Substrate Processing Apparatus and Substrate Processing Method

Abstract

To provide a novel substrate processing apparatus and substrate processing method capable of efficiently removing an object to be removed existing on the surface of a substrate.SOLUTION: A polymer film 100 including a photoreactive compound 103 whose structure is changed by light irradiation and a polymer component 101 is formed on the main surface of a substrate W held at the holding position. Light is emitted from a light emitting member 8 toward the main surface of the substrate W on which the polymer film 100 is formed. A polymer film removing process for removing the polymer film 100 is performed on the main surface of the substrate W.SELECTED DRAWING: Figure 8B

Description

Technical Field

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

Background Art

[0002] A technique for removing objects to be removed such as particles from the main surface of a substrate is required. For example, Patent Document 1 below discloses a substrate processing method in which a top coat liquid is supplied to a substrate to form a top coat film by volatilizing volatile components from the top coat liquid, and the top coat film is dissolved in a removal liquid and removed from the substrate. When the top coat film is formed from the top coat liquid, particles are separated from the substrate due to volume shrinkage that occurs.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] One object of the present invention is to provide a novel substrate processing apparatus and a substrate processing method capable of efficiently removing objects to be removed present on the surface of a substrate.

Means for Solving the Problems

[0005] One embodiment of the present invention provides a substrate processing apparatus including a substrate holding member that holds a substrate at a holding position, a polymer film forming member that forms a polymer film containing a photoreactive compound and a polymer component whose structure changes upon light irradiation on a main surface of the substrate held at the holding position, a light emitting member that emits light toward the main surface of the substrate held at the holding position, and a polymer film removing member that performs a polymer film removing process for removing the polymer film from the main surface of the substrate held at the holding position.

[0006] According to this Configuration the structure of the photoreactive compound contained in the polymer film on the main surface of the substrate changes upon light irradiation. Therefore, the polymer film is deformed by the light irradiation, and at least a part of the polymer film is separated from the main surface of the substrate. By separating the polymer film from the main surface of the substrate, the object to be removed held by the polymer film can be separated from the main surface of the substrate. By removing the polymer film from the main surface of the substrate in a state where the object to be removed is separated from the main surface of the substrate together with the polymer film, the object to be removed can be effectively removed from the main surface of the substrate.

[0007] In one embodiment of the present invention, the photoreactive compound includes at least one of a diallyl ethene-based compound and an azobenzene-based compound.

[0008] The diallyl ethene-based compound and the azobenzene-based compound change their structures upon light irradiation. Due to the structural change of the components in the polymer film, the polymer film is deformed, and at least a part of the polymer film is separated from the main surface of the substrate. By the light irradiation, the polymer film, for example, bends. The photoreactive compound may contain a diallyl ethene compound. The light emitting member may emit light including ultraviolet light toward the main surface of the substrate held at the holding position to isomerize the diallyl ethene compound contained in the photoreactive compound from an open-ring form to a closed-ring form.

[0009] In one embodiment of the present invention, the polymer film removing member includes a stripping liquid supply member that performs a stripping liquid supply process of supplying a stripping liquid for stripping the polymer film to the main surface of the substrate as the polymer film removing process. Therefore, the stripping of the polymer film is promoted by the stripping liquid, and the object to be removed can be effectively removed from the main surface of the substrate.

[0010] In one embodiment of the present invention, the polymer film forming member forms the polymer film further containing a highly soluble substance having a higher solubility in the release liquid than the polymer component. Therefore, while dissolving the highly soluble substance with the release liquid, the polymer film can be maintained. Accordingly, while holding the object to be removed with the polymer component, the release liquid can be made to act on the interface between the polymer film and the main surface of the substrate. As a result, while quickly peeling the polymer film from the main surface of the substrate, the object to be removed can be efficiently removed from the main surface of the substrate together with the polymer film.

[0011] In one embodiment of the present invention, the polymer film removing member includes a suction member that performs a suction removing process of sucking the polymer film to remove the polymer film from the main surface of the substrate as the polymer film removing process. Since at least a part of the polymer film has been separated from the main surface of the substrate, the polymer film is more easily peeled from the main surface of the substrate than before the light irradiation. Therefore, the polymer film can be removed from the main surface of the substrate by suction.

[0012] Moreover, if the polymer film can be removed by suction without supplying the release liquid to the main surface of the substrate, the labor of drying the main surface of the substrate can be saved.

[0013] Another embodiment of the present invention provides a substrate processing method including a polymer film forming step of forming a polymer film containing a photoreactive compound whose structure changes by light irradiation and a polymer component on the main surface of a substrate, a light irradiation step of irradiating light onto the polymer film on the main surface of the substrate, and a polymer film removing step of removing the polymer film from the main surface of the substrate after the light irradiation step. According to this substrate processing method, the same effects as those of the above-described substrate processing apparatus can be obtained.

[0014] In another embodiment of the present invention, the photoreactive compound may contain at least one of a diallylethene-based compound and an azobenzene-based compound. The photoreactive compound may contain a diallyl ethene compound. The light irradiation step may include a step of irradiating the polymer film on the main surface of the substrate with light including ultraviolet light to isomerize the diallyl ethene compound contained in the photoreactive compound from an open-ring form to a closed-ring form.

[0015] In another embodiment of the present invention, the polymer film removing step may include a stripping liquid supplying step of supplying a stripping liquid for stripping the polymer film to the polymer film on the main surface of the substrate.

[0016] In another embodiment of the present invention, the polymer film forming step may include a step of forming the polymer film further containing a highly soluble substance having a higher solubility in the stripping liquid than the polymer component.

[0017] In another embodiment of the present invention, the polymer film removing step may include a suction removing step of sucking the polymer film on the main surface of the substrate to remove the polymer film from the main surface of the substrate.

[0018] In another embodiment of the present invention, the polymer film removing step may include a step of pulling the polymer film away from the main surface of the substrate by bending the polymer film by a structural change of the photoreactive compound.

Brief Description of the Drawings

[0019]

Figure 1

Figure 2

Figure 3

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Figure 7

Figure 8A

Figure 8B

Figure 8C

Figure 8D

Figure 9

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Figure 14A

Figure 14B

Figure 14C

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Figure 16

Figure 17

[0020] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

[0021] <Configuration of Substrate Processing Apparatus According to First Embodiment> FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to the first embodiment of the present invention.

[0022] The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates W one by one. In this embodiment, the substrate W has a circular shape. The substrate W has a pair of main surfaces. The substrate processing apparatus 1 includes a plurality of processing units 2 that process the substrate W, a load port LP on which a carrier C that accommodates a plurality of substrates W to be processed by the processing units 2 is placed, transfer robots IR and CR that transfer the substrate W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.

[0023] The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing units 2. The transfer robots IR and CR are arranged on a transfer path TR that extends from a plurality of load ports LP toward a plurality of processing units 2.

[0024] The plurality of processing units 2 have, for example, a similar configuration. The plurality of processing units 2 form four processing towers TW respectively arranged at four horizontally separated positions. Each processing tower TW includes a plurality (for example, three) of processing units 2 stacked in the vertical direction. The four processing towers TW are arranged in pairs on both sides of the transport path TR.

[0025] The processing unit 2 is a wet processing unit 2W that processes the substrate W with a processing liquid. Examples of the processing liquid supplied toward the substrate W in the wet processing unit 2W include a polymer-containing liquid, a stripping liquid, and a residue dissolving liquid.

[0026] FIG. 2 is a schematic diagram for explaining the configuration of the wet processing unit 2W.

[0027] The wet processing unit 2W includes a spin chuck 5 that rotates the substrate W around the rotation axis A1 while holding the substrate W at a predetermined holding position, a light emitting member 8 that emits light toward the upper surface of the substrate W held by the spin chuck 5, a plurality of processing liquid nozzles (a polymer-containing liquid nozzle 9, a stripping liquid nozzle 10, and a residue dissolving liquid nozzle 11) that discharge the processing liquid toward the upper surface (upper main surface) of the substrate W held by the spin chuck 5, a processing cup 7 that receives the liquid scattered from the substrate W held by the spin chuck 5, and a chamber 4 that houses the spin chuck 5, the processing cup 7, the light emitting member 8, and the plurality of processing liquid nozzles.

