Substrate processing method and substrate processing apparatus

Abstract

The substrate processing method includes: an etching step of forming a semi-solid coating film containing a first polymer having an etching function and a second polymer having a solid formation function on the surface of the substrate, and etching the surface layer portion of the substrate through the first polymer on the substrate; and an etching stop step of solidifying the second polymer in the coating film through solid formation treatment to convert the coating film into a solidified film, thereby stopping the etching of the surface layer portion of the substrate.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Substrates to be processed include, for example, semiconductor wafers, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, substrates for solar cells, and substrates for flat panel displays (FPDs) such as liquid crystal display devices, plasma display devices, and organic EL (Electroluminescence) display devices. Background Art

[0002] As an etching solution for etching the surface of a substrate, hydrofluoric acid can be used (see Patent Document 1 below). After processing the substrate with the etching solution, the surface of the substrate is cleaned with a rinsing solution such as DIW.

[0003] Prior Art Documents

[0004] Patent Documents

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

[0006] Problems to be Solved by the Invention

[0007] In such an etching process, the drainage volume of the etching solution and the rinsing solution mixed with the etching solution is large, imposing a heavy environmental burden. Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of reducing the usage amount of etching components.

[0008] Means for Solving the Problems

[0009] One embodiment of the present invention provides a substrate processing method, which includes: an etching step of forming a semi-solid coating film containing a first polymer having an etching function and a second polymer having a solid forming function on the surface of a substrate, and etching the surface layer portion of the substrate through the first polymer on the substrate; and an etching stop step of solidifying the second polymer in the coating film by a solid formation treatment to convert the coating film into a solidified film, thereby stopping the etching of the surface layer portion of the substrate.

[0010] By this method, a semi-solid coating film containing a first polymer and a second polymer is formed on the surface of a substrate. The surface layer portion of the substrate is etched by the first polymer in the coating film on the substrate. The second polymer in the coating film is solidified by a solid formation treatment. Thus, the coating film is transformed into a solidified film. The first polymer is less likely to diffuse in the solidified film than in the coating film. Therefore, by transforming the coating film into a solidified film, etching of the surface layer portion of the substrate based on the first polymer can be stopped.

[0011] Different from this method, in a method of etching the surface layer portion of a substrate while continuously supplying a continuous flow of an etching solution such as hydrofluoric acid to the surface of the substrate, the etching solution is continuously discharged to the outside of the substrate.

[0012] On the other hand, the fluidity of the semi-solid coating film is lower than that of the continuous flow of the etching solution. Therefore, the amount of the first polymer discharged to the outside of the substrate, that is, the consumption amount of the etching component, can be reduced.

[0013] In one embodiment of the present invention, the etching step includes: a liquid film etching step of forming a liquid film containing a mixture of the first polymer and the second polymer, and etching the surface layer portion of the substrate by the first polymer in the liquid film of the mixture; and a coating film etching step of forming the coating film from the liquid film of the mixture and etching the surface layer portion of the substrate by the first polymer in the coating film.

[0014] By this method, the surface layer portion of the substrate is etched not only by the first polymer in the coating film, but also by the first polymer in the liquid film of the mixture that forms the coating film. The first polymer in the portion of the liquid film of the mixture that contacts the surface of the substrate disappears by etching the surface layer portion of the substrate. The fluidity of the mixture is higher than that of the semi-solid coating film. Therefore, compared with etching based on the coating film, when the first polymer near the surface of the substrate disappears by etching, the first polymer in the liquid film easily diffuses, so that the concentration of the first polymer in the portion of the liquid film that contacts the surface of the substrate does not decrease. Therefore, a decrease in the concentration of the first polymer near the surface of the substrate can be suppressed, and thus, the surface layer portion of the substrate can be etched quickly.

[0015] In addition, since etching is performed in a state where a liquid film of the mixture is formed on the surface of the substrate, the amount of the first polymer discharged to the outside of the substrate, that is, the consumption amount of the etching component, can be reduced compared with a method of etching the surface layer portion of the substrate while continuously supplying a continuous flow of an etching solution such as hydrofluoric acid to the surface of the substrate.

[0016] In one embodiment of the present invention, the liquid film etching process includes: a mixed liquid film forming process of ejecting the aforementioned mixed liquid from a nozzle facing the surface of the aforementioned substrate onto the surface of the aforementioned substrate to form a liquid film of the aforementioned mixed liquid.

[0017] By this method, a mixed liquid pre-containing a first polymer and a second polymer can be supplied to the surface of the substrate. Since it is not necessary to mix the first polymer and the second polymer on the surface of the substrate, a coating film can be formed quickly. Furthermore, the time required for substrate processing can be shortened.

[0018] In one embodiment of the present invention, the liquid film etching process includes: a mixed liquid film forming process of supplying a first polymer liquid containing the aforementioned first polymer and a second polymer liquid containing the aforementioned second polymer to the surface of the aforementioned substrate to form a liquid film of a mixed liquid of the aforementioned first polymer liquid and the aforementioned second polymer liquid on the surface of the aforementioned substrate.

[0019] By this method, the first polymer liquid and the second polymer liquid are mixed on the surface of the substrate. Therefore, when the first polymer and the second polymer react with each other, it is possible to suppress the reaction between the first polymer and the second polymer before supplying the first polymer and the second polymer to the surface of the substrate.

[0020] In one embodiment of the present invention, the aforementioned mixed liquid forming process includes: a process of simultaneously performing the supply of the aforementioned first polymer liquid to the surface of the aforementioned substrate and the supply of the aforementioned second polymer liquid to the surface of the aforementioned substrate. When the supply of the first polymer liquid and the supply of the second polymer liquid are simultaneously carried out, compared with the method of sequentially supplying the first polymer liquid and the second polymer liquid to the surface of the substrate, the time required for forming the coating film can be shortened. Furthermore, the time required for substrate processing can be shortened.

[0021] In one embodiment of the present invention, the aforementioned mixed liquid forming process includes: a first polymer liquid supply process of supplying the aforementioned first polymer liquid to the surface of the aforementioned substrate; and a second polymer liquid supply process of supplying the aforementioned second polymer liquid to the surface of the aforementioned substrate after the aforementioned first polymer liquid supply process to form the aforementioned mixed liquid on the surface of the aforementioned substrate.

[0022] By this method, the first polymer liquid is supplied to the surface of the substrate before the second polymer liquid. Therefore, a liquid film not mixed with the second polymer liquid can be formed on the surface of the substrate. The concentration of the first polymer in the first polymer liquid is higher than the concentration of the first polymer in the mixed liquid. Therefore, before forming the mixed liquid, the surface layer portion of the substrate can be quickly etched by the high-concentration first polymer.

[0023] Furthermore, after the first polymer is consumed to a certain extent as etching progresses, the first polymer liquid and the second polymer liquid are mixed on the surface of the substrate. Therefore, when the first polymer reacts with the second polymer, the reaction between the first polymer and the second polymer can be further suppressed.

[0024] In one embodiment of the present invention, the solid formation treatment includes a heat treatment for the coating film, and the second polymer is a thermosetting resin. Therefore, the thermosetting resin as the second polymer in the coating film is cured by heating. Through the curing of the thermosetting resin, the coating film is transformed into a solidified film. Since the solidified film is formed by the curing of the thermosetting resin, the diffusion of the first polymer can be further suppressed. Therefore, the etching of the surface layer portion of the substrate based on the first polymer can be stopped more reliably.

[0025] In one embodiment of the present invention, the solid formation treatment includes a light irradiation treatment for the coating film, and the second polymer is a photocurable resin. Therefore, the photocurable resin as the second polymer in the coating film is cured by light irradiation. Through the curing of the photocurable resin, the coating film is transformed into a solidified film. Since the solidified film is formed by the curing of the photocurable resin, the diffusion of the etching component can be further suppressed. Therefore, the etching of the surface layer portion of the substrate based on the etching component can be stopped more reliably.

[0026] In one embodiment of the present invention, the substrate treatment method further includes: a solidified film removing step of supplying a stripping liquid to the surface of the solidified film, thereby peeling the solidified film from the surface of the substrate, and thus removing the solidified film from the surface of the substrate.

[0027] When etching the surface layer portion of the substrate using the first polymer in the coating film, etching residues are likely to adhere to the surface of the substrate. Therefore, in the solidified film removing step, if the solidified film is removed from the surface of the substrate by being peeled off rather than being dissolved in the stripping liquid, the solidified film is peeled off from the surface of the substrate while holding the etching residues. As a result, the etching residues can be removed from the surface of the substrate together with the solidified film.

[0028] In one embodiment of the present invention, in the etching stop step, a solidified film containing a dissolution component that is more soluble in the stripping liquid than the second polymer is formed. Moreover, the dissolution component in the solidified film is dissolved by the stripping liquid supplied in the solidified film removing step.

[0029] By this method, a dissolved component is contained in the solidified film. The dissolved component in the solidified film is then dissolved by a stripping liquid supplied to the surface of the substrate. By dissolving the dissolved component in the solidified film with the stripping liquid, gaps (through-holes) can be formed in the solidified film. Therefore, the stripping liquid can reach the interface between the solidified film and the substrate quickly through the through-holes formed in the solidified film. The stripping liquid enters the interface between the substrate and the solidified film, and strips the solidified film from the surface of the substrate. Thus, after the etching of the first polymer is completed, the solidified film can be quickly stripped from the surface of the substrate.

[0030] In one embodiment of the present invention, in the aforementioned etching process, the surface layer portion of the aforementioned substrate is etched to form etching residues. The aforementioned etching residues are held by the aforementioned solidified film formed in the aforementioned etching stop process. Moreover, the aforementioned solidified film removing process includes: a process of removing the aforementioned etching residues and the aforementioned solidified film together while the aforementioned etching residues are held by the aforementioned solidified film.

[0031] By this method, the etching residues generated by the etching of the surface layer portion of the substrate are removed from the surface of the substrate together with the solidified film in the solidified film removing process. Therefore, after removing the solidified film, there is no need to perform a process for separately removing the etching residues.

[0032] Another embodiment of the present invention provides a substrate processing apparatus, which includes: a coating film forming unit that forms a coating film containing a first polymer having an etching function and a second polymer having a solid formation function on the surface of a substrate; a solid formation unit that performs a solid formation process of solidifying or curing the second polymer in the coating film on the surface of the substrate to form a solidified film; a stripping liquid supply unit that supplies a stripping liquid for stripping the solidified film from the surface of the substrate to the surface of the substrate; and a controller that controls the coating film forming unit, the solid formation unit, and the stripping liquid supply unit.

[0033] In this substrate processing apparatus, the aforementioned controller is programmed to execute the following processes: an etching process of forming a coating film on the surface of the substrate by the aforementioned coating film forming unit and etching the surface layer portion of the substrate by the first polymer in the aforementioned coating film; an etching stop process of curing the second polymer in the coating film to convert the coating film into a solidified film by the aforementioned solid formation process of the aforementioned solid formation unit, thereby stopping the etching of the surface layer portion of the substrate; and a solidified film removing process of supplying a stripping liquid to the surface of the solidified film to strip the solidified film from the surface of the substrate, thereby removing the solidified film from the surface of the substrate.

[0034] With this device, the same effects as those of the invention of the substrate processing method described above are achieved.

[0035] The above-described or further other objects, features, and effects of the present invention will be described with reference to the accompanying drawings and the description of the embodiments described below. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 Figure 1 FIG. is a schematic top view showing the layout of a substrate processing apparatus according to a first embodiment of the present invention.

[0037] Figure 2 Figure 2 FIG. is a schematic partial cross-sectional view showing the schematic structure of a processing unit included in the substrate processing apparatus described above.

