JP7717606B2 - SUBSTRATE PROCESSING APPARATUS AND SUBSTRATE PROCESSING METHOD - Google Patents

Description

This invention relates to a substrate processing apparatus and a substrate processing method for processing substrates. Substrates that can be processed include, for example, semiconductor wafers, substrates for FPDs (Flat Panel Displays) such as liquid crystal display devices and organic EL (Electroluminescence) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

There is a need for a method for removing particles and other objects from the main surface of a substrate. For example, Patent Document 1 below discloses a substrate treatment method in which a topcoat liquid is supplied to a substrate and volatile components are evaporated from the topcoat liquid to form a topcoat film, which is then dissolved in a removal liquid and removed from the substrate. The volume shrinkage that occurs when the topcoat film is formed from the topcoat liquid causes particles to detach from the substrate.

JP 2014-197717 A

One object of the present invention is to provide a novel substrate processing apparatus and substrate processing method that can efficiently remove materials present on the surface of a substrate.

One embodiment of the present invention provides a substrate processing apparatus that includes a substrate holding member that holds a substrate in a holding position; a polymer film forming member that forms a polymer film containing a photoreactive compound and a polymer component whose structure changes when irradiated with light on a major surface of the substrate held in the holding position; a light emitting member that emits light toward the major surface of the substrate held in the holding position; and a polymer film removal member that performs a polymer film removal process to remove the polymer film from the major surface of the substrate held in the holding position.

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 light irradiation, and at least a portion of the polymer film is detached from the main surface of the substrate. By detaching the polymer film from the main surface of the substrate, the object to be removed held by the polymer film can be detached from the main surface of the substrate. By removing the polymer film from the main surface of the substrate while the object to be removed is detached 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.

In one embodiment of the present invention, the photoreactive compound includes at least one of a diarylethene compound and an azobenzene compound.

The diarylethene-based compound and the azobenzene-based compound undergo structural changes upon irradiation with light. The structural change of the components in the polymer film causes the polymer film to deform, and at least a portion of the polymer film is detached from the main surface of the substrate. The polymer film, for example, is curved upon irradiation with light.
The photoreactive compound may include a diarylethene compound. The light emitting member may emit light including ultraviolet light toward a main surface of the substrate held at the holding position, thereby isomerizing the diarylethene compound included in the photoreactive compound from an open-ring form to a closed-ring form.

In one embodiment of the present invention, the polymer film removal member includes a remover liquid supply member that performs the polymer film removal process by supplying a remover liquid to the main surface of the substrate, which removes the polymer film. Therefore, the remover liquid promotes the removal of the polymer film, and the target material can be effectively removed from the main surface of the substrate.

In one embodiment of the present invention, the polymer film-forming member forms the polymer film, which further contains a highly soluble substance that is more soluble in the stripping solution than the polymer component. Therefore, the highly soluble substance can be dissolved by the stripping solution while the polymer film is maintained. Therefore, the polymer component can hold the object to be removed, while the stripping solution can be applied to the interface between the polymer film and the main surface of the substrate. As a result, the polymer film can be quickly stripped from the main surface of the substrate, while the object to be removed can be efficiently removed from the main surface of the substrate along with the polymer film.

In one embodiment of the present invention, the polymer film removal member includes a suction member that performs a suction removal process, as the polymer film removal process, by sucking the polymer film and removing it from the main surface of the substrate. Because at least a portion of the polymer film is detached from the main surface of the substrate, the polymer film is more likely to peel off from the main surface of the substrate than before light irradiation. Therefore, the polymer film can be removed from the main surface of the substrate by suction.

Furthermore, if the polymer film can be removed by suction without supplying a stripping liquid to the main surface of the substrate, the effort of drying the main surface of the substrate can be eliminated.

Another embodiment of the present invention provides a substrate processing method including a polymer film formation step of forming a polymer film containing a photoreactive compound and a polymer component, whose structure changes upon light irradiation, 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; and a polymer film removal step of removing the polymer film from the main surface of the substrate after the light irradiation step. This substrate processing method achieves the same effects as the substrate processing apparatus described above.

In another embodiment of the present invention, the photoreactive compound may include at least one of a diarylethene compound and an azobenzene compound.
The photoreactive compound may include a diarylethene 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 diarylethene compound included in the photoreactive compound from an open-ring form to a closed-ring form.

In another embodiment of the present invention, the polymer film removal process may include a stripping liquid supply process of supplying a stripping liquid that strips the polymer film to the polymer film on the main surface of the substrate.

In another embodiment of the present invention, the polymer film formation step may include a step of forming the polymer film further containing a highly soluble substance that is more soluble in the stripping solution than the polymer component.

In another embodiment of the present invention, the polymer film removal process may include a suction removal process in which the polymer film on the main surface of the substrate is sucked to remove the polymer film from the main surface of the substrate.

In another embodiment of the present invention, the polymer film removal step may include a step of detaching the polymer film from the main surface of the substrate by bending the polymer film due to a structural change in the photoreactive compound.