[0028] The rotation axis A1 is a central axis passing through the central portion of the upper surface of the substrate W. The holding position is a position where the rotation axis A1 passes through the central portion of the upper surface of the substrate W and the upper surface of the substrate W is horizontal.

[0029] Chamber 4 includes a chamber body 4a, an opening 4b provided in the chamber body 4a, and a shutter unit 4c that opens and closes the opening 4b. With the shutter unit 4c open at the opening 4b, the transfer robot CR can carry the substrate W into the chamber body 4a or carry the substrate W out from the chamber body 4a. The chamber body 4a and the shutter unit 4c have light-shielding properties, and when the shutter unit 4c closes the opening 4b, light from outside the chamber 4 is blocked.

[0030] The spin chuck 5 is surrounded by the processing cup 7. The spin chuck 5 includes a spin base 21 having a disk shape along the horizontal direction, a plurality of chuck pins 20 that grip the substrate W above the spin base 21 and grip the peripheral edge of the substrate W above the spin base 21, a rotating shaft 22 connected to the spin base 21 and extending in the vertical direction, and a rotation drive mechanism 23 that rotates the rotating shaft 22 around its central axis (rotation axis A1).

[0031] The plurality of chuck pins 20 are arranged on the upper surface of the spin base 21 at intervals in the circumferential direction of the spin base 21. The rotation drive mechanism 23 includes an actuator such as an electric motor. The rotation drive mechanism 23 rotates the rotating shaft 22, causing the spin base 21 and the plurality of chuck pins 20 to rotate around the rotation axis A1. Thereby, the substrate W is rotated around the rotation axis A1 together with the spin base 21 and the plurality of chuck pins 20.

[0032] The plurality of chuck pins 20 are movable between a closed position where they contact the peripheral edge of the substrate W to grip the substrate W and an open position where the grip on the substrate W is released. The plurality of chuck pins 20 are moved by an opening and closing mechanism (not shown).

[0033] When the plurality of chuck pins 20 are in the closed position, they grip the peripheral portion of the substrate W and hold the substrate W in the holding position. When the plurality of chuck pins 20 are in the open position, while releasing the grip on the substrate W, they support the peripheral portion of the substrate W from below. The opening and closing mechanism includes, for example, a link mechanism and an actuator that applies a driving force to the link mechanism.

[0034] The plurality of processing liquid nozzles include a polymer-containing liquid nozzle 9 that discharges a continuous flow of a polymer-containing liquid toward the upper surface of the substrate W held by the spin chuck 5, a stripping liquid nozzle 10 that discharges a continuous flow of a stripping liquid toward the upper surface of the substrate W held by the spin chuck 5, and a residue dissolving liquid nozzle 11 that discharges a continuous flow of a residue dissolving liquid toward the upper surface of the substrate W held by the spin chuck 5.

[0035] The polymer-containing liquid discharged from the polymer-containing liquid nozzle 9 contains a solute and a solvent. The solute of the polymer-containing liquid includes a photoreactive compound whose structure changes upon light irradiation, a polymer component that forms a solid or semi-solid film (polymer film) when at least a part of the solvent evaporates (volatilizes), and a highly soluble substance that has a higher solubility in the stripping liquid than the polymer component.

[0036] The polymer-containing liquid contains a component (polymer component described later) that forms a solid or semi-solid film (polymer film). The semi-solid state is a state in which a solid component and a liquid component are mixed. The solid state is a state in which no liquid component is contained and it is composed only of the solid component. The polymer film with the solvent remaining is semi-solid, and the polymer film with the solvent completely disappeared is solid.

[0037] Since the polymer component has a lower solubility in the stripping liquid described later than the highly soluble substance, it is also referred to as a low solubility substance. The polymer component is, for example, novolak. The highly soluble substance is, for example, 2,2-bis(4-hydroxyphenyl)propane. Details of the polymer component and the highly soluble substance will be described later.

[0038] The photoreactive compound changes from the first structure to the second structure by light having a first wavelength, and changes from the second structure to the first structure by light having a second wavelength different from the first wavelength. The photoreactive compound includes, for example, at least one of diallylethene compounds and azobenzene compounds.

[0039] As the diallylethene compound, for example, the compounds shown in the following Chemical Formulas 1 to 6 can be used.

[0040]

Chemical Formula

[0041]

Chemical Formula

[0042]

Chemical Formula

[0043]

Chemical Formula

[0044]

Chemical Formula

[0045]

Chemical Formula

[0046] As shown in Figure 3, the structure of the diallylethene compound changes by light irradiation. 。WellMore specifically, when a diallyl ethene compound is irradiated with light having a wavelength (first wavelength) of 200 nm or more and 380 nm or less, it is isomerized from an open-ring form (first structure) to a closed-ring form (second structure). When a diallyl ethene compound is irradiated with light having a wavelength (second wavelength) of 400 nm or more and 760 nm or less, it is isomerized from a closed-ring form (second structure) to an open-ring form (first structure). That is, a diallyl ethene compound is isomerized from an open-ring form to a closed-ring form by irradiation with ultraviolet light, and is isomerized from a closed-ring form to an open-ring form by irradiation with visible light. When the diallyl ethene compound contained in the polymer film is isomerized from an open-ring form to a closed-ring form, the polymer film is deformed so as to curve.

[0047] As the azobenzene compound, for example, the compounds shown in Chemical Formula 7 and Chemical Formula 8 below can be used.

[0048] [Chemical formula]

[0049] [Chemical formula]

[0050] As shown in FIG. 4, the structure of the azobenzene compound also changes by light irradiation. More specifically, when an azobenzene compound is irradiated with light having a wavelength (first wavelength) of 200 nm or more and 380 nm or less, it is isomerized from a trans form (first structure) to a cis form (second structure). When an azobenzene compound is irradiated with light having a wavelength (second wavelength) of 400 nm or more and 760 nm or less, it is isomerized from a cis form (second structure) to a trans form (first structure). That is, an azobenzene compound is isomerized from a trans form to a cis form by irradiation with ultraviolet light, and is isomerized from a cis form to a trans form by irradiation with visible light. When the azobenzene compound contained in the polymer film is isomerized from a trans form to a cis form, the polymer film is deformed so as to curve.

[0051] The solvent contained in the polymer-containing liquid may be any substance that is liquid at room temperature (for example, a temperature of 5°C or higher and 25°C or lower, also referred to as room temperature) and can dissolve the solute. The polymer-containing liquid is, for example, an organic solvent such as IPA (isopropanol). The organic solvent contained in the polymer-containing liquid includes, for example, at least one of aliphatic hydrocarbons, aromatic hydrocarbons, esters, alcohols, and ethers.

[0052] Specifically, the organic solvents are alcohols such as 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. Also, the solvent may be a mixture of an organic solvent and water such as DIW (deionized water).

[0053] A polymer-containing liquid pipe 40 for guiding the polymer-containing liquid to the polymer-containing liquid nozzle 9 is connected to the polymer-containing liquid nozzle 9. A polymer-containing liquid valve 50 for opening and closing the flow path in the polymer-containing liquid pipe 40 is provided in the polymer-containing liquid pipe 40. That the valve is provided in the pipe may mean that the valve is interposed in the pipe. When the polymer-containing liquid valve 50 is opened, the polymer-containing liquid is discharged from the polymer-containing liquid nozzle 9.

[0054] The stripping liquid discharged from the stripping liquid nozzle 10 is a liquid for stripping the polymer film and removing it from the main surface of the substrate W. The stripping liquid is, for example, aqueous ammonia, but may be an alkaline aqueous solution (alkaline liquid) other than aqueous ammonia. Specific examples of alkaline aqueous solutions other than aqueous ammonia include aqueous TMAH (tetramethylammonium hydroxide) solution, aqueous choline solution, and any combination thereof. The stripping liquid may be pure water (preferably DIW), or may be a neutral or acidic aqueous solution (non-alkaline aqueous solution).

[0055] A stripping liquid pipe 41 for guiding the stripping liquid to the stripping liquid nozzle 10 is connected to the stripping liquid nozzle 10. A stripping liquid valve 51 for opening and closing the flow path in the stripping liquid pipe 41 is provided in the stripping liquid pipe 41. When the stripping liquid valve 51 is opened, the stripping liquid is discharged from the stripping liquid nozzle 10.