[0038] Figure 3 Figure 3 FIG. is a block diagram showing the electrical structure of the main part of the substrate processing apparatus described above.

[0039] Figure 4 Figure 4 FIG. is a flowchart for explaining an example of substrate processing based on the substrate processing apparatus described above.

[0040] Figure 5A Figure 5A FIG. is a schematic view for explaining the case of the mixed liquid supply step (step S2) of the substrate processing described above.

[0041] Figure 5B Figure 5B FIG. is a schematic view for explaining the case of the coating film formation step (step S3) of the substrate processing described above.

[0042] Figure 5C Figure 5C FIG. is a schematic view for explaining the case of the solid film formation step (step S4) of the substrate processing described above.

[0043] Figure 5D Figure 5D FIG. is a schematic view for explaining the case of the solid film removal step (step S5) of the substrate processing described above.

[0044] Figure 5E Figure 5E FIG. is a schematic view for explaining the case of the solid film removal step (step S5) of the substrate processing described above.

[0045] Figure 5F Figure 5F FIG. is a schematic view for explaining the case of the rinsing step (step S6) of the substrate processing described above.

[0046] ​​​​​​​​​​​​​​​​​​​​Figure 6A Figure 6A It is a schematic diagram for explaining the situation near the surface of the substrate in the aforementioned substrate processing.

[0047] Figure 6B Figure 6B It is a schematic diagram for explaining the situation near the surface of the substrate in the aforementioned substrate processing.

[0048] Figure 6C Figure 6C It is a schematic diagram for explaining the situation near the surface of the substrate in the aforementioned substrate processing.

[0049] Figure 6D Figure 6D It is a schematic diagram for explaining the situation near the surface of the substrate in the aforementioned substrate processing.

[0050] Figure 6E Figure 6E It is a schematic diagram for explaining the situation near the surface of the substrate in the aforementioned substrate processing.

[0051] Figure 7 Figure 7 It is a schematic partial cross-sectional view showing the schematic structure of the processing unit included in the substrate processing apparatus according to the second embodiment.

[0052] Figure 8 Figure 8 It is a schematic diagram for explaining the first example of the mixed liquid supply step (step S2) in the substrate processing based on the substrate processing apparatus according to the second embodiment.

[0053] Figure 9A Figure 9A It is a schematic diagram for explaining the second example of the mixed liquid supply step (step S2) in the substrate processing based on the substrate processing apparatus according to the second embodiment.

[0054] Figure 9B Figure 9B It is a schematic diagram for explaining the second example of the mixed liquid supply step (step S2) in the substrate processing based on the substrate processing apparatus according to the second embodiment.

[0055] Figure 10 Figure 10 It is a schematic diagram showing the schematic structure of the processing unit included in the substrate processing apparatus according to the third embodiment.

[0056] Figure 11 Figure 11 It is a schematic diagram for explaining an example of the solidified film formation step (step S4) in the substrate processing based on the substrate processing apparatus according to the third embodiment. ​​​​​​​​​​​​​​​​​​​​​​

[0057] Figure 12 Figure 12 It is a schematic diagram for explaining the situation near the surface of a substrate in the solid film formation process (step S4) of substrate processing according to the third embodiment.

[0058] Figure 13 Figure 13 It is a schematic diagram for explaining a modified example of the substrate processing apparatus according to the third embodiment.

[0059] Figure 14 Figure 14 It is a schematic diagram for explaining a first modified example of the light irradiation unit provided in the processing unit according to the third embodiment.

[0060] Figure 15 Figure 15 It is a schematic diagram for explaining a second modified example of the light irradiation unit provided in the processing unit according to the third embodiment.

[0061] Figure 16 Figure 16 It is a schematic diagram for explaining the structure of the substrate processing apparatus according to the fourth embodiment. Detailed Embodiments

[0062] <First Embodiment>

[0063] Figure 1 It is a schematic top view showing the layout of the substrate processing apparatus 1 according to one embodiment of the present invention.

[0064] The substrate processing apparatus 1 is a single - wafer type apparatus that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a circular plate - shaped substrate. As the substrate W, a substrate in which an etchable component is exposed on the surface can be used. As the substrate W, it is preferable to use a substrate in which at least one of SiO2 (silicon oxide), TiN (titanium nitride), Cu (copper), Ru (ruthenium), Co (cobalt), Mo (molybdenum), and W (tungsten) is exposed on the surface. It is possible to expose only one of the above substances on the surface of the substrate W, or multiple of the above substances can be exposed on the surface of the substrate W.

[0065] The substrate processing apparatus 1 includes: a plurality of processing units 2 that process the substrate W with a fluid; a load port LP that mounts a container C that houses a plurality of substrates W processed in the processing unit 2; transfer robots IR and CR that transfer the substrate W between the load port LP and the processing unit 2; and a controller 3 that controls the substrate processing apparatus 1.

[0066] ​​​​​​​​​​Transfer robot IR transfers substrate W between container C and transfer robot CR. Transfer robot CR transfers substrate W between transfer robot IR and processing unit 2. The plurality of processing units 2 have the same structure, for example. As will be described later in detail, the fluid supplied to substrate W in processing unit 2 includes a mixed solution, a first polymer solution, a second polymer solution, a stripping solution, a rinsing solution, and the like.

[0067] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in chamber 4, and processing of substrate W is performed within processing cup 7. An entrance / exit (not shown) for loading or unloading substrate W by transfer robot CR is formed in chamber 4. A shutter unit (not shown) for opening and closing the entrance / exit is provided in chamber 4.

[0068] Figure 2 It is a schematic diagram for explaining a structural example of processing unit 2. Processing unit 2 further includes a rotary chuck 5, a heater unit 6, a first moving nozzle 9, a second moving nozzle 10, and a third moving nozzle 11.

[0069] Rotary chuck 5 is an example of a substrate holding and rotating unit that holds substrate W horizontally and rotates substrate W about a rotation axis A1 (vertical axis). Rotation axis A1 is a vertical straight line passing through the central portion of substrate W. Rotary chuck 5 includes a plurality of chuck pins 20, a rotary base 21, a rotary shaft 22, and a rotary motor 23.

[0070] Rotary base 21 has a disk shape in the horizontal direction. On the upper surface of rotary base 21, a plurality of chuck pins 20 for gripping the periphery of substrate W are arranged at intervals along the circumferential direction of rotary base 21.

[0071] The plurality of chuck pins 20 are opened and closed by a pin opening / closing unit 24. The plurality of chuck pins 20 are in a closed state by using pin opening / closing unit 24 to hold (clamp) substrate W horizontally. The plurality of chuck pins 20 are in an open state by using pin opening / closing unit 24 to release substrate W. The plurality of chuck pins 20 support substrate W from below in the open state.

[0072] Rotary base 21 and the plurality of chuck pins 20 constitute a substrate holding unit for holding substrate W horizontally. The substrate holding unit is also referred to as a substrate holder.

[0073] The rotation axis 22 extends in the vertical direction along the rotation axis line A1. The upper end portion of the rotation axis 22 is connected to the center of the lower surface of the rotation base 21. The rotation motor 23 supplies a rotational force to the rotation axis 22. By rotating the rotation axis 22 using the rotation motor 23, the rotation base 21 is rotated. Thus, the substrate W rotates around the rotation axis line A1. The rotation motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis line A1.

[0074] The heater unit 6 is an example of a substrate heating unit that heats the entire substrate W. The heater unit 6 has the form of a disk-shaped heating plate. The heater unit 6 is disposed between the upper surface of the rotation base 21 and the lower surface of the substrate W. The heater unit 6 has an opposing surface 6a that faces the lower surface of the substrate W from below.

[0075] The heater unit 6 includes a plate body 61 and a heater 62. The plate body 61 is slightly smaller than the substrate W in a top view. The upper surface of the plate body 61 constitutes the opposing surface 6a. The heater 62 can be a resistor built into the plate body 61. By energizing the heater 62, the opposing surface 6a can be heated. The opposing surface 6a can be heated to 195°C, for example.

[0076] The processing unit 2 includes: a heater power supply unit 64 that supplies power to the heater 62 via a power feed line 63; and a heater lifting unit 65 that relatively raises and lowers the heater unit 6 with respect to the rotation base 21. The heater power supply unit 64 is a power source, for example. The heater lifting unit 65 includes, for example: a ball screw mechanism (not shown); and an electric motor (not shown) that supplies a driving force to the ball screw. The heater lifting unit 65 is also referred to as a heater lifter.

[0077] An elevating shaft 66 that extends in the vertical direction along the rotation axis line A1 is connected to the lower surface of the heater unit 6. The elevating shaft 66 passes through a through hole 21a formed in the central portion of the rotation base 21 and the hollow rotation axis 22. The power feed line 63 passes through the inside of the elevating shaft 66.

[0078] The heater lifting unit 65 raises and lowers the heater unit 6 via the elevating shaft 66. The heater unit 6 can be raised and lowered by the heater lifting unit 65 and can be located at a lower position and an upper position. The heater lifting unit 65 can not only dispose the heater unit 6 at the lower position and the upper position, but also dispose the heater unit 6 at any position between the lower position and the upper position.

[0079] When rising, the heater unit 6 can receive the substrate W from the plurality of chuck pins 20 in an open state. The heater unit 6 is disposed at a position in contact with the lower surface of the substrate W or a position close to the lower surface of the substrate W by the heater lifting unit 65, whereby the substrate W can be heated.

[0080] The processing cover 7 includes: a plurality of protection covers 71 that catch the liquid scattered outward from the substrate W held by the rotating chuck 5; a plurality of cups 72 that catch the liquid guided downward through the plurality of protection covers 71; and a cylindrical outer wall member 73 that surrounds the plurality of protection covers 71 and the plurality of cups 72.

[0081] In this embodiment, an example is shown in which two protection covers 71 (the first protection cover 71A and the second protection cover 71B) and two cups 72 (the first cup 72A and the second cup 72B) are provided.

[0082] The first cup 72A and the second cup 72B each have a shape of an upwardly open annular groove.

[0083] The first protection cover 71A is arranged to surround the rotating base 21. The second protection cover 71B is arranged to surround the rotating base 21 more outwardly than the first protection cover 71A.

[0084] The first protection cover 71A and the second protection cover 71B each have a substantially cylindrical shape. The upper end portions of the respective protection covers 71 are inclined inwardly toward the rotating base 21.

[0085] The first cup 72A catches the liquid guided downward through the first protection cover 71A. The second cup 72B is formed integrally with the first protection cover 71A and catches the liquid guided downward through the second protection cover 71B.

[0086] The processing unit 2 includes a protection cover lifting unit 74 that lifts and lowers the first protection cover 71A and the second protection cover 71B in the vertical direction respectively. The protection cover lifting unit 74 lifts and lowers the first protection cover 71A between a lower position and an upper position. The protection cover lifting unit 74 lifts and lowers the second protection cover 71B between a lower position and an upper position.

[0087] When the first protection cover 71A and the second protection cover 71B are both in the upper position, the liquid scattered from the substrate W is caught by the first protection cover 71A. When the first protection cover 71A is in the lower position and the second protection cover 71B is in the upper position, the liquid scattered from the substrate W is caught by the second protection cover 71B. When the first protection cover 71A and the second protection cover 71B are both in the lower position, for the loading and unloading of the substrate W, the transfer robot CR can access the rotating chuck 5.