FIG. 1 is a schematic plan view showing the layout of a substrate processing apparatus according to a first embodiment of the present invention. FIG. 2 is a schematic diagram for explaining the configuration of a processing unit provided in the substrate processing apparatus. FIG. 3 is a chemical reaction formula for explaining the structural change caused by light irradiation of the diarylethene compound as the photoreactive compound contained in the polymer-containing liquid used in the processing unit. FIG. 4 is a chemical reaction formula for explaining the structural change caused by light irradiation of an azobenzene compound as a photoreactive compound contained in the polymer-containing liquid used in the processing unit. FIG. 5 is a block diagram for explaining the electrical configuration of the substrate processing apparatus. FIG. 6 is a flowchart for explaining the first substrate processing performed by the substrate processing apparatus. FIG. 7 is a schematic diagram for explaining the state of the substrate during the first substrate processing. FIG. 8A is a schematic diagram for explaining how the polymer film is removed in the first substrate processing. FIG. 8B is a schematic diagram for explaining how the polymer film is removed in the first substrate processing. FIG. 8C is a schematic diagram for explaining how the polymer film is removed in the first substrate processing. FIG. 8D is a schematic diagram for explaining how the polymer film is removed in the first substrate processing. FIG. 9 is a flowchart for explaining the second substrate processing performed by the substrate processing apparatus. FIG. 10 is a schematic diagram for explaining how the polymer film is removed in the second substrate processing. FIG. 11 is a schematic view for explaining the configuration of a processing unit provided in a substrate processing apparatus according to the second embodiment. FIG. 12 is a flowchart for explaining the substrate processing performed by the substrate processing apparatus according to the second embodiment. FIG. 13 is a schematic view for explaining the state of a substrate during substrate processing performed by the substrate processing apparatus according to the second embodiment. FIG. 14A is a schematic view for explaining how a polymer film is removed in the substrate processing performed by the substrate processing apparatus according to the second embodiment. FIG. 14B is a schematic view for explaining how a polymer film is removed in the substrate processing performed by the substrate processing apparatus according to the second embodiment. FIG. 14C is a schematic view for explaining how a polymer film is removed in the substrate processing performed by the substrate processing apparatus according to the second embodiment. FIG. 15 is a schematic diagram for explaining a first modified example of the light output member. FIG. 16 is a schematic diagram for explaining a second modified example of the light output member. FIG. 17 is a schematic diagram for explaining a third modified example of the light output member.

The following describes an embodiment of the present invention with reference to the accompanying drawings.

<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 a first embodiment of the present invention.

The substrate processing apparatus 1 is a single-wafer processing apparatus that processes substrates W one by one. In this embodiment, the substrates W have a circular shape. The substrates W have a pair of main surfaces. The substrate processing apparatus 1 includes a plurality of processing units 2 that process the substrates W, a load port LP on which carriers C are placed that accommodate a plurality of substrates W to be processed in the processing units 2, transport robots IR and CR that transport the substrates W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.

The transport robot IR transports substrates W between the carrier C and the transport robot CR. The transport robot CR transports substrates W between the transport robot IR and the processing units 2. The transport robots IR and CR are arranged on a transport path TR that extends from multiple load ports LP toward multiple processing units 2.

The multiple processing units 2 have, for example, the same configuration. The multiple processing units 2 form four processing towers TW arranged at four horizontally spaced positions. Each processing tower TW includes multiple (for example, three) processing units 2 stacked vertically. The four processing towers TW are arranged two on each side of the transport path TR.

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 to the substrate W in the wet processing unit 2W include a polymer-containing liquid, a stripping liquid, and a residue dissolving liquid.

Figure 2 is a schematic diagram illustrating the configuration of the wet processing unit 2W.

The wet processing unit 2W includes a spin chuck 5 that rotates the substrate W about a rotation axis A1 while holding the substrate W in a predetermined holding position; a light emitting member 8 that emits light toward the upper surface of the substrate W held on the spin chuck 5; multiple processing liquid nozzles (polymer-containing liquid nozzle 9, stripping liquid nozzle 10, and residue dissolving liquid nozzle 11) that eject processing liquid toward the upper surface (upper main surface) of the substrate W held on the spin chuck 5; a processing cup 7 that receives liquid splashed from the substrate W held on the spin chuck 5; and a chamber 4 that houses the spin chuck 5, processing cup 7, light emitting member 8, and multiple processing liquid nozzles.

The rotation axis A1 is a central axis that passes through the center of the top surface of the substrate W. The holding position is a position where the rotation axis A1 passes through the center of the top surface of the substrate W and where the top surface of the substrate W is horizontal.

The 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. When the shutter unit 4c opens the opening 4b, the transport robot CR can load and unload a substrate W into and from the chamber body 4a. The chamber body 4a and shutter unit 4c are light-blocking, and when the shutter unit 4c closes the opening 4b, light from outside the chamber 4 is blocked.

The spin chuck 5 is surrounded by the processing cup 7. The spin chuck 5 includes a spin base 21 having a horizontally extending disk shape, 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 rotation shaft 22 that is connected to the spin base 21 and extends vertically, and a rotation drive mechanism 23 that rotates the rotation shaft 22 around its central axis (rotation axis A1).

The multiple chuck pins 20 are arranged on the upper surface of the spin base 21 at intervals around the circumference 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 rotation shaft 22, causing the spin base 21 and the multiple chuck pins 20 to rotate around the rotation axis A1. As a result, the substrate W is rotated around the rotation axis A1 together with the spin base 21 and the multiple chuck pins 20.

The multiple chuck pins 20 are movable between a closed position in which they contact the peripheral edge of the substrate W to grip the substrate W, and an open position in which they release their grip on the substrate W. The multiple chuck pins 20 are moved by an opening/closing mechanism (not shown).

When positioned in the closed position, the multiple chuck pins 20 grip the peripheral edge of the substrate W and hold the substrate W in a holding position. When positioned in the open position, the multiple chuck pins 20 release their grip on the substrate W while supporting the peripheral edge of the substrate W from below. The opening/closing mechanism includes, for example, a link mechanism and an actuator that applies a driving force to the link mechanism.

The multiple processing liquid nozzles include a polymer-containing liquid nozzle 9 that sprays a continuous flow of polymer-containing liquid toward the upper surface of the substrate W held on the spin chuck 5, a stripping liquid nozzle 10 that sprays a continuous flow of stripping liquid toward the upper surface of the substrate W held on the spin chuck 5, and a residue dissolving liquid nozzle 11 that sprays a continuous flow of residue dissolving liquid toward the upper surface of the substrate W held on the spin chuck 5.

The polymer-containing liquid ejected from the polymer-containing liquid nozzle 9 contains a solute and a solvent. The solute of the polymer-containing liquid contains a photoreactive compound whose structure changes when irradiated with light, a polymer component that forms a solid or semi-solid film (polymer film) when at least a portion of the solvent evaporates (volatilizes), and a highly soluble substance that has a higher solubility in the stripper liquid than the polymer component.