[0056] The residue dissolving liquid discharged from the residue dissolving liquid nozzle 11 is a liquid for dissolving the residue remaining on the main surface of the substrate W after the polymer film is stripped by the stripping liquid and removed from the main surface of the substrate W. The residue dissolving liquid is, for example, an organic solvent such as IPA. As the organic solvent, those listed as the solvent contained in the polymer-containing liquid can be used.

[0057] A residue dissolving liquid pipe 42 for guiding the residue dissolving liquid to the residue dissolving liquid nozzle 11 is connected to the residue dissolving liquid nozzle 11. A residue dissolving liquid valve 52 for opening and closing the flow path in the residue dissolving liquid pipe 42 is provided in the residue dissolving liquid pipe 42. When the residue dissolving liquid valve 52 is opened, the residue dissolving liquid is discharged from the residue dissolving liquid nozzle 11.

[0058] The plurality of processing liquid nozzles are each movable by a plurality of nozzle moving mechanisms 35, 36, 37. The plurality of nozzle moving mechanisms 35, 36, 37 can move the corresponding processing liquid nozzle at least in the horizontal direction. Each processing liquid nozzle is movable between a center position facing the center of the upper surface of the substrate W and a retracted position located outside the processing cup 7 in a plan view. Each nozzle moving mechanism 35, 36, 37 includes a support arm (not shown) for supporting the corresponding processing liquid nozzle and a drive mechanism (not shown) for driving the support arm. The drive mechanism includes, for example, an actuator such as a motor.

[0059] The configuration of the processing cup 7 is not particularly limited. The processing cup 7 includes, for example, a plurality (two in FIG. 2) of guards 71 for receiving the processing liquid scattered outward from the substrate W held by the spin chuck 5, a plurality (two in FIG. 2) of cups 72 for receiving the processing liquid guided downward by the plurality of guards 71, and a cylindrical outer wall member 73 surrounding the plurality of guards 71 and the plurality of cups 72.

[0060] Each guard 71 has a cylindrical form surrounding the spin chuck 5 in a plan view. The upper end portion of each guard 71 is inclined toward the inside of the guard 71. Each cup 72 has a form of an upwardly open annular groove. The plurality of guards 71 and the plurality of cups 72 are coaxially arranged.

[0061] The plurality of guards 71 are individually lifted and lowered by a guard lifting and lowering drive mechanism (not shown). The guard lifting and lowering drive mechanism includes, for example, a plurality of actuators for individually lifting and lowering the plurality of guards 71. The plurality of actuators include at least one of an electric motor and an air cylinder.

[0062] The light-emitting member 8 includes an opposing member 6 that faces the upper surface (the upper side surface) of the substrate W held by the spin chuck 5 from above, and a plurality of lamps 80 as light sources attached to the opposing surface 6a.

[0063] The opposing member 6 is formed in a disc shape having a diameter equal to or larger than that of the substrate W. The opposing surface 6a is arranged substantially along a horizontal plane above the spin chuck 5. A rotation shaft 60 is fixed to the side of the opposing member 6 opposite to the opposing surface 6a. The opposing member 6 blocks the atmosphere in the space between the opposing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the opposing member 6 is also referred to as a shielding plate.

[0064] The plurality of lamps 80 are arranged at equal intervals over the entire area of the opposing surface 6a. A power supply unit 85 configured to energize or stop energization to the plurality of lamps 80 is connected to the plurality of lamps 80. The lamp 80 emits light when energized. The light emitted from each lamp 80 includes, for example, infrared rays, ultraviolet rays, visible light, etc. The lamp 80 is, for example, an excimer lamp, a xenon lamp, a mercury lamp, a deuterium lamp, an LED lamp, etc. The light emitted from the lamp 80 preferably has a wavelength of 200 nm or more and 760 nm or less.

[0065] The opposing member 6 is moved in the vertical direction by an elevating mechanism 61. The elevating mechanism 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) that supports the rotation shaft 60, and an electric motor (not shown) that applies a driving force to the ball screw mechanism. The elevating mechanism 61 is also referred to as an opposing member lifter (shielding plate lifter). The elevating mechanism 61 moves the plurality of lamps 80 in the vertical direction together with the opposing member 6. The elevating mechanism 61 is an example of a lamp elevating unit (lamp lifter).

[0066] FIG. 5 is a block diagram for explaining the electrical configuration of the substrate processing apparatus 1.

[0067] The controller 3 includes a microcomputer and controls a controlled object provided in the substrate processing apparatus 1 according to a predetermined control program.

[0068] Specifically, the controller 3 includes a processor 3A (CPU) and a memory 3B in which a control program is stored. The controller 3 is configured to execute various controls for substrate processing by the processor 3A executing the control program. In particular, the controller 3 is programmed to control the transfer robots IR, CR, the rotation drive mechanism 23, the nozzle movement mechanisms 35, 36, 37, the energization unit 85, the lifting mechanism 61, the polymer-containing liquid valve 50, the stripping liquid valve 51, the residue dissolving liquid valve 52, and the like.

[0069] Also, although typical members are illustrated in FIG. 5, it does not mean that members not illustrated are not controlled by the controller 3. The controller 3 can appropriately control each member provided in the substrate processing apparatus 1. In FIG. 5, members described in the modification examples and the second embodiment described later are also shown together, and these members are also controlled by the controller 3.

[0070] Each step shown in FIG. 6 described later is executed by the controller 3 controlling each member provided in the substrate processing apparatus 1. In other words, the controller 3 is programmed to execute each step shown in FIG. 6 described later.

[0071] <First Substrate Processing> FIG. 6 is a flowchart for explaining the first substrate processing executed by the substrate processing apparatus 1. FIG. 7 is a schematic diagram for explaining the state of the upper surface of the substrate W during the first substrate processing.

[0072] In the first substrate processing by the substrate processing apparatus 1, as shown in FIG. 6, a polymer-containing liquid supply step (step S1), a polymer film formation step (step S2), a heating step (step S3), a stripping liquid supply step (step S4), a residue dissolution step (step S5), and a spin drying step (step S6) are executed. Hereinafter, with reference mainly to FIGS. 2 and 6, the details of the first substrate processing will be described. FIG. 7 will be referred to as appropriate.

[0073] First, the unprocessed substrate W is carried from the carrier C into the wet processing unit 2W by the transfer robot CR (see FIG. 1) and passed to the spin chuck 5 (loading step). Thereby, the substrate W is held at the holding position by the spin chuck 5 (substrate holding step). The substrate W is rotated around the rotation axis A1 while being held by the spin chuck 5 (substrate rotation step). The substrate W continues to be held by the spin chuck 5 until the spin drying step (step S6) is completed.

[0074] After the substrate W is held by the spin chuck 5, a polymer-containing liquid supply step (step S1) of supplying a polymer-containing liquid to the upper surface of the substrate W is executed. Specifically, the polymer-containing liquid nozzle 9 is disposed at the processing position. The processing position is, for example, the central position. In the first substrate processing, unless otherwise specified, the processing positions of the following respective processing liquid nozzles are also the central positions.

[0075] With the polymer-containing liquid nozzle 9 at the processing position, the polymer-containing liquid valve 50 is opened. Thereby, as shown in FIG. 7(a), the polymer-containing liquid is discharged from the polymer-containing liquid nozzle 9, and the polymer-containing liquid lands on the upper surface of the substrate W. The polymer-containing liquid that has landed on the upper surface of the substrate W spreads over the upper surface of the substrate W and is spread over the entire upper surface of the substrate W (coating step). That is, the polymer-containing liquid is supplied to the upper surface of the substrate W. The polymer-containing liquid is supplied to the upper surface of the substrate W, for example, at 0.06 L / min for 4 seconds. While the polymer-containing liquid is being supplied to the upper surface of the substrate W, the substrate W is rotated at a rotation speed of, for example, 0 rpm or more and 1500 rpm or less.

[0076] Next, in a state where the supply of the polymer-containing liquid to the upper surface of the substrate W is stopped, a polymer film forming step (step S2) of forming a polymer film 100 on the upper surface of the substrate W is executed by rotating the substrate W.