[0088] The protective cover lifting unit 74 includes, for example: a first ball screw mechanism (not shown) connected to the first protective cover 71A; a first motor (not shown) that supplies driving force to the first ball screw mechanism; a second ball screw mechanism (not shown) connected to the second protective cover 71B; and a second motor (not shown) that supplies driving force to the second ball screw mechanism. The protective cover lifting unit 74 is also referred to as a protective cover lifter.

[0089] The first moving nozzle 9 is an example of a mixed liquid nozzle (mixed liquid supply unit) that supplies (ejects) a mixed liquid containing a first polymer and a second polymer to the upper surface of the substrate W held by the rotary chuck 5.

[0090] The first moving nozzle 9 can be moved in the horizontal and vertical directions by a first nozzle moving unit 35. The first moving nozzle 9 can be moved between a central position and a starting position (retracted position) in the horizontal direction. When the first moving nozzle 9 is located at the central position, it faces the central region of the upper surface of the substrate W.

[0091] When the first moving nozzle 9 is located at the starting position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 in a top view. By moving in the vertical direction, the first moving nozzle 9 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W.

[0092] The first nozzle moving unit 35 may include: an arm (not shown) connected to the first moving nozzle 9 and extending in the horizontal direction; a rotating shaft (not shown) connected to the arm and extending in the vertical direction; and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0093] The rotating shaft driving unit swings the arm by rotating the rotating shaft around a vertical axis of rotation. In addition, the rotating shaft driving unit raises and lowers the arm by raising and lowering the rotating shaft in the vertical direction. According to the swing and lift of the arm, the first moving nozzle 9 moves in the horizontal and vertical directions.

[0094] The first moving nozzle 9 is connected to a mixed liquid pipe 40 that guides the mixed liquid to the first moving nozzle 9. When the mixed liquid valve 50 installed in the mixed liquid pipe 40 is opened, the mixed liquid is ejected downward from the ejection port of the first moving nozzle 9 in a continuous flow. When the mixed liquid valve 50 is opened when the first moving nozzle 9 is located at the central position, the mixed liquid is supplied to the central region of the upper surface of the substrate W.

[0095] The mixed liquid contains a solute and a solvent. The solvent contained in the mixed liquid is, for example, an organic solvent.

[0096] Examples of the organic solvent include alcohols such as isopropyl alcohol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactate esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, lactones such as γ-butyrolactone, and the like. These organic solvents can be used alone or in combination of two or more.

[0097] In the mixed solution, as the solute, it contains a first polymer, a second polymer and a dissolved component. The first polymer is a component capable of etching the surface layer of the substrate W, that is, a component having an etching function. The first polymer is, for example, an organic acid polymer such as carboxylic acid or sulfonic acid. Examples of the carboxylic acid include polyacrylic acid represented by the following Chemical Formula 1. Examples of the sulfonic acid include polystyrene sulfonic acid represented by the following Chemical Formula 2.

[0098] [Chemical Formula 1]

[0099] Chemical Formula 1

[0100]

[0101] [Chemical Formula 2]

[0102] Chemical Formula 2

[0103]

[0104] The second polymer is a component that is solidified or cured through a solid formation process such as heating or light irradiation, that is, a component having a solid formation function. In the first embodiment, the second polymer is a thermosetting resin that is cured by heating. The thermosetting resin may include, for example, at least one of epoxy resin, phenolic resin, melamine resin, unsaturated polyester resin, and polyurethane resin.

[0105] The dissolved component is a substance that is more soluble in the stripping solution described later than the second polymer. The dissolved component is, for example, 2,2-bis(4-hydroxyphenyl)propane. The dissolved component is not limited to 2,2-bis(4-hydroxyphenyl)propane. The details of the dissolved component will be described later.

[0106] The second moving nozzle 10 is an example of a stripping liquid nozzle (stripping liquid supply unit) that supplies (ejects) a stripping liquid such as ammonia water to the upper surface of the substrate W held by the rotating chuck 5 in a continuous flow. The stripping liquid is a liquid used to strip the solidified film formed on the substrate W from the upper surface of the substrate W.

[0107] The second moving nozzle 10 is moved in the horizontal and vertical directions by the second nozzle moving unit 36. The second moving nozzle 10 can be moved between the center position and the starting position (retracted position) in the horizontal direction.

[0108] When the second moving nozzle 10 is located at the center position, it faces the central region of the upper surface of the substrate W. When the second moving nozzle 10 is located at the starting position, it does not face the upper surface of the substrate W and is located outside the processing hood 7 in a top view. By moving in the vertical direction, the second moving nozzle 10 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W.

[0109] The second nozzle moving unit 36 has the same structure as the first nozzle moving unit 35. That is, the second nozzle moving unit 36 may include: an arm (not shown) connected to the second moving nozzle 10 and extending in the horizontal direction; a rotating shaft (not shown) connected to the arm and extending in the vertical direction; and a rotating shaft driving unit (not shown) that raises or rotates the rotating shaft.

[0110] The second moving nozzle 10 is connected to a stripping liquid pipe 41 that guides the stripping liquid to the second moving nozzle 10. When the stripping liquid valve 51 installed in the stripping liquid pipe 41 is opened, the stripping liquid is ejected downward from the ejection port of the second moving nozzle 10 in a continuous flow. When the stripping liquid valve 51 is opened when the second moving nozzle 10 is located at the central position, the stripping liquid is supplied to the central region of the upper surface of the substrate W.

[0111] The stripping liquid ejected from the second moving nozzle 10 can be a liquid that is more likely to dissolve the dissolved components than the solid forming components. The stripping liquid ejected from the second moving nozzle 10 is, for example, an alkaline aqueous solution (alkaline liquid) such as ammonia water. Specific examples of the alkaline aqueous solution include ammonia water, SC1 liquid (ammonia-hydrogen peroxide mixture), TMAH (tetramethylammonium hydroxide) aqueous solution, and choline aqueous solution, as well as any combination thereof. The stripping liquid is not limited to alkaline liquids and can be pure water (preferably DIW), or any aqueous solution (non-alkaline aqueous solution) of neutral or acidic nature.

[0112] The third moving nozzle 11 is an example of a rinse liquid nozzle (rinse liquid supply unit) that supplies (ejects) a rinse liquid such as pure water to the upper surface of the substrate W held by the rotating chuck 5 in a continuous flow. The rinse liquid is a liquid that washes away the liquid attached to the surface of the substrate W.

[0113] The third moving nozzle 11 moves in the horizontal and vertical directions by a third nozzle moving unit 37. The third moving nozzle 11 can move between a central position and a starting position (retracted position) in the horizontal direction.

[0114] When the third moving nozzle 11 is located at the central position, it faces the central region of the upper surface of the substrate W. When the third moving nozzle 11 is located at the starting position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 in a top view. By moving in the vertical direction, the third moving nozzle 11 can approach the upper surface of the substrate W or retract upward from the upper surface of the substrate W.

[0115] The third nozzle moving unit 37 has the same structure as the first nozzle moving unit 35. That is, the third nozzle moving unit 37 may include: an arm (not shown) connected to the third moving nozzle 11 and extending in the horizontal direction; a rotating shaft (not shown) connected to the arm and extending in the vertical direction; and a rotating shaft driving unit (not shown) that raises, lowers, or rotates the rotating shaft.

[0116] The third moving nozzle 11 is connected to a rinse liquid pipe 42 that guides rinse liquid to the third moving nozzle 11. When a rinse liquid valve 52 installed in the rinse liquid pipe 42 is opened, the rinse liquid is ejected downward from the ejection port of the third moving nozzle 11 in a continuous flow. When the rinse liquid valve 52 is opened while the third moving nozzle 11 is located at the central position, the rinse liquid is supplied to the central region of the upper surface of the substrate W.

[0117] Examples of the rinse liquid include pure water such as DIW, carbonated water, electrolyzed ion water, hydrochloric acid water with a dilution concentration (e.g., about 1 ppm to 100 ppm), ammonia water with a dilution concentration (e.g., about 1 ppm to 100 ppm), reduced water (hydrogen water), etc.

[0118] As the rinse liquid, an organic solvent such as IPA may also be used as long as it has compatibility with the stripping liquid. Compatibility means the property that two liquids dissolve and mix with each other. In the substrate processing described later, the upper surface of the substrate W is dried by spinning off the rinse liquid on the substrate W. If the rinse 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.

[0119] Examples of the organic solvent that functions as a low surface tension liquid include a liquid containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.

[0120] The organic solvent that functions as a low surface tension liquid does not have to consist only of monomer components and can also be a liquid mixed with other components. For example, it can be a mixture of IPA and DIW, or a mixture of IPA and HFE.

[0121] Figure 3 FIG. is a block diagram showing the electrical structure of the main part of the substrate processing apparatus 1. The controller 3 includes a microcomputer and controls the controlled objects equipped in the substrate processing apparatus 1 according to a prescribed control program.

[0122] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B that stores the control program. The controller 3 is configured to execute various controls for substrate processing by executing the control program through the processor 3A.

[0123] In particular, the controller 3 is programmed to control the transfer robots IR, CR, the rotation motor 23, the pin opening / closing unit 24, the first nozzle moving unit 35, the second nozzle moving unit 36, the third nozzle moving unit 37, the heater energization unit 64, the heater lifting unit 65, the shield lifting unit 74, the mixed liquid valve 50, the stripping liquid valve 51, and the rinse liquid valve 52. By controlling the valves using the controller 3, whether to eject the processing fluid from the corresponding nozzle and the ejection flow rate of the processing fluid ejected from the corresponding nozzle are controlled.

[0124] Figure 4 FIG. is a flowchart for explaining an example of substrate processing based on the substrate processing apparatus 1. Figure 4 It mainly shows the processing implemented by executing the program by the controller 3. Figures 5A to 5E FIG. is a schematic diagram for explaining the situation of each process of substrate processing.

[0125] In the substrate processing based on the substrate processing apparatus 1, for example, as Figure 4 shown, the substrate loading process (step S1), the mixed liquid supply process (step S2), the coating film formation process (step S3), the solidified film formation process (step S4), the solidified film removal process (step S5), the rinse process (step S6), the spin drying process (step S7), and the substrate unloading process (step S8) are sequentially implemented.

[0126] Hereinafter, mainly referring to Figure 2 and Figure 4 . Appropriately referring to Figures 5A to 5E .

[0127] First, the unprocessed substrate W is transferred by the transfer robots IR, CR (refer to Figure 1)The container C is carried into the processing unit 2 and transferred to the rotary chuck 5 (step S1). Thereby, the substrate W is held horizontally by the rotary chuck 5 (substrate holding process).

[0128] When carrying in the substrate W, the heater unit 6 is arranged at a non-heating position where the substrate W is not heated with the heater 62 energized. The non-heating position is, for example, the lower position. For the heater unit 6, similar to the substrate processing, heating of the substrate W and stopping of heating can be switched by energizing or de-energizing the heater power supply unit 64.

[0129] The holding of the substrate W by the rotary chuck 5 continues until the end of the spin drying process (step S7). After the start of the substrate holding process and until the end of the spin drying process (step S7), for the shield lifting unit 74, the height positions of the first shield 71A and the second shield 71B are adjusted such that at least one shield 71 is in the upper position. With the substrate W held by the rotary chuck 5, the rotation motor 23 rotates the rotary base 21. Thereby, the rotation of the substrate W held horizontally is started (substrate rotation process).

[0130] Next, after the transfer robot CR retracts outside the processing unit 2, a mixed liquid supply process of supplying the mixed liquid to the upper surface of the substrate W is performed (step S2). 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.