A polymer-containing liquid contains components (polymer components, described below) that form a solid or semi-solid film (polymer film). A semi-solid state is a state in which solid and liquid components are mixed. A solid state is a state in which no liquid components are contained and the film is composed only of solid components. A polymer film in which solvent remains is semi-solid, and a polymer film in which the solvent has completely disappeared is solid.

Polymer components are also called low-solubility substances because they have lower solubility in the stripping solution (described below) than highly soluble substances. An example of a polymer component is novolak. An example of a highly soluble substance is 2,2-bis(4-hydroxyphenyl)propane. Details of polymer components and highly soluble substances will be provided below.

The photoreactive compound changes from a first structure to a second structure when exposed to light having a first wavelength, and changes from the second structure to the first structure when exposed to light having a second wavelength different from the first wavelength. The photoreactive compound includes, for example, at least one of a diarylethene-based compound and an azobenzene-based compound.

As diarylethene-based compounds, for example, compounds shown in the following chemical formulas 1 to 6 can be used.

As shown in Figure 3, the diarylethene compound changes structure upon irradiation with light . More specifically, the diarylethene compound is isomerized from an open-ring isomer (first structure) to a closed-ring isomer (second structure) upon irradiation with light having a wavelength (first wavelength) of 200 nm or more and 380 nm or less. The diarylethene compound is isomerized from a closed-ring isomer (second structure) to an open-ring isomer (first structure) upon irradiation with light having a wavelength (second wavelength) of 400 nm or more and 760 nm or less. That is, the diarylethene compound is isomerized from an open-ring isomer to a closed-ring isomer upon irradiation with ultraviolet light, and isomerized from a closed-ring isomer to an open-ring isomer upon irradiation with visible light. When the diarylethene compound contained in the polymer film is isomerizes from an open-ring isomer to a closed-ring isomer, the polymer film is deformed to be curved.

Examples of azobenzene-based compounds that can be used include the compounds shown in the following chemical formulas 7 and 8.

As shown in Figure 4, azobenzene compounds also undergo structural changes upon exposure to light. Specifically, when irradiated with light having a wavelength of 200 nm or more and 380 nm or less (first wavelength), the azobenzene compound isomerizes from a trans isomer (first structure) to a cis isomer (second structure). When irradiated with light having a wavelength of 400 nm or more and 760 nm or less (second wavelength), the azobenzene compound isomerizes from a cis isomer (second structure) to a trans isomer (first structure). That is, when irradiated with ultraviolet light, the azobenzene compound isomerizes from a trans isomer to a cis isomer, and when irradiated with visible light, the azobenzene compound isomerizes from a cis isomer to a trans isomer. When the azobenzene compound contained in the polymer film isomerizes from the trans isomer to the cis isomer, the polymer film deforms and curves.

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

Specific examples of organic solvents include 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, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as gamma-butyrolactone. These organic solvents can be used alone or in combination. The solvent may also be a mixture of an organic solvent and water such as DIW (deionized water).

A polymer-containing liquid pipe 40 is connected to the polymer-containing liquid nozzle 9, which guides the polymer-containing liquid to the polymer-containing liquid nozzle 9. A polymer-containing liquid valve 50 is provided in the polymer-containing liquid pipe 40, which opens and closes the flow path within the polymer-containing liquid pipe 40. "A valve is provided in the pipe" may also mean that the valve is interposed in the pipe. When the polymer-containing liquid valve 50 is opened, the polymer-containing liquid is ejected from the polymer-containing liquid nozzle 9.

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

A remover liquid pipe 41 that guides the remover liquid to the remover liquid nozzle 10 is connected to the remover liquid nozzle 10. The remover liquid pipe 41 is provided with a remover liquid valve 51 that opens and closes the flow path within the remover liquid pipe 41. When the remover liquid valve 51 is opened, the remover liquid is ejected from the remover liquid nozzle 10.

The residue dissolving liquid discharged from the residue dissolving liquid nozzle 11 is a liquid that dissolves residue remaining on the main surface of the substrate W after the polymer film has been peeled off and removed from the main surface of the substrate W by the stripping liquid. The residue dissolving liquid is, for example, an organic solvent such as IPA. As the organic solvent, any of the solvents listed as being contained in the polymer-containing liquid can be used.

A residue dissolving liquid pipe 42 is connected to the residue dissolving liquid nozzle 11, which guides the residue dissolving liquid to the residue dissolving liquid nozzle 11. The residue dissolving liquid pipe 42 is provided with a residue dissolving liquid valve 52 that opens and closes the flow path within the residue dissolving liquid pipe 42. When the residue dissolving liquid valve 52 is opened, the residue dissolving liquid is ejected from the residue dissolving liquid nozzle 11.

The multiple processing liquid nozzles can be moved by multiple nozzle movement mechanisms 35, 36, and 37. The multiple nozzle movement mechanisms 35, 36, and 37 can move the corresponding processing liquid nozzle at least in the horizontal direction. Each processing liquid nozzle can be moved between a central position facing the center of the top surface of the substrate W and a retracted position located outside the processing cup 7 in a plan view. Each nozzle movement mechanism 35, 36, and 37 includes a support arm (not shown) that supports the corresponding processing liquid nozzle and a drive mechanism (not shown) that drives the support arm. The drive mechanism includes, for example, an actuator such as a motor.

The configuration of the processing cup 7 is not particularly limited. The processing cup 7 includes, for example, a plurality of guards 71 (two in FIG. 2) that catch processing liquid splashed outward from the substrate W held on the spin chuck 5, a plurality of cups 72 (two in FIG. 2) that each catch the processing liquid guided downward by the guards 71, and a cylindrical outer wall member 73 that surrounds the guards 71 and cups 72.

Each guard 71 has a cylindrical shape that surrounds the spin chuck 5 in a plan view. The upper end of each guard 71 is inclined toward the inside of the guard 71. Each cup 72 has the shape of an annular groove that opens upward. Multiple guards 71 and multiple cups 72 are arranged coaxially.