[0077] Specifically, after the polymer-containing liquid adheres at least to the central portion of the upper surface of the substrate W, the polymer-containing liquid valve 50 is closed. As a result, the discharge of the polymer-containing liquid from the polymer-containing liquid nozzle 9 is stopped, and the supply of a new polymer-containing liquid to the upper surface of the substrate W is stopped. As at least a part of the solvent evaporates from the polymer-containing liquid adhering to the upper surface of the substrate W after the supply of the polymer-containing liquid is stopped, a polymer film 100 is formed on the upper surface of the substrate W as shown in FIG. 7(b). The polymer-containing liquid nozzle 9 is an example of a polymer film forming member that forms the polymer film 100 on the upper surface of the substrate W.

[0078] Note that the rotation of the substrate W continues even after the polymer-containing liquid valve 50 is closed. After the polymer-containing liquid valve 50 is closed, the substrate W is rotated, for example, at a rotation speed of 0 rpm or more and 2500 rpm or less for 60 seconds. The centrifugal force caused by the rotation of the substrate W acts not only on the polymer-containing liquid on the substrate W but also on the gas in contact with the polymer-containing liquid on the substrate W. Therefore, due to the action of the centrifugal force, an air flow is formed in which the gas moves from the central side to the peripheral side of the substrate W. By this air flow, the solvent in the gaseous state in contact with the polymer-containing liquid on the substrate W is excluded from the atmosphere in contact with the substrate W. Therefore, the evaporation (volatilization) of the solvent from the polymer-containing liquid on the substrate W is promoted.

[0079] Since the polymer film 100 has a lower solvent content than the polymer-containing liquid, it has a higher viscosity compared to the polymer-containing liquid. Therefore, although the substrate W is rotating, the polymer film 100 does not completely drain from the substrate W and remains on the substrate W.

[0080] Next, a light irradiation step (step S3) of irradiating light onto the polymer film 100 on the upper surface of the substrate W is executed.

[0081] Specifically, the lamp 80 is energized with the light emitting member 8 disposed at a predetermined irradiation position. Thereby, as shown in FIG. 7(c), light is emitted from the light emitting member 8 toward the upper surface of the substrate W, and the light emitted from the light emitting member 8 is irradiated onto the polymer film 100 on the upper surface of the substrate W. Although details will be described later, thereby, the structure of the photoreactive compound contained in the polymer film 100 changes, and at least a part of the polymer film 100 is peeled off from the upper surface of the substrate W. The light irradiation onto the upper surface of the substrate W is performed, for example, for 60 seconds. The rotation speed of the substrate W during the light irradiation is, for example, 0 rpm or more and 2500 rpm or less.

[0082] Next, a stripping liquid supply step (step S4) of supplying a stripping liquid to the upper surface of the substrate W is performed.

[0083] Specifically, the emission of light from the light emitting member 8 is stopped, and then the stripping liquid nozzle 10 is disposed at the processing position. With the stripping liquid nozzle 10 disposed at the processing position, the stripping liquid valve 51 is opened. Thereby, as shown in FIG. 7(d), the stripping liquid is discharged from the stripping liquid nozzle 10 toward the upper surface of the substrate W. The stripping liquid discharged toward the upper surface of the substrate W dissolves the highly soluble substance contained in the polymer film 100 and peels off the polymer film 100. By continuing the discharge of the stripping liquid from the stripping liquid nozzle 10, as shown in FIG. 7(e), the polymer film 100 is removed from the upper surface of the substrate W (polymer film removing step). Thus, the stripping liquid nozzle 10 functions as a stripping liquid supply member that performs a stripping liquid supply process of supplying a stripping liquid to the upper surface of the substrate W. Further, the stripping liquid nozzle 10 is an example of a polymer film removing member that performs a polymer film removing process of removing the polymer film 100 from the upper surface of the substrate W.

[0084] The stripping liquid is supplied to the upper surface of the substrate W, for example, at 2 L / min for 60 seconds. While the stripping liquid is being supplied to the upper surface of the substrate W, the substrate W is rotated, for example, at a rotation speed of 0 rpm or more and 2500 rpm or less.

[0085] Next, a residue dissolving step (step S5) of supplying a residue dissolving liquid to the upper surface of the substrate W is performed.

[0086] Specifically, the stripping liquid valve 51 is closed. Instead, the residue dissolving liquid nozzle 11 is arranged at the processing position and the residue dissolving liquid valve 52 is opened. Thereby, the discharge of the stripping liquid from the stripping liquid nozzle 10 is stopped, and as shown in FIG. 7(f), the residue dissolving liquid is discharged from the residue dissolving liquid nozzle 11 toward the upper surface of the substrate W. The residue removing liquid discharged toward the upper surface of the substrate W dissolves the residue remaining on the upper surface of the substrate W after the polymer film 100 is removed by the stripping liquid. The residue dissolving liquid is supplied to the upper surface of the substrate W, for example, at 1 L / min for 30 seconds. While the residue dissolving liquid is being supplied to the upper surface of the substrate W, the substrate W is rotated at a rotational speed of, for example, 0 rpm or more and 2500 rpm or less.

[0087] Next, a spin-drying step (step S6) of rotating the substrate W at a high speed to dry the upper surface of the substrate W is executed. Specifically, the residue dissolving liquid valve 52 is closed. Thereby, the supply of the residue dissolving liquid to the upper surface of the substrate W is stopped.

[0088] Then, the rotation driving mechanism 23 accelerates the rotation of the substrate W to rotate the substrate W at a high speed. The substrate W is rotated at a spin-drying speed, for example, 1500 rpm. Thereby, a large centrifugal force acts on the residue dissolving liquid on the substrate W, and the residue dissolving liquid on the substrate W is thrown off around the substrate W. Then, the rotation driving mechanism 23 stops the rotation of the substrate W. The transfer robot CR enters the wet processing unit 2W, scoops up the processed substrate W from the spin chuck 5, and carries it out of the wet processing unit 2W (carrying-out step). The substrate W is passed from the transfer robot CR to the transfer robot IR and stored in the carrier C by the transfer robot IR.

[0089] Next, an example of the mechanism by which the polymer film 100 is removed in the first substrate treatment will be described with reference to FIGS. 8A to 8D. It is not necessarily the case that the polymer film 100 is removed from the upper surface of the substrate W based on the mechanism described below. As long as at least a part of the polymer film 100 is separated from the upper surface of the substrate W due to the structural change of the photoreactive compound and finally the polymer film 100 is removed from the upper surface of the substrate W. FIGS. 8A to 8D are schematic diagrams for explaining how the polymer film 100 is removed in the first substrate treatment.

[0090] The polymer film 100 formed in the polymer film forming step (step S2) holds the particles 150 (objects to be removed) adhering to the upper surface of the substrate W as shown in FIG. 8A. The polymer film 100 contains a highly soluble substance 102 (highly soluble solid) in a solid state, a polymer component 101 in a solid state, and a photoreactive compound 103 (photoreactive compound solid) in a solid state.

[0091] Referring to FIG. 8B, in the light irradiation step (step S3), when the polymer film 100 is irradiated with light such as ultraviolet light, the structure of the photoreactive compound 103 in the polymer film 100 changes from the first structure 121 (see FIG. 8A) to the second structure 122, and the polymer film 100 deforms so as to curve. Due to the curvature of the polymer film 100, the polymer film 100 splits, and a plurality of first curved film pieces 131 are formed. The first curved film piece 131 is curved such that both ends in the direction intersecting the thickness direction of the polymer film 100 are separated from the upper surface of the substrate W, for example. That is, the first curved film piece 131 may have an arcuate shape. Due to the curvature of the polymer film 100, at least a part of the polymer film 100 (both ends 131a of the first curved film piece 131) is peeled off from the upper surface of the substrate W (curvature peeling step).

[0092] When the photoreactive compound 103 is a diallyl ethene compound, the first structure 121 is an open-ring form and the second structure 122 is a closed-ring form (see Fig. 3). In Fig. 3, Me means a methyl group. When the photoreactive compound is an azobenzene compound, the first structure 121 is a trans form and the second structure 122 is a cis form (see Fig. 4).

[0093] Referring to Fig. 8C, in the stripping liquid supply step (step S3), the stripping liquid is supplied toward the upper surface of the substrate W. The stripping liquid enters the interface between the polymer film 100 (the first curved film piece 131) and the upper surface of the substrate W through the gap G between the first curved film pieces 131. Thereby, the peeling of the polymer film 100 is promoted. Note that the relationship between the thickness of the liquid film of the stripping liquid and the thickness of the polymer film 100 is not limited to that shown in Fig. 8C.