[0131] With the first moving nozzle 9 in the processing position, the mixed liquid valve 50 is opened. Thereby, as Figure 5A shown, the mixed liquid can be supplied (sprayed) from the first moving nozzle 9 to the central region of the upper surface of the rotating substrate W (mixed liquid supply process, mixed liquid spraying process). The mixed liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force, and a liquid film 101 of the mixed liquid is formed on the entire upper surface of the substrate W (mixed liquid film forming process). The surface layer portion of the substrate W can be etched by the first polymer (organic acid polymer) in the liquid film 101 of the mixed liquid (etching process, liquid film etching process).

[0132] The supply of the mixed liquid from the first moving nozzle 9 can continue for a specified time, for example, 2 seconds to 4 seconds. In the mixed liquid supply process, the substrate W can rotate at a specified mixed liquid rotation speed, for example, 10 rpm to 1500 rpm. The amount of the mixed liquid coated on the upper surface of the substrate W is about 2 cc.

[0133] The rotational speed of the mixed liquid is preferably a speed such that the mixed liquid does not scatter outside the substrate W, and the liquid film 101 of the mixed liquid preferably forms a puddle state on the substrate W. The puddle state means a state in which the upper surface of the substrate W is covered with the liquid film 101 and the substrate W is stationary in the rotational direction or rotating at a low rotational speed (50 rpm or less).

[0134] Next, as Figure 5B shown, a coating film forming step (step S3) of evaporating the solvent from the mixed liquid on the substrate W to form a coating film 102 is performed.

[0135] Specifically, the mixed liquid valve 50 is closed. Then, the first moving nozzle 9 is moved to the starting position by the first nozzle moving unit 35.

[0136] The centrifugal force generated by the rotation of the substrate W acts not only on the mixed liquid on the substrate W but also on the gas in contact with the liquid film 101. Therefore, due to the action of the centrifugal force, the gas forms an air flow from the center side to the peripheral side of the substrate W. Through this air flow, the solvent in the gas state in contact with the liquid film 101 is removed from the atmosphere in contact with the substrate W. Therefore, the evaporation (volatilization) of the solvent from the mixed liquid on the substrate W can be promoted, and a semi-solid coating film 102 (coating film forming step) can be formed. The so-called semi-solid state is a state in which a solid component and a liquid component are mixed. The first moving nozzle 9 and the rotation motor 23 are an example of a coating film forming unit.

[0137] The surface layer portion of the substrate W is etched by the first polymer (organic acid polymer) in the coating film 102 (etching step). The coating film 102 has a higher viscosity than the liquid film 101. In the coating film forming step, the rotation motor 23 functions as an evaporation unit (evaporation promoting unit) for evaporating the solvent in the mixed liquid.

[0138] The coating film forming step (step S3) continues for, for example, 30 seconds. In the coating film forming step (step S3), the substrate W can rotate at a prescribed coating film forming speed, for example, 800 rpm.

[0139] Next, a solidified film forming step (step S4) of forming a solidified film 100 by solidifying the coating film 102 on the substrate W is performed.

[0140] Specifically, the heater lifting unit 65 disposes the heater unit 6 at the heating position. The heating position is, for example, a spaced heating position for heating the substrate W at a position spaced from the lower surface of the substrate W. Thus, as Figure 5C shown, the coating film 102 can be heated through the substrate W by the heater unit 6 (coating film heating step).

[0141] By heating the coating film 102, the second polymer (thermosetting resin) in the coating film 102 can be cured. By curing the second polymer, a solidified film 100 can be formed (solidified film forming process). By heating to cure the second polymer in the coating film 102 and thereby convert the coating film 102 into the solidified film 100, the etching of the surface layer portion of the substrate W can be stopped (etching stop process). Since the solidified film 100 is formed by heating, heating is an example of a solid formation process. The heater unit 6 is an example of a solid formation unit.

[0142] The heating of the coating film 102 can be continued for a predetermined time, for example, 30 seconds. In the solidified film forming process (step S4), the substrate W can be rotated at a predetermined solidified film forming speed, for example, 800 rpm.

[0143] Next, as Figure 5D and Figure 5E shown, a solidified film removing process (step S5) is performed in which a stripping liquid is supplied to the upper surface of the substrate W to strip and remove the solidified film 100 from the upper surface of the substrate W.

[0144] Specifically, the heater lifting unit 65 moves the heater unit 6 to the non-heating position. Then, the second nozzle moving unit 36 moves the second moving nozzle 10 to the processing position. The processing position of the second moving nozzle 10 is, for example, the central position.

[0145] With the second moving nozzle 10 in the processing position, the stripping liquid valve 51 is opened. Thus, as Figure 5D shown, the stripping liquid can be supplied (sprayed) from the second moving nozzle 10 to the central region of the upper surface of the rotating substrate W (stripping liquid supply process, stripping liquid spraying process). The stripping liquid supplied to the upper surface of the substrate W spreads over the entire substrate W by centrifugal force. The stripping liquid supplied to the upper surface of the substrate W dissolves the dissolved components in the solidified film 100 while reaching the interface between the upper surface of the substrate W and the solidified film 100 and enters between the solidified film 100 and the upper surface of the substrate W. As Figure 5E shown, by continuously supplying the stripping liquid, the solidified film 100 can be stripped and removed from the upper surface of the substrate W (solidified film removing process).

[0146] The supply of the stripping liquid can be continued for, for example, 30 seconds. In the solidified film removing process (step S5), the substrate W can be rotated at a predetermined removal rotation speed, for example, 800 rpm.

[0147] Next, as Figure 5FAs shown, a rinsing process (step S6) of washing off the stripping liquid from the upper surface of the substrate W is performed. Specifically, the stripping liquid valve 51 is closed, and the second nozzle moving unit 36 moves the second moving nozzle 10 to the retracted position. Then, 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.

[0148] Then, with the third moving nozzle 11 in the processing position, the rinsing liquid valve 52 is opened. Thus, as Figure 5F shown, rinsing liquid is supplied (sprayed) from the third moving nozzle 11 to the central region of the upper surface of the rotating substrate W (rinsing liquid supply process, rinsing liquid spraying process). The rinsing liquid supplied to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force. Thus, the stripping liquid attached to the upper surface of the substrate W is discharged outside the substrate W together with the rinsing liquid and is replaced by the rinsing liquid (rinsing process, stripping liquid discharge process).

[0149] The supply of the rinsing liquid to the upper and lower surfaces of the substrate W can continue for a specified time, for example, 30 seconds. In the rinsing process (step S6), the substrate W can rotate at a specified cleaning rotation speed, for example, 800 rpm.

[0150] Next, a spin drying process (step S7) of drying the upper surface of the substrate W by rotating the substrate W at high speed is performed. Specifically, the rinsing liquid valve 52 is closed. Thus, the supply of the rinsing liquid to the upper surface of the substrate W can be stopped.

[0151] Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at high speed. The substrate W in the spin drying process can rotate at a drying speed, for example, 1500 rpm. The spin drying process can be performed for a specified time, for example, 30 seconds. Thus, a large centrifugal force acts on the rinsing liquid on the substrate W, and the rinsing liquid on the substrate W is thrown off to the periphery of the substrate W.

[0152] Then, the rotation motor 23 stops the rotation of the substrate W. The shield lifting unit 74 moves the first shield 71A and the second shield 71B to the lower position.

[0153] The transfer robot CR enters the processing unit 2, obtains the processed substrate W from the chuck pins 20 of the rotary chuck 5, and carries it out of the processing unit 2 (step S8). This substrate W is transferred from the transfer robot CR to the transfer robot IR and is stored in the container C by the transfer robot IR.

[0154] Next, use Figures 6A to 6E to describe in detail the situation near the surface of the substrate W during substrate processing. Figures 6A to 6E is a schematic diagram for explaining the situation near the surface of the substrate W during substrate processing.

[0155] The coating film 102 formed in the coating film forming step (step S3) contains a first polymer (organic acid polymer), a second polymer (thermosetting resin), and a dissolving component. The first polymer in the coating film 102 can be used to etch the surface portion 150 of the substrate W (etching step). The surface portion 150 of the substrate W refers to a portion near the surface of the substrate W.

[0156] The first polymer in the portion of the coating film 102 in contact with the upper surface 151 of the substrate W disappears due to etching of the surface layer 150 of the substrate W. Therefore, in order to prevent the concentration of the first polymer in the portion of the coating film 102 in contact with the upper surface 151 of the substrate W from decreasing, the first polymer in the coating film 102 moves toward the upper surface 151 of the substrate W. Figure 6B As shown, the etching of the surface layer portion 150 of the substrate W is gradually progressed, and the upper surface 151 of the substrate W retreats toward the lower surface side of the substrate W. As the surface layer portion 150 of the substrate W is etched, etching residues 104 are formed.

[0157] Then, the coating film 102 is heated through the substrate W, as shown in FIG. Figure 6C As shown, the coating film 102 is converted into a solidified film 100. The solidified film 100 includes a first polymer, a second polymer, and a dissolved component in a solid state. The first polymer in a solid state is referred to as a first polymer solid 110. The second polymer in a solid state is referred to as a second polymer solid 111. The dissolved component in a solid state is referred to as a dissolved component solid 112. The solidified film 100 (especially the second polymer solid 111) retains an etching residue 104 formed by the etching process.

[0158] Next, refer to Figure 6D The soluble component solid 112 is selectively dissolved by the stripping liquid. That is, the solidified film 100 is partially dissolved (dissolution step, partial dissolution step).

[0159] The phrase "solid state dissolved component solid 112 is selectively dissolved" means that not only solid state dissolved component solid 112 is dissolved. The phrase "solid state dissolved component solid 112 is selectively dissolved" means that most of solid state dissolved component solid 112 is dissolved, although solid state second polymer solid 111 is also slightly dissolved.

[0160] Triggered by the selective dissolution of the dissolved component solid 112 , the through-holes 106 are formed in the portion of the solidified film 100 where the dissolved component solid 112 is concentrated (through-hole forming step).

[0161] In a portion where the solid 112 of the dissolved component exists with segregation, not only the solid 112 of the dissolved component exists, but also the second polymer solid 111 exists. The stripping liquid not only dissolves the solid 112 of the dissolved component, but also dissolves the second polymer solid 111 around the solid 112 of the dissolved component. Therefore, the formation of the through-hole 106 can be promoted.

[0162] In a top view, the through-hole 106 is, for example, on the order of several nm in diameter. The through-hole 106 does not need to be clearly formed to an observable degree. That is, for the through-hole 106, it is sufficient that a path for the stripping liquid to move from the upper surface of the solidified film 100 to the upper surface 151 of the substrate is formed in the solidified film 100, and as long as the path as a whole penetrates the solidified film 100.

[0163] Here, when the solvent remains moderately in the solidified film 100, the stripping liquid partially dissolves the solidified film 100 while dissolving in the solvent remaining in the solidified film 100. Specifically, the stripping liquid dissolves the solid 112 of the dissolved component in the solidified film 100 while dissolving in the solvent remaining in the solidified film 100 to form the through-hole 106. Therefore, the stripping liquid easily enters the solidified film 100 (dissolution entry process).

[0164] The stripping liquid that has reached the upper surface 151 of the substrate W acts on the interface between the solidified film 100 and the substrate W, strips the solidified film 100, and removes the stripped solidified film 100 from the upper surface 151 of the substrate W (stripping and removing process).

