical Formula 1]

[0309]

[0310] [Chemical Formula 2]

[0311]

[0312] [Chemical Formula 3]

[0313]

[0314] (An asterisk * indicates a bond with an adjacent constituent unit.)

[0315] [Chemical Formula 4]

[0316]

[0317] (R represents C) 1～4 Alkyl groups and other substituents. An asterisk (*) indicates a bond with an adjacent constituent unit.

[0318] [Chemical Formula 5]

[0319]

[0320] [Chemical Formula 6]

[0321]

[0322] [Chemical Formula 7]

[0323]

[0324] (Me represents methyl. The asterisk * indicates a bond with an adjacent building block.)

[0325] (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.

[0326] (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.

[0327] Phenolic varnishes: SHOUWA KASEI Co., Ltd., ASAHI YUKIZAI CORPORATION, Gun Ei Chemical Industry Co., Ltd., and Sumitomo Bakelite Co., Ltd. (Japan).

[0328] Polyhydroxystyrene: NIPPON SODA Co., Ltd., Maruzen Petrochemical Co., Ltd., TOHO Chemical Industry Co., Ltd.

[0329] Polyacrylic acid derivatives: Nippon Shokubai Co., Ltd.

[0330] Polycarbonate: Sigma-Aldrich Co. LLC.

[0331] Polymethacrylic acid derivatives: Sigma-Aldrich Co., LLC.

[0332] Compared to the total mass of the treatment solution, (A) the low-soluble component is 0.1% to 50% by mass, preferably 0.5% to 30% by mass, more preferably 1% to 20% by mass, and even more preferably 1% to 10% by mass. That is, with the total mass of the treatment solution set to 100% by mass, (A) the low-soluble component is 0.1% to 50% by mass. In other words, "compared to..." can be changed to "based on...". The same applies below unless otherwise specified.

[0333] [Second most soluble component]

[0334] (B) The second 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.

[0335] 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 liquid has dried, and the treatment film is peeled off by a stripping liquid, the second highly soluble component (B) is generated, which becomes the catalyst for the peeling of the treatment film. Therefore, it is preferable that the second highly soluble component (B) is a component whose solubility in the stripping liquid is higher than that of the less soluble component (A). As a crack-promoting component (B'), it includes a ketone in the form of a carbonyl group, and cyclic hydrocarbons can be cited as examples. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0336] In a more specific form, (B) the second highly soluble component is represented by at least one of (B-1), (B-2) and (B-3) below.

[0337] (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.

[0338] [Chemical Formula 8]

[0339]

[0340] 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 .

[0341] R 40 C, each independently 1～5 Alkyl groups, preferably methyl, ethyl, propyl, or butyl. The above C 1～5 Alkyl groups can be either straight-chain or branched.

[0342] 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.

[0343] 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.

[0344] [Chemical Formula 9]

[0345]

[0346] 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.

[0347] 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,R 40 It is a methyl group.

[0348] [Chemical Formula 10]

[0349]

[0350] (B-2) is represented by the following chemical formula 11.

[0351] [Chemical Formula 11]

[0352]

[0353] R 41 R 42 R 43 and R 44 Each can be independently hydrogen or C. 1～5 Alkyl groups, preferably hydrogen, methyl, ethyl, tert-butyl, or isopropyl, are preferred, and more preferably methyl or ethyl.

[0354] Connector L 21 and connector L 22 C, each independently 1～20 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 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 The alkylene group or acetylene, more preferably acetylene.

[0355] n b2 It can be 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0356] 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.

[0357] (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.

[0358] [Chemical Formula 12]

[0359]

[0360] Here, R 45 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.

[0361] 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.

[0362] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0363] 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... 45 For -H, R is in other constituent units.45 It is -COOH.

[0364] [Chemical Formula 13]

[0365]

[0366] Needless to say, the treatment solution may also contain one or more of the above-mentioned preferred embodiments as the second highly soluble component (B). For example, the second highly soluble component (B) may also contain 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0367] (B) The molecular weight of the second highly soluble component may also be 80 to 10,000. The molecular weight of the second highly soluble component is preferably 90 to 5,000, more preferably 100 to 3,000. In the case where the second highly soluble component in (B) is a resin, polymer, or a polymer, the molecular weight is expressed as weight-average molecular weight (Mw).

[0368] (B) The second most soluble component 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.

[0369] [solvent]

[0370] (C) The solvent is preferably an organic solvent. (C) The solvent may also be volatile. Volatility means that it is more volatile than water.

[0371] 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.

[0372] [Other Implementation Methods]

[0373] The present invention is not limited to the embodiments described above, and may be further implemented in other ways.

[0374] 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.

[0375] In the substrate processing of the above embodiment, the opening and closing of the gate 82 switches between light illumination and the cessation of light illumination based on the light illumination unit 8. However, it is also possible to switch between light illumination and the cessation of light illumination based on the light illumination unit 8 by energizing and stopping the lamp 80.