[0094] Further, when the stripping liquid contacts the polymer film 100 (the first curved film piece 131), the highly soluble substance 102 is selectively dissolved in the stripping liquid. That is, the polymer film 100 is partially dissolved (dissolution step, partial dissolution step). Here, when the solvent of the polymer-containing liquid is miscible with the stripping liquid and an appropriate amount of the solvent remains in the polymer film 100, the stripping liquid can dissolve the highly soluble substance 102 while dissolving in the solvent remaining in the polymer film 100. Therefore, the highly soluble substance 102 can be dissolved rapidly.

[0095] "The highly soluble substance 102 is selectively dissolved" does not mean that only the highly soluble substance 102 is dissolved. "The highly soluble substance 102 is selectively dissolved" means that although the polymer component 101 is also slightly dissolved, most of the highly soluble substance 102 is dissolved.

[0096] Triggered by the selective dissolution of the highly soluble substance 102, cracks 104 are formed starting from the portions where the highly soluble substance 102 is unevenly distributed in the polymer film 100 (crack formation step).

[0097] Referring to FIG. 8D, due to the formation of the crack 104, the first curved film piece 131 further splits, and a plurality of second curved film pieces 132 finer than the first curved film piece 131 are formed. In this way, the polymer film 100 can be peeled off from the upper surface of the substrate W while promoting the splitting of the polymer film 100 by the stripping liquid.

[0098] Then, by continuing to supply the stripping liquid, the polymer film 100 that has become a plurality of second curved film pieces 132 is washed away by the stripping liquid while holding the particles 150. In other words, a plurality of second curved film pieces 132 holding the particles 150 are pushed out of the substrate W and removed from the upper surface of the substrate W (polymer film removal step, object to be removed removal step). Thereby, the upper surface of the substrate W can be cleaned well. Thereafter, a residue removal step (step S5) is executed (see also FIG. 6).

[0099] <Second substrate processing> FIG. 9 is a flowchart for explaining the second substrate processing executed by the substrate processing apparatus 1. FIG. 10 is a schematic diagram for explaining how the polymer film 100 is peeled off in the second substrate processing.

[0100] The main difference between the second substrate processing and the first substrate processing (see FIG. 6) is that the light irradiation step (step S3) and the stripping liquid supply step (step S4) are performed in parallel. Specifically, while irradiating the upper surface of the substrate W in a state where the polymer film 100 is formed with light from the light emitting member 8, the stripping liquid discharged from the stripping liquid nozzle 10 is supplied to the upper surface of the substrate W. The light irradiation does not need to be performed during the entire period of the supply of the stripping liquid, and the light irradiation may be performed during a part of the period of the supply of the stripping liquid.

[0101] The mechanism of the second substrate processing shown in FIG. 10 is different from the mechanism shown in the first substrate processing (see FIGS. 8A to 8D). While deforming the polymer film 100 to be curved by light irradiation, the highly soluble substance 102 can be selectively dissolved by the stripping liquid.

[0102] According to the first embodiment, the structure of the photoreactive compound 103 contained in the polymer film 100 on the upper surface of the substrate W changes upon light irradiation. Therefore, the polymer film 100 is deformed by light irradiation, and at least a part of the polymer film 100 is separated from the upper surface of the substrate W. By separating the polymer film 100 from the upper surface of the substrate W, the particles 150 held by the polymer film 100 can be separated from the upper surface of the substrate W. By removing the polymer film 100 from the upper surface of the substrate W in a state where the particles 150 are separated from the upper surface of the substrate W together with the polymer film 100, the particles 150 can be effectively removed from the upper surface of the substrate W.

[0103] Also, according to the first embodiment, the photoreactive compound 103 contains at least one of a diallylethene-based compound and an azobenzene-based compound. The diallylethene-based compound and the azobenzene-based compound change in structure upon light irradiation. Due to the change in the structure of the components in the polymer film 100, the polymer film 100 is deformed, and at least a part of the polymer film 100 is separated from the upper surface of the substrate W.

[0104] Also, according to the first embodiment, a stripping liquid supply process is executed as the polymer film removal process. Therefore, the stripping liquid promotes the separation of the polymer film 100, and the particles 150 can be effectively removed from the upper surface of the substrate W.

[0105] Also, according to the first embodiment, the polymer film 100 formed on the upper surface of the substrate W contains a highly soluble substance 102 in addition to the polymer component 101 and the photoreactive compound 103. Therefore, while dissolving the highly soluble substance 102 with the stripping liquid, the polymer film 100 can be maintained on the upper surface of the substrate W. Therefore, while holding the particles 150 with the polymer component 101, the stripping liquid can be made to act on the interface between the polymer film 100 and the upper surface of the substrate W. As a result, while quickly separating the polymer film 100 from the upper surface of the substrate W, the particles 150 can be efficiently removed from the upper surface of the substrate W together with the polymer film 100.

[0106] In addition, light irradiation of the polymer film 100 is performed inside the light-shielding chamber 4. Therefore, unintended structural changes in the photoreactive compound 103 in the polymer film 100 can be suppressed. Therefore, the polymer film 100 can be effectively deformed by the light emitted from the light-emitting member 8.

[0107] <Configuration of the substrate processing apparatus according to the second embodiment> Next, the configuration of the substrate processing apparatus 1A according to the second embodiment will be described. The layout of the substrate processing apparatus 1A is the same as that of the substrate processing apparatus 1 according to the first embodiment (see FIG. 1). FIG. 11 is a schematic diagram for explaining the configuration of the wet processing unit 2W provided in the substrate processing apparatus 1A. In FIG. 11, the same components as those shown in FIGS. 1 to 10 described above are denoted by the same reference numerals as in FIG. 1 and the description thereof is omitted. The same applies to FIGS. 12 to 14 described later.

[0108] The main differences between the processing unit 2 according to the second embodiment and the wet processing unit 2W according to the first embodiment (see FIG. 2) are that a suction nozzle 12 is provided instead of the peeling liquid nozzle 10, and that the polymer-containing liquid does not contain highly soluble substances.

[0109] The suction nozzle 12 is an example of a suction member that performs a suction removal process of sucking the polymer film 100 on the upper surface of the substrate W and removing the polymer film 100 from the upper surface of the substrate W as a polymer film removal process. The suction nozzle 12 is connected to a suction pipe 43. The suction pipe 43 is connected to a suction device 55 such as a vacuum pump. The suction device 55 may be a part of the substrate processing apparatus 1A, or may be a separate device from the substrate processing apparatus 1A provided in the facility where the substrate processing apparatus 1A is installed. The suction pipe 43 is provided with a suction valve 53 for opening and closing the suction pipe 43. By opening the suction valve 53, the suction nozzle 12 sucks the atmosphere in contact with the suction port 12a of the suction nozzle 12.

[0110] The suction nozzle 12 is movable by a nozzle moving mechanism 38. The nozzle moving mechanism 38 can move the suction nozzle 12 in the horizontal direction. The suction nozzle 12 is movable between a center position facing the center of the upper surface of the substrate W and a retracted position located outside the processing cup 7 in a plan view. The configuration of the nozzle moving mechanism 38 is the same as those of the other nozzle moving mechanisms 35, 36, and 37.

[0111] <Substrate processing by the substrate processing apparatus according to the second embodiment> Next, an example of substrate processing by the substrate processing apparatus 1A will be described. FIG. 12 is a flowchart for explaining the substrate processing executed by the substrate processing apparatus 1A. FIG. 13 is a schematic diagram for explaining the state of the substrate W during the substrate processing executed by the substrate processing apparatus 1A.

[0112] In the substrate processing by the substrate processing apparatus 1A according to the second embodiment, as shown in FIG. 12, a polymer-containing liquid supply step (step S1), a polymer film formation step (step S2), a light irradiation step (step S3), and a suction removal step (step S7) are executed. Hereinafter, with reference mainly to FIGS. 11 and 12, the details of the substrate processing will be described centering on the differences from the first substrate processing (refer to FIGS. 6 and 7) by the substrate processing apparatus 1 according to the first embodiment. FIG. 13 will be referred to as appropriate.