[0165] Specifically, the solubility of the second polymer solid 111 with respect to the stripping liquid is lower than the solubility of the solid 112 of the dissolved component with respect to the stripping liquid, and most of the second polymer solid 111 maintains a solid state. Therefore, only the surface vicinity of the second polymer solid 111 is slightly dissolved by the stripping liquid. Therefore, the stripping liquid that has reached the vicinity of the upper surface 151 of the substrate W via the through-hole 106 only slightly dissolves the portion of the second polymer solid 111 near the upper surface 151 of the substrate W. Thus, as Figure 6D shown in the enlarged view, the stripping liquid slowly dissolves the solid second polymer solid 111 near the upper surface 151 of the substrate W and enters the gap G between the solidified film 100 and the upper surface 151 of the substrate W (stripping liquid entry process).

[0166] Moreover, for example, starting from the periphery of the through-hole 106, cracks are formed in the solidified film 100. Therefore, the solid 112 of the dissolved component is also referred to as a crack generating component. The solidified film 100 is split by the formation of cracks and becomes the film pieces 108. As Figure 6EAs shown, the diaphragm 108 of the solidified film 100 is peeled off from the substrate W while holding the etching residue 104 (solidified film splitting process, solidified film peeling process).

[0167] Moreover, by continuously supplying the stripping liquid, the solidified film 100 that has become the diaphragm 108 is washed away by the stripping liquid while holding the etching residue 104. In other words, the diaphragm 108 holding the etching residue 104 is discharged outside the substrate W and removed from the upper surface 151 of the substrate W (solidified film removal process, etching residue removal process). Thereby, the upper surface 151 of the substrate W can be cleaned well.

[0168] Through the first embodiment, the following effects are achieved.

[0169] Through the first embodiment, a semi-solid coating film 102 containing the first polymer and the second polymer is formed on the upper surface 151 of the substrate W. The surface layer portion 150 of the substrate W is etched by the first polymer in the coating film 102. By heat treatment (solid formation treatment), the second polymer in the coating film 102 is solidified. As a result, the coating film 102 is transformed into the solidified film 100. Compared with the coating film 102, the first polymer is less likely to diffuse in the solidified film 100. Therefore, by transforming the coating film 102 into the solidified film 100, the etching of the surface layer portion 150 of the substrate W by the first polymer can be stopped.

[0170] In contrast to this method, in a method of etching the surface layer portion 150 of the substrate W while continuously supplying a continuous flow of an etching liquid such as hydrofluoric acid to the upper surface 151 of the substrate W, the etching liquid is continuously discharged to the outside of the substrate W.

[0171] On the other hand, the fluidity of the semi-solid coating film 102 is lower than that of the continuous flow of the etching liquid. Therefore, the amount of the mixed liquid discharged to the outside of the substrate W can be reduced. Therefore, the consumption amount of the first polymer, that is, the consumption amount of the etching component, can be reduced.

[0172] When the surface layer portion 150 of the substrate W is etched using the first polymer in the coating film 102, the etching residue 104 easily adheres to the upper surface 151 of the substrate W. In the method according to the first embodiment, in the solidified film removal process, the solidified film 100 is not dissolved in the stripping liquid and removed from the upper surface 151 of the substrate W, but is peeled off and removed from the upper surface 151 of the substrate W. Therefore, the solidified film 100 is peeled off from the upper surface 151 of the substrate W while holding the etching residue 104. As a result, the etching residue 104 can be removed from the upper surface 151 of the substrate W together with the solidified film 100.

[0173] In addition, through the first embodiment, the etching process includes a liquid film etching process and a coating film etching process. Therefore, not only is the surface layer portion 150 of the substrate W etched by the first polymer in the coating film 102, but also the surface layer portion 150 of the substrate W is etched by the first polymer in the liquid film 101 of the mixed solution that forms the basis of the coating film 102. In the liquid film 101 of the mixed solution, the first polymer in the portion in contact with the upper surface 151 of the substrate W disappears by etching the surface layer portion 150 of the substrate W. The fluidity of the mixed solution is higher than that of the semi-solid coating film 102.

[0174] Therefore, compared with the etching based on the coating film 102, when the first polymer near the upper surface 151 of the substrate W disappears by etching, the first polymer in the liquid film 101 of the mixed solution is more likely to diffuse quickly compared to the first polymer in the coating film 102. Therefore, a decrease in the concentration of the first polymer near the upper surface 151 of the substrate W can be suppressed, and thus, the surface layer portion 150 of the substrate W can be etched quickly.

[0175] In addition, since the etching is performed in a state where the liquid film 101 of the mixed solution is formed on the upper surface of the substrate W, the amount of the first polymer discharged to the outside of the substrate W, that is, the consumption amount of the etching component, can be reduced compared to a method of etching the surface layer portion 150 of the substrate W while continuously supplying a continuous flow of an etching solution such as hydrofluoric acid to the upper surface 151 of the substrate W.

[0176] The liquid film etching process includes a mixed liquid film forming process of forming a liquid film of the mixed solution on the upper surface 151 of the substrate W from the first moving nozzle 9 facing the upper surface 151 of the substrate W. Therefore, the first polymer and the second polymer are supplied to the upper surface 151 of the substrate W in a pre-mixed state. Since it is not necessary to mix the first polymer and the second polymer on the upper surface 151 of the substrate W, the coating film 102 can be formed quickly. Furthermore, the time required for substrate processing can be shortened.

[0177] In addition, through the first embodiment, the thermosetting resin as the second polymer in the coating film 102 is cured by heating. By curing the thermosetting resin, the coating film 102 is transformed into a solidified film 100. Since the solidified film 100 is formed by curing the thermosetting resin, the diffusion of the first polymer can be further suppressed. Therefore, the etching of the surface layer portion 150 of the substrate W based on the first polymer can be stopped more reliably.

[0178] In addition, according to the first embodiment, the solidified film 100 contains a dissolved component that is more soluble in the stripping liquid than the second polymer. Moreover, the dissolved component solid 112 in the solidified film 100 is dissolved by the stripping liquid. By dissolving the dissolved component solid 112 in the solidified film 100 using the stripping liquid, through-holes 106 can be formed in the solidified film 100. Therefore, the stripping liquid can quickly reach the interface between the solidified film 100 and the substrate W via the through-holes 106 formed in the solidified film 100. The stripping liquid enters the interface between the substrate W and the solidified film 100, and the solidified film 100 is peeled off from the upper surface 151 of the substrate W. Thus, after the etching of the first polymer is completed, the solidified film 100 can be quickly peeled off from the upper surface 151 of the substrate W.

[0179] Since the second polymer can be maintained in a solid state, even after the dissolved component solid 112 is dissolved, the etching residue 104 can be retained by the second polymer solid 111. Even when the solidified film 100 is removed from the upper surface of the substrate W by the supply of the stripping liquid, the state in which the etching residue 104 is retained by the solidified film 100 can be maintained. Therefore, compared with the case where the etching residue 104 is not retained by the solidified film 100, the energy (physical force) received due to the flow of the stripping liquid can be increased. As a result, the etching residue 104 can be effectively removed from the upper surface of the substrate W by the stripping liquid.

[0180] In addition, according to the first embodiment, the etching residue 104 generated by the etching of the surface layer portion 150 of the substrate W is removed from the upper surface 151 of the substrate W together with the solidified film 100 in the solidified film removing step. Therefore, after the solidified film 100 is removed, there is no need to perform a process for separately removing the etching residue 104.

[0181] In addition, in the first embodiment, an organic acid polymer having a higher viscosity than an organic acid such as acetic acid which is not a polymer can be used as the first polymer. Therefore, by using the organic acid polymer, when covering the upper surface of the substrate W as an etching component, the amount of liquid discharged from the substrate W can be reduced. Therefore, the usage amount of the etching component can be reduced.

[0182] <Second Embodiment>

[0183] Figure 7 FIG. is a schematic partial cross-sectional view showing a schematic structure of a processing unit 2 provided in a substrate processing apparatus 1P according to the second embodiment. Figure 7 Among them, for a structure equivalent to the structure shown in the foregoing Figures 1 to 6E the same reference numerals as Figure 1 etc. are assigned, and their descriptions are omitted (the same applies to the following Figures 8 to 9B ).

[0184] The main difference between the substrate processing apparatus 1P according to the second embodiment and the substrate processing apparatus 1 according to the first embodiment is that the processing unit 2 of the substrate processing apparatus 1P is configured such that the first polymer and the second polymer are ejected from their respective nozzles.

[0185] Specifically, the processing unit 2 includes a first moving nozzle 9P that supplies the first polymer liquid containing the first polymer to the upper surface of the substrate W, and a fourth moving nozzle 12 that supplies the second polymer liquid containing the second polymer to the upper surface of the substrate W.

[0186] The first moving nozzle 9P is an example of a first polymer liquid nozzle (first polymer liquid supply unit) that supplies (ejects) the first polymer liquid to the upper surface of the substrate W held by the rotary chuck 5.

[0187] Similar to the first moving nozzle 9 according to the first embodiment, the first moving nozzle 9P can be moved in the horizontal and vertical directions by the first nozzle moving unit 35. The first moving nozzle 9P can be moved in the horizontal direction between the central position and the starting position (retracted position).

[0188] The first moving nozzle 9P is connected to a first polymer liquid pipe 40P that guides the first polymer liquid to the first moving nozzle 9P. When the first polymer liquid valve 50P installed in the first polymer liquid pipe 40P is opened, the first polymer liquid is ejected downward from the ejection port of the first moving nozzle 9P in a continuous flow. When the first polymer liquid valve 50P is opened while the first moving nozzle 9P is in the central position, the first polymer liquid is supplied to the central region of the upper surface of the substrate W.

[0189] The first polymer liquid contains a solute and a solvent. The solvent contained in the first polymer liquid is, for example, an organic solvent. As the organic solvent, the organic solvents listed as the solvents that can be contained in the mixed liquid according to the first embodiment can be used.

[0190] In the first polymer liquid, the first polymer is contained as a solute. As the first polymer, the polymers listed as the first polymers that can be contained in the mixed liquid according to the first embodiment can be used.

[0191] The fourth moving nozzle 12 is an example of a second polymer liquid nozzle (second polymer liquid supply unit) that supplies (ejects) the second polymer liquid to the upper surface of the substrate W held by the rotary chuck 5.

[0192] The fourth moving nozzle 12 can be moved in the horizontal and vertical directions by the fourth nozzle moving unit 38. The fourth moving nozzle 12 can be moved in the horizontal direction between the central position and the starting position (retracted position).

[0193] When the fourth moving nozzle 12 is located at the central position, it faces the central region of the upper surface of the substrate W. When the fourth moving nozzle 12 is located at the starting position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 in a top view. The fourth moving nozzle 12 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0194] The fourth nozzle moving unit 38 has the same structure as the first nozzle moving unit 35. That is, the fourth nozzle moving unit 38 may include an arm (not shown) connected to the fourth moving nozzle 12 and extending in the horizontal direction, a rotating shaft (not shown) connected to the arm and extending in the vertical direction, and a rotating shaft driving unit (not shown) for raising, lowering, or rotating the rotating shaft.

[0195] The fourth moving nozzle 12 is connected to a second polymer liquid pipe 43 that guides the second polymer liquid to the fourth moving nozzle 12. When the second polymer liquid valve 53 installed in the second polymer liquid pipe 43 is opened, the second polymer liquid is ejected downward from the ejection port of the fourth moving nozzle 12 in a continuous flow. When the second polymer liquid valve 53 is opened when the fourth moving nozzle 12 is located at the central position, the second polymer liquid is supplied to the central region of the upper surface of the substrate W.

[0196] The second polymer liquid contains a solute and a solvent. The solvent contained in the second polymer liquid is, for example, an organic solvent. As the organic solvent, the organic solvents listed as the solvents that may be contained in the mixture according to the first embodiment can be used.