The multiple guards 71 are individually raised and lowered by a guard lifting drive mechanism (not shown). The guard lifting drive mechanism includes, for example, multiple actuators that drive the multiple guards 71 to raise and lower. The multiple actuators include at least one of an electric motor and an air cylinder.

The light output member 8 includes a facing member 6 that faces from above the top surface (upper surface) of the substrate W held by the spin chuck 5, and a plurality of lamps 80 attached to the facing surface 6a as light sources.

The facing member 6 is formed in the shape of a disk with a diameter approximately the same as or greater than that of the substrate W. The facing surface 6a is disposed above the spin chuck 5 and along an approximately horizontal plane. A rotation shaft 60 is fixed to the opposite side of the facing member 6 from the facing surface 6a. The facing member 6 isolates the atmosphere in the space between the facing surface 6a and the upper surface of the substrate W from the atmosphere outside that space. For this reason, the facing member 6 is also referred to as a shielding plate.

The multiple lamps 80 are arranged at equal intervals across the entire opposing surface 6a. A power supply unit 85 configured to turn on and off the power to the multiple lamps 80 is connected to the multiple lamps 80. The lamps 80 emit light when powered on. Examples of light emitted from each lamp 80 include infrared, ultraviolet, and visible light. Examples of lamps 80 include excimer lamps, xenon lamps, mercury lamps, deuterium lamps, and LED lamps. The light emitted from the lamps 80 preferably has a wavelength of 200 nm or more and 760 nm or less.

The opposing member 6 is moved vertically by a lifting mechanism 61. The lifting mechanism 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) that supports the rotating shaft 60, and an electric motor (not shown) that provides driving force to the ball screw mechanism. The lifting mechanism 61 is also called an opposing member lifter (shield lifter). The lifting mechanism 61 moves the opposing member 6 and the multiple lamps 80 vertically. The lifting mechanism 61 is an example of a lamp lifting unit (lamp lifter).

Figure 5 is a block diagram illustrating the electrical configuration of the substrate processing apparatus 1.

The controller 3 is equipped with a microcomputer and controls the control objects provided in the substrate processing apparatus 1 according to a predetermined control program.

Specifically, the controller 3 includes a processor 3A (CPU) and a memory 3B that stores a control program. The controller 3 is configured so that the processor 3A executes the control program to perform various controls for substrate processing. In particular, the controller 3 is programmed to control the transfer robots IR and CR, the rotation drive mechanism 23, the nozzle movement mechanisms 35, 36, and 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.

Furthermore, while Figure 5 illustrates representative components, this does not mean that components not illustrated are not controlled by the controller 3, and the controller 3 can appropriately control each component provided in the substrate processing apparatus 1. Figure 5 also illustrates components described in the modified examples and second embodiment described below, and these components are also controlled by the controller 3.

The processes shown in FIG. 6, which will be described later, are executed by the controller 3 controlling the components provided in the substrate processing apparatus 1. In other words, the controller 3 is programmed to execute the processes shown in FIG. 6, which will be described later.

<First Substrate Processing>
Fig. 6 is a flowchart for explaining the first substrate processing performed 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.

As shown in FIG. 6, the first substrate processing by the substrate processing apparatus 1 involves a polymer-containing liquid supplying step (step S1), a polymer film forming step (step S2), a heating step (step S3), a stripping liquid supplying step (step S4), a residue dissolving step (step S5), and a spin-drying step (step S6). Below, the first substrate processing will be described in detail, primarily with reference to FIGS. 2 and 6. FIG. 7 will also be referenced as appropriate.

First, an unprocessed substrate W is loaded from the carrier C into the wet processing unit 2W by the transport robot CR (see Figure 1) and handed over to the spin chuck 5 (loading process). The substrate W is then held in a holding position by the spin chuck 5 (substrate holding process). While held by the spin chuck 5, the substrate W is rotated around the rotation axis A1 (substrate rotation process). The substrate W continues to be held by the spin chuck 5 until the spin dry process (step S6) is completed.

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

With the polymer-containing liquid nozzle 9 in the processing position, the polymer-containing liquid valve 50 is opened. As a result, as shown in FIG. 7(a), the polymer-containing liquid is ejected 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 distributed over the entire upper surface of the substrate W, coating the entire upper surface of the substrate W (coating process). 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, for example, at a rotational speed of 0 rpm or more and 1500 rpm or less.

Next, the polymer film formation process (step S2) is performed, in which the supply of the polymer-containing liquid to the upper surface of the substrate W is stopped and the substrate W is rotated to form a polymer film 100 on the upper surface of the substrate W.

Specifically, after the polymer-containing liquid has adhered to at least the center of the upper surface of the substrate W, the polymer-containing liquid valve 50 is closed. This stops the ejection of the polymer-containing liquid from the polymer-containing liquid nozzle 9, and stops the supply of new polymer-containing liquid to the upper surface of the substrate W. When the supply of the polymer-containing liquid is stopped and at least a portion of the solvent evaporates from the polymer-containing liquid adhering to the upper surface of the substrate W, 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.

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 60 seconds, for example, at a rotation speed of 0 rpm or more and 2500 rpm or less. 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, the centrifugal force forms an airflow that directs the gas from the center to the periphery of the substrate W. This airflow removes the gaseous solvent in contact with the polymer-containing liquid on the substrate W from the atmosphere in contact with the substrate W. This promotes evaporation (volatilization) of the solvent from the polymer-containing liquid on the substrate W.

The polymer film 100 contains less solvent than the polymer-containing liquid, and therefore has a higher viscosity than the polymer-containing liquid. Therefore, even though the substrate W is rotating, the polymer film 100 is not completely removed from the substrate W and remains on the substrate W.

Next, a light irradiation process (step S3) is performed in which light is irradiated onto the polymer film 100 on the upper surface of the substrate W.

Specifically, the lamp 80 is energized with the light emitting member 8 positioned at a predetermined irradiation position. As a result, 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. As will be described in more detail below, this changes the structure of the photoreactive compound contained in the polymer film 100, causing at least a portion of the polymer film 100 to peel off from the upper surface of the substrate W. The upper surface of the substrate W is irradiated with light for, for example, 60 seconds. The rotation speed of the substrate W during light irradiation is, for example, between 0 rpm and 2500 rpm.