[0113] Similar to the first substrate processing, as shown in FIG. 13(a), a polymer-containing liquid supply step (step S1) of supplying a polymer-containing liquid to the upper surface of the substrate W is executed, and then, as shown in FIG. 13(b), a polymer film 100 is formed on the upper surface of the substrate W (polymer film formation step: step S2). Further thereafter, as shown in FIG. 13(c), a light irradiation step (step S3) of irradiating light onto the polymer film 100 on the upper surface of the substrate W is executed.

[0114] Next, a suction removal step (step S7) of sucking the polymer film 100 on the upper surface of the substrate W and removing the polymer film 100 from the upper surface of the substrate W is executed.

[0115] Specifically, the emission of light from the light emitting member 8 is stopped, and then the suction nozzle 12 is disposed at a position facing the upper surface of the substrate W. With the suction nozzle 12 facing the upper surface of the substrate W, the suction valve 53 is opened. As a result, as shown in FIG. 13(d), the polymer film 100 on the upper surface of the substrate W is sucked from the suction port 12a of the suction nozzle 12. By continuing the suction by the suction nozzle 12, as shown in FIG. 13(e), the polymer film 100 is removed from the upper surface of the substrate W (polymer film removal step). After the suction valve 53 is opened, the nozzle moving mechanism 38 moves the suction nozzle 12 horizontally while facing the upper surface of the rotating substrate W, so that the polymer film 100 can be uniformly removed from the entire upper surface of the substrate. The suction flow rate of the suction nozzle 12 is, for example, executed at a suction flow rate of 2 L / min for 60 seconds, and while the suction by the suction nozzle 12 is being performed, the substrate W is rotated at, for example, 0 rpm or more and 100 rpm or less.

[0116] Thus, the suction nozzle 12 functions as a suction removal member that executes a suction removal process of sucking the polymer film 100 from the upper surface of the substrate W and removing it from the upper surface of the substrate W. Further, the suction nozzle 12 is an example of a polymer film removal member that executes a polymer film removal process of removing the polymer film 100 from the upper surface of the substrate W.

[0117] Next, with reference to FIGS. 14A to 14C, an example of a mechanism for removing the polymer film 100 in the substrate processing according to the second embodiment will be described. It is not necessarily the case that the polymer film 100 is removed from the upper surface of the substrate W based on the mechanism described below, but at least a part of the polymer film 100 is separated from the upper surface of the substrate W due to a structural change of the photoreactive compound, and finally the polymer film 100 may be removed from the upper surface of the substrate W. FIGS. 14A to 14C are schematic diagrams for explaining how the polymer film 100 is removed in the substrate processing according to the second embodiment.

[0118] In the polymer film formation step (step S2), the polymer film 100 formed holds particles 150 (objects to be removed) adhering to the upper surface of the substrate W, as shown in FIG. 14A. The polymer film 100 contains a polymer component 101 in a solid state and a photoreactive compound 103 (solid photoreactive compound) in a solid state.

[0119] Referring to FIG. 14B, in the light irradiation step (step S3), when the polymer film 100 is irradiated with light such as ultraviolet light, the structure of the photoreactive compound 103 in the polymer film 100 changes from the first structure 121 (see FIG. 14A) to the second structure 122, and the polymer film 100 deforms to curve. Due to the curvature of the polymer film 100, the polymer film 100 splits, and a plurality of curved film pieces 133 are formed.

[0120] When the photoreactive compound 103 is a diallyl ethene-based compound, the first structure 121 is an open-ring form, and the second structure 122 is a closed-ring form. When the photoreactive compound is an azobenzene-based compound, the first structure 121 is a trans form, and the second structure 122 is a cis form.

[0121] Referring to FIG. 14C, in the suction removal step (step S7), the plurality of curved film pieces 133 on the upper surface of the substrate W are suctioned by the suction nozzle 12. Thereby, the plurality of curved film pieces 133 are removed from the upper surface of the substrate W. Since at least a part of the polymer film 100 is peeled off from the upper surface of the substrate W by light irradiation and the polymer film 100 is split, it is easier to be pulled off from the upper surface of the substrate W by the suction force of the suction nozzle 12 compared to the case of pulling off the non-light-irradiated polymer film 100 from the substrate W.

[0122] According to the second embodiment, the structure of the photoreactive compound 103 contained in the polymer film 100 on the upper surface of the substrate W changes upon light irradiation. Therefore, the polymer film 100 deforms due to light irradiation, and at least a part of the polymer film 100 is separated from the upper surface of the substrate W. By separating the polymer film 100 from the upper surface of the substrate W, the particles 150 held by the polymer film 100 can be separated from the upper surface of the substrate W. By removing the polymer film 100 from the upper surface of the substrate W in a state where the particles 150 are separated from the upper surface of the substrate W together with the polymer film 100, the particles 150 can be effectively removed from the upper surface of the substrate W.

[0123] Also according to the second embodiment, the photoreactive compound 103 contains at least one of a diallylethene-based compound and an azobenzene-based compound. The structures of the diallylethene-based compound and the azobenzene-based compound change upon light irradiation. Due to such a structural change, the polymer film 100 deforms, and at least a part of the polymer film 100 is separated from the upper surface of the substrate W.

[0124] Also according to the second embodiment, since at least a part of the polymer film 100 is separated from the upper surface of the substrate W, the polymer film 100 is more easily peeled off from the upper surface of the substrate W than before light irradiation. Therefore, the polymer film 100 can be removed from the upper surface of the substrate W by suction.

[0125] Also, if the polymer film 100 can be removed by suction without supplying a release liquid to the upper surface of the substrate W, the labor of drying the upper surface of the substrate W can be saved.

[0126] <Modification example of the light emitting member> Next, a modification example of the light emitting member 8 will be described. The configuration of the light emitting member 8 is not limited to that shown in FIGS. 2 and 11, and may be configured to be able to irradiate the polymer film 100 formed on the main surface of the substrate W with desired light. For example, the light emitting member can adopt the configurations shown in FIGS. 15 to 17.

[0127] FIG. 15 is a schematic diagram for explaining a first modification example of the light emitting member. FIG. 16 is a schematic diagram for explaining a second modification example of the light emitting member. FIG. 17 is a schematic diagram for explaining a third modification example of the light emitting member.

[0128] Referring to FIG. 15, the light emitting member 8 may be configured to move horizontally between an irradiation position and a home position (retracted position) by a moving mechanism 86 provided in the chamber 4.

[0129] The irradiation position is a position where the light emitting member 8 faces the upper surface of the substrate W. The irradiation position is a position where light can be irradiated from the light emitting member 8 to the upper surface of the substrate W. The retracted position is a position where light is not irradiated from the light emitting member 8 to the upper surface of the substrate W. When the light emitting member 8 is located at the irradiation position, the light emitting member 8 faces the upper surface of the substrate W. When the light emitting member 8 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view.

[0130] The light emitting member 8 according to the first modification example includes a lamp 80 and a lamp holder 81 that houses the lamp 80. The moving mechanism 86 includes an arm 87 that supports the lamp holder 81, a rotation shaft 89 that is connected to the arm 87 and extends vertically, and an arm drive mechanism 88 that moves the arm 87 via the rotation shaft 89. The arm drive mechanism 88 includes, for example, a motor that rotates the rotation shaft 89 around its central axis (rotation axis A2) to horizontally move the arm 87, and a ball screw mechanism that moves the arm 87 up and down together with the rotation shaft 89.

[0131] In the first modification example, light can be irradiated onto the upper surface of the substrate W while moving the light emitting member 8 in a direction parallel to the upper surface of the substrate W.

[0132] In the second modification example shown in FIG. 16, the lamp 80 is rod-shaped and disposed within an arm 87 that extends linearly. In this case, light can be irradiated over a wider range than in the first modification example shown in FIG. 15.

[0133] In the third modification example shown in FIG. 17, the light emitting member 8 is provided with a light emitting member 202 in a dry processing unit 2D provided in the substrate processing apparatuses 1 and 1A separately from the wet processing unit 2W shown in FIGS. 2, 9, and 11.

[0134] The dry processing unit 2D includes a dry chamber 200, a mounting table 201 disposed in the dry chamber 200 for mounting the substrate W, and a light emitting member 202 that emits light toward the upper surface of the substrate W mounted on the mounting table 201. The light emitting member 202 includes an opposing member 203 having an opposing surface 203a opposing the upper surface of the substrate W on the mounting table 201, and a plurality of lamps 204 as light sources attached to the opposing member 203. A power supply unit 205 configured to energize or stop energization of the plurality of lamps 204 is connected to the lamp 204. Details of the lamp 204 are the same as those of the lamp 80 (see FIG. 2) described above.