[0197] In the second polymer liquid, as the solute, it contains a second polymer and a dissolved component. The second polymer can be a thermosetting resin as in the first embodiment. The thermosetting resin can contain, for example, at least one of epoxy resin, phenolic resin, melamine resin, unsaturated polyester resin, and polyurethane resin as in the first embodiment. The details of the dissolved component will be described later.

[0198] The substrate processing apparatus 1P according to the second embodiment can be used to perform the same substrate processing as the substrate processing apparatus 1 according to the first embodiment (refer to Figure 4 ).

[0199] However, in the substrate processing based on the substrate processing apparatus 1P according to the second embodiment, by mixing the first polymer liquid and the second polymer liquid on the upper surface of the substrate W, a mixed liquid can be formed on the upper surface of the substrate W. Figure 8 It is a schematic diagram for explaining the first example of the mixed liquid supply process (step S2) in the substrate processing based on the substrate processing apparatus 1P according to the second embodiment.

[0200] Specifically, in a state where the first moving nozzle 9P and the fourth moving nozzle 12 are located at the processing positions, the first polymer liquid valve 50P and the second polymer liquid valve 53 are opened. Thereby, the first polymer liquid is ejected from the first moving nozzle 9P onto the upper surface of the substrate W, and the second polymer liquid is ejected from the fourth moving nozzle 12 onto the upper surface of the substrate W. The supply of the first polymer liquid to the upper surface of the substrate W and the supply of the second polymer liquid to the upper surface of the substrate W can be carried out simultaneously.

[0201] By mixing the first polymer liquid and the second polymer liquid supplied to the upper surface of the substrate W on the upper surface of the substrate W, a mixed liquid is formed on the upper surface of the substrate W (mixed liquid forming step). Thereby, the mixed liquid can be supplied to the upper surface of the substrate W (mixed liquid supply step). The first polymer liquid and the second polymer liquid are mixed while spreading on the upper surface of the substrate W by centrifugal force. Thereby, a liquid film 101 of the mixed liquid can be formed on the entire upper surface of the substrate W (mixed liquid film forming step). The ejection of the first polymer liquid and the ejection of the second polymer liquid can start simultaneously. The liquid film 101 of the mixed liquid is preferably in a liquid-covered state.

[0202] The surface layer portion of the substrate W can be etched by the first polymer (organic acid polymer) in the liquid film 101 of the mixed liquid (etching step, liquid film etching step).

[0203] The supply of the first polymer liquid from the first moving nozzle 9P and the supply of the second polymer liquid from the fourth moving nozzle 12 can continue for a specified time, for example, 2 seconds to 4 seconds. In the mixed liquid supply step, the substrate W can rotate at a specified mixed liquid rotation speed, for example, 10 rpm to 1500 rpm. The amount of the mixed liquid coated on the upper surface of the substrate W is about 2 cc.

[0204] The rotation speed of the substrate W in the mixed liquid supply step (step S2) is preferably a speed such that the mixed liquid does not scatter to the outside of the substrate W, and the liquid film 101 of the mixed liquid is preferably in a liquid-covered state on the substrate W.

[0205] Then, the first polymer liquid valve 50P and the second polymer liquid valve 53 are closed, and the first moving nozzle 9P and the fourth moving nozzle 12 are moved to the starting positions. Moreover, as described in the first embodiment, under the action of the air flow generated by the action of centrifugal force, the evaporation (volatilization) of the solvent from the mixed liquid formed on the substrate W can be promoted. Thereby, as Figure 5B shown, a semi-solid coating film 102 can be formed (coating film forming step). The surface layer portion of the substrate W is etched by the first polymer (organic acid polymer) in the coating film 102 (etching step, coating film etching step). In the second embodiment, the coating film forming unit is composed of the first moving nozzle 9P, the fourth moving nozzle 12, and the rotation motor 23.

[0206] Etching of the surface layer portion of the substrate W starts simultaneously with the start of attachment of the first polymer solution to the upper surface of the substrate W, and ends with the formation of the solidified film 100.

[0207] In the first example of the substrate processing according to the second embodiment, the first polymer solution and the second polymer solution are mixed on the substrate W to form a mixed solution. Therefore, assuming that the first polymer and the second polymer react with each other, the reaction between the first polymer and the second polymer can be suppressed before the first polymer and the second polymer are supplied to the upper surface of the substrate W.

[0208] In addition, compared with the method of sequentially supplying the first polymer solution and the second polymer solution to the upper surface of the substrate W, the time required for forming the coating film 102 can be shortened. Furthermore, the time required for substrate processing can be shortened.

[0209] In the substrate processing apparatus 1P according to the second embodiment, substrate processing different from the substrate processing of the first example shown in Figure 8 may also be performed. For example, in the mixed solution supply step (step S2), substrate processing of the second example may also be performed, that is, the first polymer solution is supplied to the upper surface of the substrate W, and after the supply of the first polymer solution is completed, the second polymer solution is supplied to the upper surface of the substrate W. Figure 9A And Figure 9B is a schematic diagram for explaining the second example of the mixed solution supply step (step S2) in the substrate processing based on the substrate processing apparatus 1P.

[0210] The substrate processing of the second example based on the substrate processing apparatus 1P will be described in detail. First, with the first moving nozzle 9P in the processing position, the first polymer solution valve 50P is opened. Thereby, the first polymer solution (first polymer solution supply step, first polymer solution ejection step) can be supplied (ejected) from the first moving nozzle 9P to the upper surface of the substrate W. The first polymer solution attached to the upper surface of the substrate W spreads over the entire upper surface of the substrate W by centrifugal force, and a liquid film 120 of the first polymer solution is formed on the entire upper surface of the substrate W (first polymer solution film formation step). The liquid film 120 is preferably in a liquid-covered state.

[0211] The supply of the first polymer solution from the first moving nozzle 9P may continue for a predetermined time, for example, 2 seconds to 4 seconds. In the first polymer solution supply step, the substrate W may rotate at a predetermined first polymer solution rotation speed, for example, 10 rpm to 1500 rpm. The amount of the first polymer solution coated on the upper surface of the substrate W is about 2 cc.

[0212] If a liquid film 120 of the first polymer solution is formed on the upper surface of the substrate W, the first polymer solution valve 50P is closed, and the first moving nozzle 9P is moved to the starting position. On the other hand, the fourth moving nozzle 12 is moved to the processing position. With the fourth moving nozzle 12 in the processing position, the second polymer solution valve 53 is opened. Thereby, the second polymer solution can be supplied (sprayed) from the fourth moving nozzle 12 to the upper surface of the substrate W (second polymer solution supply process, second polymer solution spraying process).

[0213] By supplying the second polymer solution to the liquid film 120 of the first polymer solution, the first polymer solution and the second polymer solution are mixed to form a mixed solution (mixed solution formation process). Thereby, the mixed solution can be supplied to the upper surface of the substrate W (mixed solution supply process). By mixing the second polymer solution with the liquid film 120 of the first polymer solution, a liquid film 101 of the mixed solution is formed on the entire upper surface of the substrate W (mixed solution liquid film formation process). The liquid film 101 of the mixed solution is preferably in a liquid-overlying state.

[0214] The spraying of the second polymer solution from the fourth moving nozzle 12 can be started before the spraying of the first polymer solution from the first moving nozzle 9P ends.

[0215] The surface layer portion of the substrate W is etched by the first polymer (organic acid polymer) in the liquid film 101 of the mixed solution (etching process, liquid film etching process).

[0216] The supply of the second polymer solution from the fourth moving nozzle 12 can continue for a specified time, for example, 2 seconds to 4 seconds. In the second polymer solution supply process, the substrate W can rotate at a specified second polymer solution rotation speed, for example, 10 rpm to 1500 rpm. The amount of the second polymer solution coated on the upper surface of the substrate W is about 2 cc.

[0217] The rotation speed of the substrate W in the second polymer solution supply process is preferably a speed such that the second polymer solution does not scatter outside the substrate W, and the liquid film 101 of the second polymer solution preferably becomes a liquid-overlying state on the substrate W.

[0218] Then, the second polymer solution valve 53 is closed, and the fourth moving nozzle 12 is moved to the starting position. Moreover, as described in the first embodiment, the evaporation (volatilization) of the solvent from the mixed solution formed on the substrate W can be promoted by the airflow generated by the centrifugal force. Thereby, as Figure 5B shown, a semi-solid coating film 102 can be formed (coating film formation process). The surface layer portion of the substrate W is etched by the first polymer (organic acid polymer) in the coating film 102 (etching process, coating film etching process).

[0219] Etching of the surface layer portion of the substrate W starts simultaneously with the start of attachment of the first polymer solution to the upper surface of the substrate W, and ends with the formation of the solidified film 100.

[0220] In the second example of the substrate processing according to the second embodiment, the first polymer solution and the second polymer solution are mixed on the substrate W to form a mixed solution. Therefore, assuming that the first polymer and the second polymer react with each other, the reaction between the first polymer and the second polymer can be suppressed before the first polymer and the second polymer are supplied to the upper surface of the substrate W.

[0221] In addition, the first polymer solution is supplied to the upper surface of the substrate W before the second polymer solution. Therefore, the second polymer solution is not mixed into the liquid film 120 on the upper surface of the substrate W. Therefore, the concentration of the first polymer in the liquid film 120 of the first polymer solution is higher than the concentration of the first polymer in the liquid film 101 of the mixed solution. Therefore, the surface layer portion of the substrate W can be etched in a short time by the first polymer in the liquid film 120 of the first polymer solution.

[0222] In addition, as the etching progresses, after the first polymer is consumed to a certain extent, the first polymer solution and the second polymer solution are mixed on the upper surface of the substrate W. Therefore, in the case where the first polymer and the second polymer react with each other, the reaction between the first polymer and the second polymer can be further suppressed.

[0223] <Third Embodiment>

[0224] Figure 10 FIG. is a schematic diagram showing a schematic structure of the processing unit 2 provided in the substrate processing apparatus 1Q according to the third embodiment. Figure 10 Among them, for the structure equivalent to the structure shown in the foregoing Figures 1 to 9B the same reference numerals as Figure 1 etc. are assigned, and the description thereof is omitted (the same applies to the following Figure 11 ).

[0225] The main difference between the substrate processing apparatus 1Q according to the third embodiment and the substrate processing apparatus 1 according to the first embodiment is that: instead of the heater unit 6, a light irradiation unit 8 is provided.

[0226] The light irradiation unit 8 includes: a relative member 13 having a relative surface 13a facing the upper surface (upper side surface) of the substrate W held by the rotary chuck 5 from above; and a plurality of lamps 80 mounted on the relative surface 13a.

[0227] The relative member 13 is formed in a disk shape having a diameter substantially equal to or larger than the diameter of the substrate W. The relative surface 13a is disposed along a substantially horizontal plane at a position above the rotary chuck 5.

[0228] On the side of the opposing member 13 opposite to the opposing surface 13a, a rotating shaft 130 is fixed.

[0229] The opposing member 13 separates the atmosphere in the space between the opposing surface 13a and the upper surface of the substrate W from the atmosphere outside this space. Therefore, the opposing member 13 is also referred to as a partition plate.

[0230] A plurality of lamps 80 are arranged at equal intervals over the entire range of the opposing surface 13a. The processing unit 2 further includes a lamp power supply unit 85 configured to energize or stop energizing the plurality of lamps 80. The lamps 80 emit light when energized. Examples of the light emitted from each lamp 80 include infrared rays, ultraviolet rays, visible light, etc.

[0231] The processing unit 2 further includes: an opposing member lifting unit 131 for lifting the opposing member 13; and an opposing member rotating unit 132 for rotating the opposing member 13 about the rotation axis A1.