[0376] In addition, such as Figure 15 As shown, the heater 62 can also be configured such that it has a plurality of regions divided along the rotational radial direction, and each region can be set with a different temperature. The temperature of the heater 62 can also be set for each region, for example, such that it becomes high-temperature as it moves away from the rotational center of the substrate W. Conversely, the temperature of the heater 62 can also be set for each region such that it becomes high-temperature as it approaches the rotational center of the substrate W.

[0377] In addition, such as Figure 16 As shown, the light irradiation unit 8 can also be configured to move between an irradiation position and a starting position (retreat position) via a lamp moving unit 87 disposed within the chamber 4. The irradiation position is the position where the light irradiation unit 8 faces the upper surface of the substrate W. The irradiation position is the position where light can be irradiated from the light irradiation unit 8 towards the upper surface of the substrate W. The retreat position is the position where light is not irradiated from the light irradiation unit 8 towards the upper surface of the substrate W. When the light irradiation unit 8 is in the irradiation position, it faces the upper surface of the substrate W. When the light irradiation unit 8 is in the starting position, it does not face the upper surface of the substrate W, but is located on the processing cover 7 (see reference 7) when viewed from above. Figure 2 The outer direction of ).

[0378] The lamp moving unit 87 includes: an arm 87A supporting the lamp cover 81; and an arm moving unit 87B for moving the arm 87A. The arm moving unit 87B includes, for example: a motor for rotating the arm 87A about a rotation axis A2 to move the arm 87A horizontally; and a ball screw mechanism for raising and lowering the arm 87A.

[0379] In addition, such as Figure 17 As shown, the light irradiation unit 8 can also be located on the outside of the side wall 4c of the chamber 4. In this case, the light emitted from the light irradiation unit 8 enters the chamber 4 through the slit 4d provided on the side wall 4c and is reflected by the reflector 88 disposed in the chamber 4, thereby irradiating the upper surface of the substrate W.

[0380] Furthermore, the light irradiation unit 8 can also be a projector. In this case, the intensity of the light irradiating the upper surface of the substrate W can be changed by adjusting the brightness of the image projected by the projector.

[0381] In the above embodiments, the etching component is formed by the decomposition reaction of the first reactant, and the first highly soluble component is formed by the decomposition reaction of the second reactant. However, it is also possible to configure the first reactant to become the etching component through a reaction other than the decomposition reaction (e.g., a dislocation reaction). Similarly, it is also possible to configure the second reactant to become the first highly soluble component through a reaction other than the decomposition reaction (e.g., a dislocation reaction, an oxidation reaction).

[0382] The first and second embodiments described above can also be combined. For example, the substrate treatment of the first embodiment can also be performed using a processing solution containing a low-soluble component as a solute, a first reactive component, and a second high-soluble component (e.g., Figure 6 In this case, since the first highly soluble component is formed through a highly soluble component formation process, the processed film 100 after the highly soluble component formation process contains both the first highly soluble component and the second highly soluble component. During the processed film removal process, a stripping solution is supplied to the upper surface of the substrate W, whereby the first highly soluble component and the second highly soluble component are dissolved, thereby forming through-holes 106 in the processed film 100. Furthermore, in this case, two components can also be used as low-soluble components. Specifically, the processed solution can contain: a first low-soluble component, whose solubility in the stripping solution is lower than that of the first highly soluble component; and a second low-soluble component, whose solubility in the stripping solution is lower than that of the second highly soluble component.

[0383] Furthermore, in the above embodiment, the processing liquid, stripping liquid, cleaning liquid (decomposition promoting liquid), and residue removal liquid are ejected from the first to the fourth moving nozzles, respectively. However, each liquid may also be configured to be ejected from a solid nozzle, the solid nozzle being fixed in position relative to the substrate W.

[0384] In this specification, when “to” (i.e., “~” or “-”) is used to indicate a range of values, unless otherwise specified, it includes two endpoints and the unit is common.

[0385] Although embodiments of the present invention have been described in detail, these embodiments are merely specific examples used to clarify the technical content of the present invention, and the present invention should not be construed as limited to these specific examples. The present invention is defined only by the appended claims.

[0386] This application corresponds to Japanese Patent Application No. 2020-126876 filed with the Japan Patent Office on July 27, 2020, and all contents of Japanese Patent Application No. 2020-126876 are incorporated herein by reference.

[0387] Explanation of reference numerals in the attached figures

[0388] 1: Substrate processing device

[0389] 1P: Substrate processing apparatus

[0390] 3: Controller

[0391] 6: Heater Unit (Etching Component Formation Processing Unit)

[0392] 8: Light Irradiation Unit (Etching Composition Formation Processing Unit)

[0393] 9: First moving nozzle (processing fluid supply unit)

[0394] 10: Second moving nozzle (stripping fluid supply unit)

[0395] 11: Third moving nozzle (etching composition formation processing unit)

[0396] 23: Rotating motor (processing membrane forming unit)

[0397] 100: Processing membrane

[0398] 104: Etching Residue

[0399] 106: Through hole

[0400] 110: First reaction component

[0401] 111: Low-soluble components (first low-soluble component, second low-soluble component)