[0135] In the third modification example, the spin chuck 5 of the wet processing unit 2W functions as a first substrate holding member that holds the substrate W in the first holding position, and the mounting table 201 of the dry processing unit 2D functions as a second substrate holding member that holds the substrate W in the second holding position. The first substrate holding member and the second substrate holding member constitute the substrate holding member.

[0136] The substrate W is conveyed between the wet processing unit 2W and the dry processing unit 2D by a transfer robot CR. Therefore, the polymer film forming step (step S2) is performed in the wet processing unit 2W, and the substrate W is conveyed to the dry processing unit 2D. Thereafter, the light irradiation step (step S3) is performed in the dry processing unit 2D, and the substrate W is conveyed to the wet processing unit 2W. Then, in the wet processing unit 2W, the peeling liquid supply step (step S4) to the spin drying step (step S6) of the first substrate processing according to the first embodiment (see FIG. 6), or the suction removal step (step S7) of the substrate processing according to the second embodiment (see FIG. 13) is executed.

[0137] Hereinafter, the polymers and highly soluble substances used in each of the above-described embodiments will be described.

[0138] Hereinafter, the notations such as "C" x~y ", "C" x~ C" y " and "C" x " mean the number of carbons in a molecule or substituent. For example, C 1~6 alkyl means an alkyl chain having 1 to 6 carbons (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0139] When a polymer has a plurality of types of repeating units, these repeating units copolymerize. Unless otherwise particularly limited, these copolymerizations may be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When showing a polymer or resin by a structural formula, n, m, etc. written in parentheses indicate the number of repetitions.

[0140] <Polymer component (low solubility substance) contained in the polymer-containing liquid> (A) The polymer component includes at least one of novolak, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, (A) the polymer component may include at least one of novolak, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, (A) the polymer component may include at least one of novolak, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. The novolak may be phenol novolak.

[0141] The polymer-containing liquid may contain, as the (A) polymer component, one or a combination of two or more of the above preferred examples. For example, the (A) polymer component may contain both novolak and polyhydroxystyrene.

[0142] (A) The polymer component forms a film when dried, and in a preferred embodiment, the film is peeled off while holding the object to be removed without being mostly dissolved by the peeling liquid. Note that an embodiment in which a very small part of the (A) polymer component is dissolved by the peeling liquid is allowed.

[0143] Preferably, the (A) polymer component does not contain fluorine and / or silicon, and more preferably does not contain both.

[0144] The copolymerization is preferably random copolymerization or block copolymerization.

[0145] Although there is no intention to limit the scope of rights, specific examples of the (A) polymer component include the compounds shown in Chemical Formulas 9 to 15 below.

[0146]

Chem.

[0147]

Chem.

[0148]

Chem.

[0149] (The asterisk * indicates a bond to an adjacent structural unit.)

[0150]

Chem.

[0151] (R means a substituent such as C 1~4 alkyl. The asterisk * indicates a bond to an adjacent structural unit.)

[0152]

Chem.

[0153]

Chem.

[0154]

Chem.

[0155] (Me means a methyl group.) (A) The weight average molecular weight (Mw) of the polymer component is preferably 150 to 500,000, more preferably 300 to 300,000, still more preferably 500 to 100,000, and even more preferably 1,000 to 50,000.

[0156] The solubility can be evaluated by a known method. For example, under the conditions of 20°C to 35°C (more preferably 25 ± 2°C), 100 ppm of the above (A) or (B) described below is added to 5.0 mass% aqueous ammonia in a flask, the flask is covered, and shaken for 3 hours with a shaker to determine whether (A) or (B) is dissolved. Shaking may be stirring. Dissolution can also be judged visually. If it does not dissolve, the solubility is less than 100 ppm, and if it dissolves, the solubility is 100 ppm or more. A solubility of less than 100 ppm is defined as insoluble or hardly soluble, and a solubility of 100 ppm or more is defined as soluble. In a broad sense, soluble includes slightly soluble. Insoluble, hardly soluble, and soluble are in the order of decreasing solubility. In a narrow sense, slightly soluble has a lower solubility than soluble and a higher solubility than hardly soluble.

[0157] <Highly soluble substances contained in the polymer-containing liquid> (B) The highly soluble substance is a (B’) crack promoting component. The (B’) crack promoting component contains a hydrocarbon and further contains a hydroxy group (-OH) and / or a carbonyl group (-C(=O)-). When the (B’) crack promoting component is a polymer, one type of constituent unit contains a hydrocarbon for each unit and further has a hydroxy group and / or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, enone, and carboxylic acid is preferred.

[0158] Although there is no intention to limit the scope of rights and it is not bound by theory, when the polymer-containing liquid is dried to form a polymer film on the substrate and the stripping liquid strips the polymer film, it is considered that the (B) highly soluble substance creates a portion that triggers the peeling of the polymer film. For this reason, it is preferable that the solubility of the (B) highly soluble substance in the stripping liquid is higher than that of the (A) polymer. Examples of the aspect in which the (B’) crack promoting component contains a ketone as the carbonyl group include cyclic hydrocarbons. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0159] In a more specific aspect, the (B) highly soluble substance is represented by at least any one of the following (B-1), (B-2), and (B-3). (B-1) is a compound comprising 1 to 6 (preferably 1 to 4) of the following chemical formula 16 as constituent units, and each constituent unit is bonded by a linking group (linker L1). Here, the linker L1 may be a single bond or C 1~6 alkylene. The C 1~6 alkylene links the constituent units as a linker and is not limited to a divalent group. It is preferably 2 to 4 valent. The C 1~6 alkylene may be either linear or branched.

[0160]

Chemical formula

[0161] Cy1 is C5~30 It is a hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. As a preferred embodiment, the linker L1 links a plurality of Cy1s.

[0162] Each R1 is independently C 1~5 alkyl, preferably methyl, ethyl, propyl, or butyl. The C 1~5 alkyl can be either straight-chain or branched.

[0163] 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.

[0164] The following Chemical Formula 17 is a chemical formula representing the structural unit described in Chemical Formula 16 using the linker L9. The linker L9 is preferably a single bond, methylene, ethylene, or propylene.

[0165]

Chemical Formula

[0166] Although there is no intention to limit the scope of rights, preferred examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These may be obtained by polymerization or condensation.

[0167] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following Chemical Formula 18 will be taken and explained. In (B-1), this compound has three structural units of Chemical Formula 16, and the structural units are linked by a linker L1 (methylene). n b1 =n b1’ = 1, and R1 is methyl.

[0168]

Chemical formula

[0169] (B-2) is represented by the following Chemical Formula 19.

[0170]

Chemical formula

[0171] R 21 、R 22 、R 23 、and R 24 are each independently hydrogen or an alkyl of C 1~5 , preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

[0172] Linker L 21 and linker L 22 are each independently an alkylene of C 1~20 , a cycloalkylene of C 1~20 , an alkenylene of C 2~4 , an alkynylene of C 2~4 , or an arylene of C 6~20 . These groups may be substituted with an alkyl or hydroxy of C 1~5 . Here, alkenylene means a divalent hydrocarbon having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. Linker L 21 and linker L 22is preferably C 2~4 alkylene, acetylene (C2 alkynylene) or phenylene of, more preferably C 2~4 alkylene or acetylene of, still more preferably acetylene.

[0173] n b2 is 0, 1 or 2, preferably 0 or 1, more preferably 0.

[0174] Although there is no intention to limit the scope of rights, preferred examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol, 2,5-dimethyl-3-hexyne-2,5-diol. As another form, 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, 1,4-benzenedimethanol are also cited as preferred examples of (B-2).

[0175] (B-3) comprises a structural unit represented by the following Chemical Formula 20 and is a polymer 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.

[0176] [Chemical Formula]

[0177] Here, R 25 is -H, -CH3, or -COOH, preferably -H, or -COOH. It is also acceptable that one (B-3) polymer comprises two or more structural units each represented by Chemical Formula 20.

[0178] Although there is no intention to limit the scope of rights, preferred examples of the (B-3) polymer include polymers of acrylic acid, maleic acid, or combinations thereof. Polyacrylic acid, maleic acid-acrylic acid copolymer are more preferred examples.