[0232] The opposing member lifting unit 131 can position the opposing member 13 at any position (height) in the vertical direction from the lower position to the upper position. The lower position is the position where the opposing surface 13a is closest to the substrate W within the movable range of the opposing member 13. The upper position is the position where the opposing surface 13a is farthest from the substrate W within the movable range of the opposing member 13. When the opposing member 13 is in the upper position, in order to carry in and out the substrate W, the transfer robot CR can access the rotating chuck 5.

[0233] The opposing member lifting unit 131 includes, for example, a ball screw mechanism (not shown) connected to a support member (not shown) that supports the rotating shaft 130, and an electric motor (not shown) that supplies driving force to the ball screw mechanism. The opposing member lifting unit 131 is also referred to as an opposing member lifter (partition plate lifter). The opposing member rotating unit 132 includes, for example, a motor (not shown) that rotates the rotating shaft 130.

[0234] The opposing member lifting unit 131 lifts the plurality of lamps 80 together with the opposing member 13. The opposing member lifting unit 131 is an example of a lamp lifting unit (lamp lifter). The opposing member rotating unit 132 rotates the plurality of lamps 80 together with the opposing member 13. The opposing member rotating unit 132 is an example of a lamp rotating unit (lamp rotating motor).

[0235] Different from the third embodiment, the opposing member 13 can be, for example, mounted and fixed to the upper wall of the chamber 4.

[0236] The solvent contained in the mixture is, for example, an organic solvent. As the organic solvent, the organic solvents listed as the solvents that can be contained in the mixture according to the first embodiment can be used. As the first polymer contained in the mixture, the polymers listed as the first polymers that can be contained in the mixture according to the first embodiment can be used.

[0237] The second polymer contained in the mixture according to the third embodiment is different from the second polymer contained in the mixture according to the first embodiment and is a photocurable resin that is cured by irradiation with light. Examples of the photocurable resin include epoxy resins and acrylic resins.

[0238] The lamp energization unit 85, the relative member lifting unit 131, and the relative member rotation unit 132 are controlled by the controller 3 (see Figure 3 ).

[0239] The substrate processing apparatus 1Q according to the third embodiment can perform the same substrate processing as the substrate processing according to the first embodiment (see Figure 4 ). However, in the solidification film formation step (step S4), light is irradiated onto the coating film 102.

[0240] Specifically, after the coating film formation step (step S3), the relative member 13 is disposed at a processing position between the upper position and the lower position by the relative member lifting unit 131. By energizing the lamp 80 while the relative member 13 is in the processing position, light can be irradiated onto the coating film 102 on the substrate W (see Figure 5B ). Thereby, as Figure 11 shown, the solidification film 100 is formed, and the etching of the surface layer portion of the substrate W is stopped (etching stop step). Since the solidification film 100 is formed by light irradiation, light irradiation is an example of a solid formation process. The light irradiation unit 8 is an example of a solid formation unit.

[0241] As Figure 12 shown, by irradiating the coating film 102 with light, the coating film 102 is converted into the solidification film 100. In addition, regarding the situation near the surface of the substrate W in the substrate processing, it is substantially the same as in the first embodiment.

[0242] By the third embodiment, the same effects as those of the first embodiment are achieved.

[0243] In addition, the solid formation process includes a light irradiation process on the coating film 102, and the second polymer is a photocurable resin. Therefore, the photocurable resin as the second polymer in the coating film is cured by the irradiation of light. Through the curing of the photocurable resin, the coating film 102 is transformed into the solidified film 100. Since the solidified film 100 is formed by the curing of the photocurable resin, the diffusion of the etching component can be further suppressed. Therefore, the etching of the surface portion 150 of the substrate W based on the etching component can be stopped more reliably.

[0244] The substrate processing apparatus 1Q of the third embodiment can be configured to be able to mix the first polymer liquid and the second polymer liquid on the substrate W. Specifically, instead of the first moving nozzle 9, as Figure 13 shown, the first moving nozzle 9P and the fourth moving nozzle 12 according to the second embodiment can be provided. If this structure is adopted, the same substrate processing as that of the substrate processing according to the second embodiment (see Figures 8 to 9B ) can be implemented.

[0245] Next, using Figure 14 and Figure 15 , a modified example of the light irradiation unit 8 will be described. Figure 14 FIG. is a schematic diagram for explaining the first modified example of the light irradiation unit 8. Figure 15 FIG. is a schematic diagram for explaining the second modified example of the light irradiation unit 8.

[0246] For example, as in the first modified example shown in Figure 14 , the light irradiation unit 8 is configured to move between the irradiation position and the starting position (retracted position) by a lamp moving unit 86 provided in the chamber 4.

[0247] The irradiation position is a position where the light irradiation unit 8 faces the upper surface of the substrate W (for example, the position indicated by the two-dot chain line in Figure 14 ). The irradiation position is a position where light can be irradiated from the light irradiation unit 8 to the upper surface of the substrate W. The retracted position is a position where light cannot be irradiated from the light irradiation unit 8 to the upper surface of the substrate W (for example, the position indicated by the solid line in Figure 14 ). When the light irradiation unit 8 is located at the irradiation position, the light irradiation unit 8 faces the upper surface of the substrate W. When the light irradiation unit 8 is located at the starting position, it does not face the upper surface of the substrate W and is located outside the processing cover 7 in a top view.

[0248] Figure 14In the structure shown, the light irradiation unit 8 includes a lamp 80 and a lamp holder 81 that houses the lamp 80. The lamp moving unit 86 includes an arm 87 that supports the lamp holder 81, a rotating shaft 89 that is connected to the arm 87 and extends vertically, and an arm moving unit 88 that moves the arm 87 via the rotating shaft 89. The arm moving unit 88 includes, for example, a motor that rotates the rotating shaft 89 about its central axis (rotation axis A2) to horizontally move the arm 87, and a ball screw mechanism that raises and lowers the arm 87 together with the rotating shaft 89.

[0249] In addition, as Figure 15 shown in the second modification, the lamp 80 can be rod-shaped and disposed within the arm 87 that extends linearly.

[0250] <Fourth Embodiment>

[0251] Figure 16 It is a schematic diagram for explaining the structure of the substrate processing apparatus 1R according to the fourth embodiment. The main difference between the substrate processing apparatus 1R according to the fourth embodiment and the substrate processing apparatus 1Q according to the third embodiment is that the substrate processing apparatus 1R is configured such that the formation of the solidified film 100 and the peeling of the solidified film 100 are performed in different chambers 4A and 4B, respectively.

[0252] The substrate processing apparatus 1R includes a solidified film forming processing unit 2A for forming the solidified film 100 and a solidified film removing processing unit 2B for removing the solidified film 100.

[0253] The solidified film forming processing unit 2A includes a rotating chuck 5A that rotates the substrate W while keeping it horizontal, a first moving nozzle 9 that supplies a mixed liquid to the upper surface of the substrate W, and a chamber 4A that houses the rotating chuck 5A and the first moving nozzle 9.

[0254] In the chamber 4A, an entrance / exit 4Aa is formed for loading or unloading the substrate W by a transfer robot CR. In the chamber 4A, a shutter unit 4Ab is provided to open and close the entrance / exit.

[0255] The solidified film forming processing unit 2A further includes a light irradiation unit 8 that irradiates light onto the substrate W passing through the entrance / exit 4Aa of the chamber 4A. The light irradiation unit 8 includes, for example, a lamp that emits infrared rays, ultraviolet rays, visible light, etc. The light irradiation unit 8 is mounted on the side wall of the chamber 4A.

[0256] The solidified film removing processing unit 2B includes a rotating chuck 5B that rotates the substrate W while keeping it horizontal, a second moving nozzle 10 that supplies a peeling liquid to the upper surface of the substrate W, a third moving nozzle 11 that supplies a rinsing liquid to the upper surface of the substrate W, and a chamber 4B that houses the rotating chuck 5B, the second moving nozzle 10, and the third moving nozzle 11.

[0257] An entrance / exit 4Ba for loading or unloading the substrate W by the transfer robot CR is formed in the chamber 4B. A shutter unit 4Bb for opening and closing the entrance / exit is provided in the chamber 4B.

[0258] In the substrate processing based on the substrate processing apparatus 1R according to the fourth embodiment, after the substrate W is loaded into the chamber 4A (first chamber) of the solidification film forming processing unit 2A by the transfer robot CR, in the chamber 4A, the Figure 4 shown mixed liquid supply process (step S2) and coating film forming process (step S3) are performed. That is, during the period from the start of the mixed liquid supply process (step S2) to the end of the coating film forming process (step S3), the substrate W is held by the rotary chuck 5A in the chamber 4A (first substrate holding process).

[0259] Then, as Figure 16 shown, the substrate W having the coating film 102 formed on its upper surface is unloaded from the chamber 4A of the solidification film forming processing unit 2A by the transfer robot CR (unloading process). When the substrate W passes through the entrance / exit 4Aa of the chamber 4A, the second polymer in the coating film 102 is cured by the light irradiation unit 8 to form the solidification film 100. That is, the solidification film forming process (step S4) can be performed in the unloading process. The substrate W is loaded into the chamber 4B (loading process) of the solidification film removing processing unit 2B in a state where the solidification film 100 is formed on its upper surface. The transfer robot CR is an example of the transfer unit.

[0260] Moreover, in the chamber 4B, the Figure 4 shown solidification film removing process (step S5), rinsing process (step S6) and rotary drying process (step S7) are performed. That is, during the period from the start of the solidification film removing process (step S5) to the end of the rotary drying process (step S7), the substrate W is held by the rotary chuck 5B in the chamber 4B (second substrate holding process).

[0261] By the fourth embodiment, the same effects as those of the third embodiment are achieved. In addition, by the fourth embodiment, in the configuration where the formation and removal of the solidification film 100 are performed in different chambers 4A and 4B, the solidification film 100 can be formed during the transfer of the substrate W. Therefore, the time required for substrate processing can be shortened.

[0262] Although not shown in Figure 16 , a processing hood 7 (see Figure 2 ) may also be provided in the solidification film forming processing unit 2A and the solidification film removing processing unit 2B.

[0263] <Details of the Dissolved Components>

[0264] Hereinafter, the dissolution components that can be used in the above-described embodiments will be described.

[0265] Hereinafter, "C x～y ", "C x ~C y ", and "C x " and the like indicate the number of carbons in a molecule or substituent. For example, C 1～6 alkyl represents an alkyl chain having 1 or more and 6 or less carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0266] When the polymer has a plurality of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations can be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When representing a polymer or resin by a structural formula, n, m, etc. described together with parentheses indicate the number of repetitions.

[0267] The dissolution component is a crack promoting component. The crack promoting component contains a hydrocarbon, and further contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). When the crack promoting component is a polymer, one kind of structural unit contains a hydrocarbon in each unit, and further has a hydroxyl group and / or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and ketene, and carboxylic acid is preferred.

[0268] It is not intended to limit the scope of the claims, and without being limited by theory, it is considered that when the coating film is dried to form a solidified film on the substrate and the stripping liquid strips the solidified film, the dissolution component generates a part that becomes the beginning of stripping the solidified film. Therefore, the dissolution component is preferably a substance having a higher solubility in the stripping liquid than the low-solubility component. As a form in which a ketone is included as the carbonyl group in the crack promoting component, a cyclic hydrocarbon can be cited. As a specific example, 1,2-cyclohexanedione and 1,3-cyclohexanedione can be cited.

[0269] In a more specific embodiment, the dissolution component is represented by at least any one of the following (A), (B), and (C).