[0402] 112: Etching components

[0403] 113: Second reaction component

[0404] 114: The most highly soluble component

[0405] 116: The second most soluble component

[0406] 150: Surface layer

[0407] 151: Upper surface

[0408] 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 component formation process involves subjecting the treated film to an etching component formation process, thereby forming etching components in the treated film. An etching process, wherein the surface layer of the substrate is etched using an etching component formed in the etching component formation process; In the process of removing the treatment film, a stripping liquid is supplied to the surface of the treatment film, thereby peeling the treatment film off the surface of the substrate and removing the treatment film from the surface of the substrate. as well as A high-soluble component formation process is performed on the treated film after the etching component formation process and before the treated film removal process, thereby forming a first high-soluble component in the treated film. This first high-soluble component has higher solubility in the stripping solution compared to other components in the treated film. In the film removal process, the stripping solution is supplied to the surface of the substrate, thereby dissolving the first highly soluble component in the film. In the process of forming the treated membrane, a treated membrane containing the first reactive component is formed. In the etching component formation process, the first reactive component is decomposed by the etching component formation treatment, thereby forming a second reactive component and the etching component in the treated film. In the highly soluble component formation process, the second reactive component is decomposed by the highly soluble component formation treatment, thereby forming the first highly soluble component in the treated membrane.

2. The substrate processing method as described in claim 1, wherein, The process further includes a decomposition accelerator supply step, in which a decomposition accelerator is supplied to the surface of the substrate, wherein the decomposition accelerator promotes the decomposition of the first reactive component in the etching component formation step.

3. The substrate processing method as described in claim 2, wherein, The decomposition of the second reactive component is promoted by the decomposition promoting liquid supplied to the surface of the substrate during the decomposition promoting liquid supply process.

4. The substrate processing method as described in claim 1, wherein, The etching component formation process includes at least one of the following: heating the processing film, supplying water to the processing film, and irradiating the processing film with light.

5. The substrate processing method as described in claim 1, wherein, The highly soluble component formation process involves irradiating the treated membrane with light.

6. The substrate processing method as described in claim 1, wherein, The first highly soluble component is dissolved by the stripping solution, thereby forming through-pores in the treated membrane.

7. The substrate processing method as described in claim 1, wherein, In the process of forming the treatment film, a treatment film containing a first low-soluble component is formed, wherein the first low-soluble component has a lower solubility in the stripping solution than the first high-soluble component.

8. The substrate processing method as described in claim 1, wherein, The first reactant is a carboxylic acid ester or a sulfonate ester.

9. The substrate processing method as described in claim 1, wherein, In the etching process, the surface layer of the substrate is etched, thereby forming etching residue. The etching residue is retained by the treatment film formed in the treatment film formation process. 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.

10. 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 present on the surface of the substrate, thereby forming a processing film on the surface of the substrate; An etching component formation processing unit performs an etching component formation process on the processed film; A high-soluble component formation processing unit performs a high-soluble component formation processing on the processed membrane; A stripping fluid supply unit supplies stripping fluid to the surface of the substrate to peel the treatment film off the surface of the substrate; as well as The controller controls the processing liquid supply unit, the processing film formation unit, the etching component formation processing unit, the highly soluble component formation processing unit, and the stripping liquid 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 supplied to 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. The etching component formation process involves performing the etching component formation treatment process by the etching component formation treatment unit, thereby forming etching components in the treatment film. An etching process, wherein the surface layer of the substrate is etched using an etching component formed in the etching component formation process; In the process of removing the treatment film, a stripping liquid is supplied from the stripping liquid supply unit toward the surface of the substrate, thereby peeling the treatment film off the surface of the substrate and removing the treatment film from the surface of the substrate; as well as A high-soluble component formation process is performed after the etching component formation process and before the processed film removal process. The processed film is treated with a high-soluble component formation unit to form a highly soluble component in the processed film. This highly soluble component has higher solubility in the stripping solution compared to other components in the processed film. In the film removal process, the stripping solution is supplied to the surface of the substrate, thereby dissolving the highly soluble components in the film. In the process of forming the treated membrane, a treated membrane containing the first reactive component is formed. In the etching component formation process, the first reactive component is decomposed by the etching component formation treatment, thereby forming a second reactive component and the etching component in the treated film. In the highly soluble component formation process, the second reactive component is decomposed by the highly soluble component formation treatment, thereby forming the highly soluble component in the treated membrane.

11. A treatment liquid, wherein, It forms a treatment film through curing or hardening, and the treatment film can be peeled off from the surface of the substrate using a stripping liquid. The treatment liquid has a first reaction component and a solid state maintenance component. The first reactive component is decomposed by an etching component formation process, thereby forming an etching component and a second reactive component in the processed film to etch the surface portion of the substrate. The solid state maintaining component also maintains a solid state in the treated film after the etching component formation process. The second reactive component is decomposed by subjecting the treated membrane to a highly soluble component formation treatment, thereby forming a highly soluble component in the treated membrane. This highly soluble component has higher solubility in the stripping solution compared to other components in the treated membrane.

Images