Next, a stripping liquid supply process (step S4) is performed to supply a stripping liquid to the top surface of the substrate W.

Specifically, the light emission from the light emitting member 8 is stopped, and then the stripping liquid nozzle 10 is positioned at the processing position. With the stripping liquid nozzle 10 positioned at the processing position, the stripping liquid valve 51 is opened. As a result, as shown in FIG. 7(d), stripping liquid is ejected from the stripping liquid nozzle 10 toward the upper surface of the substrate W. The stripping liquid ejected toward the upper surface of the substrate W dissolves the highly soluble substances contained in the polymer film 100, thereby peeling the polymer film 100. By continuing to eject the stripping liquid from the stripping liquid nozzle 10, the polymer film 100 is removed from the upper surface of the substrate W (polymer film removal process) as shown in FIG. 7(e). In this way, the stripping liquid nozzle 10 functions as a stripping liquid supplying member that executes a stripping liquid supplying process that supplies stripping liquid to the upper surface of the substrate W. Furthermore, the stripping liquid nozzle 10 is an example of a polymer film removal member that executes a polymer film removal process that removes the polymer film 100 from the upper surface of the substrate W.

The stripping liquid is supplied to the upper surface of the substrate W at, for example, 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 at a rotational speed of, for example, 0 rpm or more and 2500 rpm or less.

Next, a residue dissolving process (step S5) is performed in which a residue dissolving liquid is supplied to the upper surface of the substrate W.

Specifically, the remover valve 51 is closed, and instead, the residue dissolving liquid nozzle 11 is positioned at the processing position and the residue dissolving liquid valve 52 is opened. This stops the discharge of the remover liquid from the remover liquid nozzle 10, 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 removal liquid discharged toward the upper surface of the substrate W dissolves residue remaining on the upper surface of the substrate W after the polymer film 100 has been removed by the remover liquid. The residue dissolving liquid is supplied to the upper surface of the substrate W at a rate of 1 L/min for 30 seconds, for example. 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.

Next, a spin-drying process (step S6) is performed in which the substrate W is rotated at high speed to dry the top surface of the substrate W. Specifically, the residue dissolving liquid valve 52 is closed, thereby stopping the supply of the residue dissolving liquid to the top surface of the substrate W.

Then, the rotation drive mechanism 23 accelerates the rotation of the substrate W, causing it to rotate at high speed. The substrate W is rotated at a spin dry speed, for example, 1500 rpm. As a result, a large centrifugal force acts on the residue dissolving solution on the substrate W, causing the residue dissolving solution on the substrate W to be scattered around the substrate W. The rotation drive mechanism 23 then stops the rotation of the substrate W. The transport robot CR enters the wet processing unit 2W, scoops up the processed substrate W from the spin chuck 5, and transports it out of the wet processing unit 2W (transport step). The substrate W is then handed over from the transport robot CR to the transport robot IR, which stores it in the carrier C.

Next, an example of the mechanism by which the polymer film 100 is removed in the first substrate processing will be described using Figures 8A to 8D. The polymer film 100 is not necessarily removed from the upper surface of the substrate W based on the mechanism described below; rather, it is sufficient that at least a portion of the polymer film 100 is detached from the upper surface of the substrate W due to a structural change in the photoreactive compound, and the polymer film 100 is ultimately removed from the upper surface of the substrate W. Figures 8A to 8D are schematic diagrams used to explain how the polymer film 100 is removed in the first substrate processing.

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

8B, in the light irradiation process (step S3), the polymer film 100 is irradiated with light such as ultraviolet light, causing the structure of the photoreactive compound 103 in the polymer film 100 to change from a first structure 121 (see FIG. 8A) to a second structure 122, and the polymer film 100 to deform and curve. The bending of the polymer film 100 splits the polymer film 100, forming multiple first curved film pieces 131. The first curved film pieces 131 are curved, for example, so that both ends in a direction intersecting the thickness direction of the polymer film 100 are spaced apart from the top surface of the substrate W. That is, the first curved film pieces 131 may have a bow shape. The bending of the polymer film 100 causes at least a portion of the polymer film 100 (both ends 131a of the first curved film pieces 131) to peel off from the top surface of the substrate W (bending and peeling process).

When the photoreactive compound 103 is a diarylethene-based compound, the first structure 121 is an open-ring isomer and the second structure 122 is a closed-ring isomer (see Figure 3). In Figure 3, Me means a methyl group. When the photoreactive compound is an azobenzene-based compound, the first structure 121 is a trans isomer and the second structure 122 is a cis isomer (see Figure 4).

Referring to Figure 8C, in the stripping liquid supply process (step S3), stripping liquid is supplied toward the upper surface of the substrate W. The stripping liquid passes through the gaps G between the first curved film pieces 131 and enters the interface between the polymer film 100 (first curved film pieces 131) and the upper surface of the substrate W. This promotes the stripping of the polymer film 100. Note that the relationship between the thickness of the stripping liquid film and the thickness of the polymer film 100 is not limited to that shown in Figure 8C.

Furthermore, when the remover liquid comes into contact with the polymer film 100 (first curved film piece 131), the highly soluble substance 102 is selectively dissolved in the remover liquid. That is, the polymer film 100 is partially dissolved (dissolving process, partial dissolving process). Here, if the solvent of the polymer-containing liquid and the remover liquid are miscible and an appropriate amount of solvent remains in the polymer film 100, the remover 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 quickly dissolved.

"Highly soluble substance 102 is selectively dissolved" does not mean that only the highly soluble substance 102 is dissolved. "Highly soluble substance 102 is selectively dissolved" means that the polymer component 101 is also dissolved to a small extent, but most of the highly soluble substance 102 is dissolved.

The selective dissolution of the highly soluble substance 102 triggers the formation of cracks 104, starting from the areas of the polymer film 100 where the highly soluble substance 102 is unevenly distributed (crack formation process).