[0270] (A) is a compound containing 1 to 6 (preferably 1 to 4) of the following chemical formula 3 as a structural unit, and each structural unit is connected by a linking group (linking group L1). Here, the linking group L1 can be a single bond or C 1～6 alkylene. The above-mentioned C 1～6 alkylene connects the structural units as a linking group, and is not limited to a divalent group. It is preferably 2 to 4 valent. The above-mentioned C 1～6 alkylene can be either straight-chain or branched-chain.

[0271] [Chemical Formula 3]

[0272] Chemical Formula 3

[0273]

[0274] Cy1 is a hydrocarbon ring having 5 to 30 carbon atoms, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. As a preferred embodiment, the linking group L1 links a plurality of Cy1s.

[0275] Each R1 is independently a C 1～5 alkyl group, preferably methyl, ethyl, propyl, or butyl. The aforementioned C 1～5 alkyl group can be either straight-chain or branched-chain.

[0276] n b1 is 1, 2 or 3, preferably 1 or 2, more preferably 1. n b1 ’ is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0277] The following Chemical Formula 4 is a chemical formula representing the structural unit described in Chemical Formula 3 with the linking group L9. The linking group L9 is preferably a single bond, methylene, ethylene, or propylene.

[0278] [Chemical Formula 4]

[0279] Chemical Formula 4

[0280]

[0281] It is not intended to limit the scope of the claims. As a preferred example of (A), 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, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane can be cited. They can be obtained by polymerization or condensation.

[0282] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following Chemical Formula 5 will be described. For this compound, in (A), it has 3 structural units of Chemical Formula 3, and the structural units are linked by the linking group L1 (methylene). n b1 = n b1 ’ = 1, and R1 is methyl.

[0283] [Chemical Formula 5]

[0284] Chemical Formula 5

[0285]

[0286] (B) is represented by the following Chemical Formula 6.

[0287] [Chemical Formula 6]

[0288] Chemical Formula 6

[0289]

[0290] R 21 、R 22 、R 23 、and R 24 are each independently hydrogen or an alkyl group of C 1～5 , preferably hydrogen, methyl, ethyl, tert-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and still more preferably methyl or ethyl.

[0291] Linking group L 21 and linking group L 22 are each independently an alkylene group of C 1～20 , a cycloalkylene group of C 1～20 , an alkenylene group of C 2～4 , an alkynylene group of C 2～4 , or an arylene group of C6 to 20 . These groups may be substituted with an alkyl group or a hydroxyl group of C1-5. Here, the alkenylene group means a divalent hydrocarbon having one or more double bonds, and the alkynylene group means a divalent hydrocarbon group having one or more triple bonds. Linking group L 21 and linking group L 22 are preferably an alkylene group of C2-4, an ethynylene group (C2 alkynylene group), or a phenylene group, more preferably an alkylene group of C2-4 or an ethynylene group, and still more preferably an ethynylene group.

[0292] n b2 is 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0293] It is not intended to limit the scope of the claims. As preferred examples of (B), 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol can be mentioned. As other examples, 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol can be mentioned as preferred examples of (B).

[0294] (C) is a polymer containing a structural unit represented by the following Chemical Formula 7 and having a weight-average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, more preferably 700 to 3,000.

[0295] [Chemical Formula 7]

[0296] Chemical Formula 7

[0297]

[0298] Here, R 25 is -H, -CH3, or -COOH, preferably -H or -COOH. It is also allowed that one (C) polymer contains two or more kinds of structural units each represented by Chemical Formula 7.

[0299] Without intending to limit the scope of the claims, as a preferred example of the (C) polymer, polymers of acrylic acid, maleic acid, or a combination thereof can be cited. Polyacrylic acid and maleic acid-acrylic acid copolymer are further preferred examples.

[0300] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0301] As an example, a maleic acid-acrylic acid copolymer represented by the following Chemical Formula 8 is described. This copolymer is included in (C), has two kinds of structural units represented by Chemical Formula 7, and in one structural unit, R 25 is -H, and in the other structural unit, R 25 is -COOH.

[0302] [Chemical Formula 8]

[0303] Chemical Formula 8

[0304]

[0305] It goes without saying that as the dissolution component, one kind of the above preferred examples or a combination containing two or more kinds can be included. For example, the dissolution component can include both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0306] The molecular weight of the dissolution component can be 80 to 10,000. The molecular weight of the dissolution component is preferably 90 to 5,000, more preferably 100 to 3,000. When the dissolution component is a resin, a polymer, or a polymer, the molecular weight is represented by the weight-average molecular weight (Mw).

[0307] The dissolution component can be synthesized, purchased, or obtained. As suppliers, Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai can be cited.

[0308] <Other Embodiments>

[0309] The present invention is not limited to the embodiments described above and can be implemented in other ways.

[0310] The rotary chuck 5 is not limited to a clamping chuck that brings a plurality of chuck pins 20 into contact with the circumferential end surface of the substrate W, and may also be a vacuum chuck that holds the substrate W horizontally by adsorbing the lower surface of the substrate W to the upper surface of the rotary base 21.

[0311] In addition, in the above-described embodiments, each liquid (mixed liquid, first polymer liquid, second polymer liquid, stripping liquid, rinsing liquid) is configured to be ejected from the moving nozzle, but each substrate processing apparatus 1, 1P, 1Q, 1R may also be configured to eject the liquid from a fixed nozzle whose position relative to the substrate W is fixed.

[0312] In the above-described embodiments, the coating film 102 is heated by the heater unit 6. However, the coating film 102 can also be heated, for example, by supplying warm water to the lower surface of the substrate W.

[0313] In the above-described embodiments, after the rinsing step, a rotary drying step is performed. However, after cleaning the upper surface of the substrate W with a rinsing liquid such as pure water in the rinsing step, an organic solvent such as IPA can be used instead of the rinsing liquid, and then the rotary drying step can be performed.

[0314] In addition, in the above-described embodiments, the coating film 102 is formed from the liquid film 101 of the mixed liquid. However, different from the above-described embodiments, a coating film 102 can also be formed on the upper surface of the substrate W by coating a high-viscosity coating agent containing the first polymer and the second polymer on the upper surface of the substrate W. The coating agent may contain a solvent, but in the case where the first polymer and the second polymer have a flowability that allows coating, the coating agent may not contain a solvent.

[0315] In this specification, when using "~" or "-" to represent a numerical range, unless otherwise specified, they include the endpoints on both sides and the units are common.

[0316] The embodiments of the invention have been described in detail, but they are merely specific examples used to illustrate the technical content of the present invention. The present invention should not be construed as being limited by these specific examples, and the scope of the present invention is only limited by the appended claims.

[0317] This application corresponds to Japanese Patent Application No. 2020-126869 filed with the Japan Patent Office on July 27, 2020, and the entire contents disclosed in this application are incorporated herein by reference.

[0318] Description of Reference Numerals

[0319] 1: Substrate processing apparatus

[0320] 1P: Substrate processing apparatus

[0321] 1Q: Substrate processing apparatus

[0322] 1R: Substrate processing apparatus

[0323] 3: Controller

[0324] 6: Heater unit (solid formation unit)

[0325] 8: Light irradiation unit (solid formation unit)

[0326] 9: First moving nozzle (coating film formation unit)

[0327] 9P: First moving nozzle (coating film formation unit)

[0328] 10: Second moving nozzle (stripping liquid supply unit)

[0329] 12: Fourth moving nozzle (coating film formation unit)

[0330] 23: Rotation motor (coating film formation unit)

[0331] 100: Solidified film

[0332] 102: Coating film

[0333] 104: Etching residue

[0334] 150: Surface layer part

[0335] 151: Upper surface (surface)

[0336] W: Substrate

Claims

1. A substrate processing method, comprising: An etching step of forming a semi-solid coating film containing a first polymer having an etching function and a second polymer having a solid forming function on the surface of the substrate, and etching the surface layer portion of the substrate through the first polymer on the substrate; And An etching stop step of curing the second polymer in the coating film by solid formation treatment to convert the coating film into a solid film, thereby stopping the etching of the surface layer portion of the substrate.

2. The substrate processing method according to claim 1, wherein, The etching step includes: a liquid film etching step of forming a liquid film containing a mixture of the first polymer and the second polymer, and etching the surface layer portion of the substrate through the first polymer in the liquid film of the mixture; and a coating film etching step of forming the coating film from the liquid film of the mixture, and etching the surface layer portion of the substrate through the first polymer in the coating film.

3. The substrate processing method according to claim 2, wherein, The liquid film etching step includes: a mixed liquid film forming step of spraying the mixed liquid from a nozzle facing the surface of the substrate onto the surface of the substrate to form a liquid film of the mixed liquid.

4. The substrate processing method according to claim 2, wherein, The liquid film etching step includes: a mixed liquid film forming step of supplying a first polymer liquid containing the first polymer and a second polymer liquid containing the second polymer to the surface of the substrate to form a liquid film of a mixture of the first polymer liquid and the second polymer liquid on the surface of the substrate.

5. The substrate processing method according to claim 4, wherein, The mixed liquid film forming step includes a step of simultaneously performing the supply of the first polymer liquid to the surface of the substrate and the supply of the second polymer liquid to the surface of the substrate.

6. The substrate processing method according to claim 4, wherein, The mixed liquid film forming step includes: a first polymer liquid supply step of supplying the first polymer liquid to the surface of the substrate; and a second polymer liquid supply step of supplying the second polymer liquid to the surface of the substrate after the first polymer liquid supply step to form a liquid film of the mixture on the surface of the substrate.

7. The substrate processing method according to any one of claims 1 to 6, wherein, The solid formation treatment includes a heat treatment for the coating film, The second polymer is a thermosetting resin.

8. The substrate processing method according to any one of claims 1 to 6, wherein, The solid formation treatment includes a light irradiation treatment for the coating film, The second polymer is a photocurable resin.

9. The substrate processing method according to any one of claims 1 to 6, further comprising: A solid film removing step of supplying a stripping liquid to the surface of the solid film, thereby peeling the solid film from the surface of the substrate to remove the solid film from the surface of the substrate.

10. The substrate processing method according to claim 9, wherein, In the etching stop step, a solid film containing a dissolution component having a higher solubility in the stripping liquid than the second polymer is formed, The dissolution component in the solid film is dissolved by the stripping liquid supplied in the solid film removing step.

11. The substrate processing method according to claim 9, wherein In the etching step, the surface layer portion of the substrate is etched to form an etching residue, The etching residue is held by the solid film formed in the etching stop step, The solid film removing step includes a step of removing the etching residue together with the solid film while the etching residue is held by the solid film.

12. Substrate processing apparatus, comprising: A coating film forming unit that forms a coating film containing a first polymer having an etching function and a second polymer having a solid forming function on the surface of a substrate; A solid forming unit that performs a solid forming process of solidifying or curing the second polymer in the coating film on the surface of the substrate to form a solidified film; A stripping liquid supply unit that supplies a stripping liquid for stripping the solidified film from the surface of the substrate to the surface of the substrate; And A controller that controls the coating film forming unit, the solid forming unit, and the stripping liquid supply unit; The controller is programmed to execute the following processes: an etching process of forming a coating film on the surface of a substrate by the coating film forming unit and etching the surface layer portion of the substrate by the first polymer in the coating film; an etching stop process of converting the coating film into a solidified film by curing the second polymer in the coating film by the solid forming process based on the solid forming unit, thereby stopping the etching of the surface layer portion of the substrate; and a solidified film removal process of removing the solidified film from the surface of the substrate by supplying a stripping liquid to the surface of the solidified film.

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