[0179] In the case of copolymerization, it is preferably random copolymerization or block copolymerization, and more preferably random copolymerization.

[0180] As an example, a maleic acid-acrylic acid copolymer represented by the following Chemical Formula 21 will be described. The copolymer is included in (B-3) and has two structural units represented by Chemical Formula 20. In one structural unit, R 25 is -H, and in another structural unit, R 25 is -COOH.

[0181]

Chemical formula

[0182] Needless to say, the polymer-containing liquid may contain one or a combination of two or more of the above preferred examples as the (B) highly soluble substance. For example, the (B) highly soluble substance may contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0183] The (B) highly soluble substance may have a molecular weight of 80 to 10,000. The highly soluble substance preferably has a molecular weight of 90 to 5000, and more preferably 100 to 3000.

[0184] <Other embodiments> This invention is not limited to the embodiments described above, and can be implemented in other forms.

[0185] (1) While the polymer-containing liquid is being discharged from the polymer-containing liquid nozzle 9, the substrate W may be rotated at a low speed (for example, 10 rpm), and then, after the discharge of the polymer-containing liquid from the polymer-containing liquid nozzle 9 is stopped, the rotation of the substrate W may be accelerated and the substrate W may be rotated at a spin-off speed (for example, 1500 rpm). Thereby, the polymer-containing liquid adhering to the central region of the upper surface of the substrate W can be thinly spread on the upper surface of the substrate W, and a thin film of the polymer-containing liquid can be formed on the upper surface of the substrate W.

[0186] (2) The polymer film removal process may be a dissolution liquid supply process in which a dissolution liquid for dissolving the polymer film 100 is supplied toward the upper surface of the substrate W after the light irradiation step. Since at least a part of the polymer film 100 has been peeled off from the upper surface of the substrate W by light irradiation, even if the dissolution liquid is supplied to dissolve the polymer film 100, due to the peeling of the polymer film 100 caused by light irradiation, the particles 150 separated from the upper surface of the substrate W are removed from the upper surface of the substrate W together with the dissolution liquid.

[0187] (3) The polymer-containing liquid discharged from the polymer-containing liquid nozzle 9 according to the second embodiment does not contain a highly soluble substance. However, the polymer-containing liquid discharged from the polymer-containing liquid nozzle 9 according to the second embodiment may also contain a highly soluble substance.

[0188] (4) The polymer film 100 does not necessarily have to be a curved film piece curved in an arc shape by light irradiation, and at least a part of the polymer film 100 may be peeled off. For example, the polymer film 100 may be deformed into a hemispherical shape by light irradiation to form a hemispherical film piece. Further, the polymer film 100 may be bent in a V shape by light irradiation, or a V-shaped film piece may be formed. Also, film pieces of various shapes may be mixed.

[0189] (5) Different from each of the above embodiments, a peeling liquid nozzle 10 and a suction nozzle 12 may be provided, and the polymer film 100 may be removed by both the supply of the peeling liquid and the suction of the polymer film 100. For example, after removing the polymer film 100 by suction, the peeling liquid may be supplied to the upper surface of the substrate W. Also, the suction of the polymer film 100 and the light irradiation may be performed in parallel.

[0190] (6) In each of the above embodiments, substrate processing is performed on the upper surface of the substrate W. However, substrate processing may be performed on the lower surface of the substrate W.

[0191] (7) In each of the above-described embodiments, the spin chuck 5 is a gripping-type spin chuck that grips the periphery of the substrate W with a plurality of chuck pins 20. However, the spin chuck 5 may be a vacuum suction-type spin chuck that sucks the substrate W onto the spin base 20., (8) The spin chuck 5 does not necessarily have to hold the substrate W horizontally. That is, the spin chuck 5 may hold the substrate W vertically, or may hold the substrate W such that the upper surface of the substrate W is inclined with respect to the horizontal plane.

[0192] (9) In each of the above-described embodiments, a plurality of fluids are each configured to be discharged from a plurality of nozzles. However, the mode of discharge of each fluid is not limited to each of the above-described embodiments.

[0193] (10) In each of the above-described embodiments, some of the illustrations of pipes, pumps, valves, actuators, etc. are omitted, but this does not mean that these members do not exist. Actually, these members are provided at appropriate positions. For example, a flow rate adjustment valve (not shown) for adjusting the flow rate of the processing liquid discharged from the corresponding processing liquid nozzle may be provided in each pipe.

[0194] (11) In each of the above-described embodiments, the controller 3 controls the entire substrate processing apparatus 1. However, the controllers for controlling each member of the substrate processing apparatus 1 may be distributed at a plurality of locations. Also, the controller 3 does not necessarily have to directly control each member, and the signal output from the controller 3 may be received by a slave controller that controls each member of the substrate processing apparatus 1.

[0195] (12) Also, in the above-described embodiment, the substrate processing apparatus 1 includes transfer robots IR and CR, a plurality of processing units 2, and a controller 3. However, the substrate processing apparatus 1 may be composed of a single processing unit 2 and a controller 3 and may not include a transfer robot. Alternatively, the substrate processing apparatus 1 may be composed of only a single processing unit 2. In other words, the processing unit 2 may be an example of the substrate processing apparatus.

[0196] In addition, various modifications can be made within the scope described in the claims.

Explanation of Reference Numerals

[0197] 1: Substrate processing apparatus 1A: Substrate processing apparatus 5: Spin chuck (substrate holding member) 8: Light emitting member 9: Polymer-containing liquid nozzle (polymer film forming member) 10: Removing liquid nozzle (removing liquid supply member, polymer film removing member) 12: Suction nozzle (suction member, polymer film removing member) 100: Polymer film 101: Polymer component 102: Highly soluble substance 103: Photo-reactive compound 201: Mounting table (substrate holding member) 202: Light emitting member W: Substrate

Claims

1. A substrate holding member for holding a substrate at a holding position, A polymer film forming member for forming a polymer film containing a photoreactive compound containing a diallyl ethene compound and a polymer component on a main surface of the substrate held at the holding position, A light emitting member for emitting light including ultraviolet light toward the main surface of the substrate held at the holding position to isomerize the diallyl ethene compound from an open-ring form to a closed-ring form, A substrate processing apparatus including a polymer film removing member for performing a polymer film removing process for removing the polymer film from the main surface of the substrate held at the holding position.

2. The substrate processing apparatus according to claim 1, wherein the polymer film removing member includes a stripping liquid supply member that performs a stripping liquid supply process of supplying a stripping liquid for stripping the polymer film to the main surface of the substrate as the polymer film removing process.

3. The substrate processing apparatus according to claim 2, wherein the polymer film forming member forms the polymer film further containing a highly soluble substance having a higher solubility in the stripping liquid than the polymer component.

4. The substrate processing apparatus according to any one of claims 1 to 3, wherein the polymer film removing member includes a suction member that performs a suction removing process of sucking the polymer film to remove the polymer film from the main surface of the substrate as the polymer film removing process.

5. The substrate processing apparatus according to any one of claims 1 to 4, wherein at least a part of the polymer film is separated from the main surface of the substrate in the polymer film removing process.

6. A polymer film forming step of forming a polymer film containing a photoreactive compound containing a diallyl ethene compound and a polymer component on a main surface of a substrate, A light irradiation step of irradiating the polymer film on the main surface of the substrate with light including ultraviolet light to isomerize the diallyl ethene compound from an open-ring form to a closed-ring form, A substrate processing method including a polymer film removing step of removing the polymer film from the main surface of the substrate after the light irradiation step.

7. The substrate processing method according to claim 6, wherein the polymer film removing step includes a stripping liquid supply step of supplying a stripping liquid for stripping the polymer film to the polymer film on the main surface of the substrate.

8. The substrate processing method according to claim 7, wherein the polymer film forming step includes a step of forming the polymer film further containing a highly soluble substance having a higher solubility in the stripping liquid than the polymer component.

9. The substrate processing method according to any one of claims 6 to 8, wherein the polymer film removing step includes a suction removing step of sucking the polymer film on the main surface of the substrate to remove the polymer film from the main surface of the substrate.

10. The substrate processing method according to any one of claims 6 to 9, wherein the polymer film removing step includes a step of separating the polymer film from the main surface of the substrate.

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