Referring to FIG. 8D , the formation of the cracks 104 causes the first curved film piece 131 to further split, forming a plurality of second curved film pieces 132 that are finer than the first curved film piece 131. In this way, the polymer film 100 can be peeled off from the upper surface of the substrate W while promoting splitting of the polymer film 100 using the peeling liquid.

Then, by continuing to supply the stripping liquid, the polymer film 100, which has become multiple second curved film pieces 132, is washed away by the stripping liquid while still holding the particles 150. In other words, the multiple second curved film pieces 132 holding the particles 150 are pushed out of the substrate W and removed from the top surface of the substrate W (polymer film removal process, removal target object removal process). This allows the top surface of the substrate W to be cleaned well. Thereafter, the residue removal process (step S5) is performed (see also FIG. 6).

<Second Substrate Processing>
Fig. 9 is a flowchart for explaining the second substrate processing performed 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.

The main difference between the second substrate processing and the first substrate processing (see Figure 6) is that the light irradiation process (step S3) and the remover solution supply process (step S4) are performed in parallel. Specifically, the upper surface of the substrate W on which the polymer film 100 has been formed is irradiated with light from the light output member 8, while the remover solution is supplied to the upper surface of the substrate W from the remover solution nozzle 10. Light irradiation does not need to be performed during the entire period in which the remover solution is supplied; light irradiation may be performed during only part of the period in which the remover solution is supplied.

The mechanism of the second substrate processing shown in Figure 10 differs from the mechanism shown in the first substrate processing (see Figures 8A to 8D) in that the polymer film 100 is deformed by light irradiation to curve, while the highly soluble substance 102 is selectively dissolved by the stripping solution.

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 when irradiated with light. Therefore, the polymer film 100 is deformed by the light irradiation, and at least a portion of the polymer film 100 is detached from the upper surface of the substrate W. By detaching the polymer film 100 from the upper surface of the substrate W, the particles 150 held on the polymer film 100 can be detached from the upper surface of the substrate W. By removing the polymer film 100 from the upper surface of the substrate W while the particles 150 are detached 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.

Furthermore, according to the first embodiment, the photoreactive compound 103 includes at least one of a diarylethene-based compound and an azobenzene-based compound. The diarylethene-based compound and the azobenzene-based compound undergo structural changes upon irradiation with light. The structural change of the components in the polymer film 100 causes the polymer film 100 to deform, and at least a portion of the polymer film 100 is pulled away from the upper surface of the substrate W.

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

Furthermore, according to the first embodiment, the polymer film 100 formed on the upper surface of the substrate W contains the highly soluble substance 102 in addition to the polymer component 101 and the photoreactive compound 103. Therefore, the highly soluble substance 102 can be dissolved by the stripping liquid while the polymer film 100 is maintained on the upper surface of the substrate W. Therefore, the polymer component 101 can hold the particles 150, while the stripping liquid can be applied to the interface between the polymer film 100 and the upper surface of the substrate W. As a result, the polymer film 100 can be quickly stripped from the upper surface of the substrate W, while the particles 150 can be efficiently removed from the upper surface of the substrate W along with the polymer film 100.

In addition, light irradiation of the polymer film 100 is performed inside a light-shielding chamber 4. This makes it possible to suppress unintended structural changes in the photoreactive compound 103 in the polymer film 100. As a result, the polymer film 100 can be effectively deformed by the light emitted from the light emitting member 8.

<Configuration of Substrate Processing Apparatus According to Second Embodiment>
Next, the configuration of a substrate processing apparatus 1A according to a 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 a wet processing unit 2W provided in the substrate processing apparatus 1A. In FIG. 11, components equivalent to those shown in the above-described FIGS. 1 to 10 are assigned the same reference numerals as in FIG. 1, etc., and descriptions thereof will be omitted. The same applies to FIGS. 12 to 14, which will be described later.

The processing unit 2 according to the second embodiment differs mainly from the wet processing unit 2W according to the first embodiment (see Figure 2) in that a suction nozzle 12 is provided instead of the stripping liquid nozzle 10, and that the polymer-containing liquid does not contain a highly soluble substance.

The suction nozzle 12 is an example of a suction member that performs a suction removal process, which is a polymer film removal process, by sucking the polymer film 100 on the upper surface of the substrate W to remove the polymer film 100 from the upper surface of the substrate W. 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 constitute part of the substrate processing apparatus 1A, or may be a device separate from the substrate processing apparatus 1A that is provided in the facility where the substrate processing apparatus 1A is installed. The suction pipe 43 is provided with a suction valve 53 that opens and closes the suction pipe 43. By opening the suction valve 53, the suction nozzle 12 sucks in the atmosphere in contact with the suction port 12a of the suction nozzle 12.

The suction nozzle 12 can be moved by a nozzle movement mechanism 38. The nozzle movement mechanism 38 can move the suction nozzle 12 horizontally. The suction nozzle 12 can be moved between a central position facing the center of the top surface of the substrate W and a retracted position located outside the processing cup 7 in a plan view. The configuration of the nozzle movement mechanism 38 is similar to that of the other nozzle movement mechanisms 35, 36, and 37.

<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 performed by the substrate processing apparatus 1A. Fig. 13 is a schematic diagram for explaining the state of the substrate W during the substrate processing performed by the substrate processing apparatus 1A.

As shown in FIG. 12, substrate processing by the substrate processing apparatus 1A according to the second embodiment involves a polymer-containing liquid supplying step (step S1), a polymer film forming step (step S2), a light irradiation step (step S3), and a suction removal step (step S7). Below, details of the substrate processing will be described, primarily with reference to FIGS. 11 and 12, focusing on differences from the first substrate processing by the substrate processing apparatus 1 according to the first embodiment (see FIGS. 6 and 7). FIG. 13 will also be referenced as appropriate.

Similar to the first substrate processing, as shown in FIG. 13(a), a polymer-containing liquid supplying process (step S1) is performed to supply a polymer-containing liquid to the upper surface of the substrate W, and then, as shown in FIG. 13(b), a polymer film 100 is formed on the upper surface of the substrate W (polymer film forming process: step S2). Then, as shown in FIG. 13(c), a light irradiation process (step S3) is performed to irradiate the polymer film 100 on the upper surface of the substrate W with light.

Next, a suction removal process (step S7) is performed in which the polymer film 100 on the upper surface of the substrate W is removed by suction from the upper surface of the substrate W.

Specifically, light emission from the light output member 8 is stopped, and then the suction nozzle 12 is positioned 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, the polymer film 100 on the upper surface of the substrate W is sucked through the suction port 12a of the suction nozzle 12, as shown in FIG. 13(d). By continuing suction with the suction nozzle 12, the polymer film 100 is removed from the upper surface of the substrate W, as shown in FIG. 13(e) (polymer film removal process). After opening the suction valve 53, the nozzle movement mechanism 38 moves the suction nozzle 12 horizontally while facing the upper surface of the rotating substrate W, thereby evenly removing the polymer film 100 from the entire upper surface of the substrate. The suction nozzle 12 is operated at a suction flow rate of, for example, 2 L/min for 60 seconds. While suction is being performed by the suction nozzle 12, the substrate W is rotated, for example, at a speed of 0 rpm or more and 100 rpm or less.

In this way, the suction nozzle 12 functions as a suction removal member that performs a suction removal process to suck the polymer film 100 from the upper surface of the substrate W and remove it from the upper surface of the substrate W. Furthermore, the suction nozzle 12 is an example of a polymer film removal member that performs a polymer film removal process to remove the polymer film 100 from the upper surface of the substrate W.

Next, an example of the mechanism by which the polymer film 100 is removed in the substrate processing according to the second embodiment will be described using Figures 14A to 14C. The polymer film 100 is not necessarily removed from the upper surface of the substrate W based on the mechanism described below; rather, it is sufficient that at least a portion of the polymer film 100 is detached from the upper surface of the substrate W due to a structural change in the photoreactive compound, and the polymer film 100 is ultimately removed from the upper surface of the substrate W. Figures 14A to 14C are schematic diagrams for explaining how the polymer film 100 is removed in the substrate processing according to the second embodiment.

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

Referring to Figure 14B, in the light irradiation process (step S3), the polymer film 100 is irradiated with light such as ultraviolet light, causing the structure of the photoreactive compound 103 in the polymer film 100 to change from a first structure 121 (see Figure 14A) to a second structure 122, and the polymer film 100 is deformed so as to curve. The bending of the polymer film 100 causes the polymer film 100 to split, forming multiple curved film pieces 133.

When the photoreactive compound 103 is a diarylethene-based compound, the first structure 121 is an open-ring isomer and the second structure 122 is a closed-ring isomer. When the photoreactive compound is an azobenzene-based compound, the first structure 121 is a trans isomer and the second structure 122 is a cis isomer.

Referring to FIG. 14C , in the suction removal process (step S7), the suction nozzle 12 sucks multiple curved film pieces 133 on the upper surface of the substrate W. This removes multiple curved film pieces 133 from the upper surface of the substrate W. Because at least a portion of the polymer film 100 has been peeled off from the upper surface of the substrate W by the light irradiation and the polymer film 100 has been split, it is easier to separate the polymer film 100 from the upper surface of the substrate W by the suction force of the suction nozzle 12 compared to separating the polymer film 100 from the substrate W that has not been irradiated with light.

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 when irradiated with light. Therefore, the polymer film 100 is deformed by the light irradiation, and at least a portion of the polymer film 100 is detached from the upper surface of the substrate W. By detaching the polymer film 100 from the upper surface of the substrate W, the particles 150 held on the polymer film 100 can be detached from the upper surface of the substrate W. By removing the polymer film 100 from the upper surface of the substrate W while the particles 150 are detached 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.

Furthermore, according to the second embodiment, the photoreactive compound 103 includes at least one of a diarylethene-based compound and an azobenzene-based compound. The diarylethene-based compound and the azobenzene-based compound undergo a structural change upon irradiation with light. This structural change deforms the polymer film 100, and at least a portion of the polymer film 100 is pulled away from the upper surface of the substrate W.

Furthermore, according to the second embodiment, at least a portion of the polymer film 100 is separated from the upper surface of the substrate W, making the polymer film 100 more likely to peel 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.

Furthermore, if the polymer film 100 can be removed by suction without supplying a stripping liquid to the top surface of the substrate W, the effort of drying the top surface of the substrate W can be eliminated.

<Modifications of Light Emitting Member>
Next, a description will be given of modified examples of the light emitting member 8. The configuration of the light emitting member 8 is not limited to those shown in Figures 2 and 11, and it may be configured so as 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 may have the configurations shown in Figures 15 to 17.

Figure 15 is a schematic diagram illustrating a first modified example of the light output member. Figure 16 is a schematic diagram illustrating a second modified example of the light output member. Figure 17 is a schematic diagram illustrating a third modified example of the light output member.

Referring to FIG. 15, the light emitting member 8 may be configured to move horizontally between the irradiation position and the home position (retracted position) by a movement mechanism 86 provided within the chamber 4.

The irradiation position is a position where the light output member 8 faces the upper surface of the substrate W. The irradiation position is a position where light can be emitted from the light output member 8 onto the upper surface of the substrate W. The retracted position is a position where light is not emitted from the light output member 8 onto the upper surface of the substrate W. When the light output member 8 is located at the irradiation position, it faces the upper surface of the substrate W. When the light output 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.

The light output member 8 according to the first modified example includes a lamp 80 and a lamp holder 81 that houses the lamp 80. The movement 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 move the arm 87 horizontally, and a ball screw mechanism that raises and lowers the arm 87 together with the rotation shaft 89.

In the first variant, light can be irradiated onto the top surface of the substrate W while moving the light output member 8 in a direction parallel to the top surface of the substrate W.

In the second variant shown in Figure 16, the lamp 80 is rod-shaped and arranged within a linearly extending arm 87. In this case, light can be emitted over a wider area than in the first variant shown in Figure 15.

In the third modified example shown in Figure 17, the light output member 8 is provided as a light output member 202 in a dry processing unit 2D provided in the substrate processing apparatus 1, 1A, separate from the wet processing unit 2W shown in Figures 2, 9, and 11.

The dry processing unit 2D includes a dry chamber 200, a mounting table 201 disposed within the dry chamber 200 for mounting a substrate W thereon, 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 a facing member 203 having a facing surface 203a that faces the upper surface of the substrate W on the mounting table 201, and a plurality of lamps 204 attached to the facing member 203 as light sources. A power supply unit 205 configured to energize and stop the power supply to the lamps 204 is connected to the lamps 204. Details of the lamps 204 are similar to those of the lamps 80 described above (see Figure 2).

In the third modified example, the spin chuck 5 of the wet processing unit 2W functions as a first substrate holding member that holds the substrate W at 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 at the second holding position. The first substrate holding member and the second substrate holding member constitute a substrate holding member.

The substrate W is transported between the wet processing unit 2W and the dry processing unit 2D by the transport robot CR. Therefore, the polymer film formation step (step S2) is performed in the wet processing unit 2W, and the substrate W is transported 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 transported to the wet processing unit 2W. Then, in the wet processing unit 2W, the stripping 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 performed.

The polymers and highly soluble substances used in each of the above-mentioned embodiments are described below.

Hereinafter, expressions such as "C _x-y ,""C _{x -C y} ," and "C _x " refer to the number of carbons in a molecule or substituent. For example, C _1-6 alkyl refers to an alkyl chain having at least one carbon, and at most six carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

When a polymer has multiple types of repeating units, these repeating units are copolymerized. Unless otherwise specified, these copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown in structural formulas, the n, m, etc. in parentheses indicate the number of repeating units.

<Polymer component (low-solubility substance) contained in polymer-containing liquid>
The (A) 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, the (A) polymer component may include at least one of novolak, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, the (A) polymer component may include at least one of novolak, polyhydroxystyrene, polycarbonate, and copolymers of combinations thereof. The novolak may be a phenolic novolak.

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

In one preferred embodiment, the (A) polymer component is dried to form a film, and the film is peeled off while retaining the object to be removed, without being largely dissolved by the stripping solution. However, embodiments in which only a small portion of the (A) polymer component is dissolved by the stripping solution are acceptable.

Preferably, the (A) polymer component does not contain fluorine and/or silicon, and more preferably does not contain either.

The copolymerization is preferably random copolymerization or block copolymerization.

While not intending to limit the scope of the rights, specific examples of the (A) polymer component include the compounds shown in Chemical Formulas 9 to 15 below.

(An asterisk * indicates a bond to an adjacent building block.)

(R represents a substituent such as _C1-4 alkyl. An asterisk * indicates a bond to an adjacent structural unit.)

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

Solubility can be evaluated using known methods. For example, 100 ppm of (A) or (B) described below is added to 5.0% by mass of aqueous ammonia at 20°C to 35°C (more preferably 25±2°C) in a flask, the flask is capped, and the flask is shaken in a shaker for 3 hours. The solution can be determined by observing whether (A) or (B) has dissolved. Shaking can be by stirring. Dissolution can also be determined visually. If no solution is found, the solubility is considered to be less than 100 ppm, and if solution is found, the solubility is considered to be 100 ppm or more. A solubility of less than 100 ppm is considered insoluble or slightly soluble, and a solubility of 100 ppm or more is considered soluble. In a broad sense, soluble includes slightly soluble. The order of decreasing solubility is insoluble, slightly soluble, and soluble. In a narrow sense, slightly soluble is less soluble than soluble, and more soluble than slightly soluble.

<Highly soluble substance contained in polymer-containing liquid>
The (B) highly soluble substance is (B') a crack-accelerating component. The (B') crack-accelerating component contains a hydrocarbon and further contains a hydroxy group (-OH) and/or a carbonyl group (-C(=O)-). When the (B') crack-accelerating component is a polymer, one of the constituent units contains a hydrocarbon on a unit-by-unit basis and further contains a hydroxy group and/or a carbonyl group. Examples of the carbonyl group include carboxylic acid (-COOH), aldehyde, ketone, ester, amide, and enone, with carboxylic acid being preferred.

Without intending to limit the scope of the rights or being bound by theory, it is believed that when the polymer-containing liquid dries to form a polymer film on the substrate and the stripper liquid strips the polymer film, the highly soluble substance (B) creates a portion that triggers the polymer film to peel off. For this reason, it is preferable that the highly soluble substance (B) has a higher solubility in the stripper liquid than the polymer (A). Examples of embodiments in which the crack-promoting component (B') contains a ketone as the carbonyl group include cyclic hydrocarbons. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

In a more specific embodiment, the highly soluble substance (B) is represented by at least one of the following (B-1), (B-2), and (B-3):
(B-1) is a compound containing 1 to 6 (preferably 1 to 4) structural units of the following chemical formula 16, and each structural unit is linked by a linking group (linker L ₁ ). Here, the linker L ₁ may be a single bond or a C _1-6 alkylene. The C _1-6 alkylene links the structural units as a linker and is not limited to a divalent group. It is preferably a divalent to tetravalent group. The C _1-6 alkylene may be linear or branched.

Cy ₁ is a _C5-30 hydrocarbon ring, preferably phenyl, cyclohexane or naphthyl, more preferably phenyl. In a preferred embodiment, the linker L ₁ connects multiple Cy _1s .

Each _R1 is independently a _C1-5 alkyl, preferably methyl, ethyl, propyl, or butyl. The _C1-5 alkyl may be linear or branched.

n _b1 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. _{n b1′} is 0, 1, 2, 3 or 4, and preferably 0, 1 or 2.

The following chemical formula 17 is a chemical formula that represents the structural unit described in chemical formula 16 using a linker L _9. The linker L ₉ is preferably a single bond, methylene, ethylene, or propylene.

While not intending to limit the scope of the rights, suitable 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, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These may also be obtained by polymerization or condensation.

As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol shown in the following chemical formula 18 will be explained. In (B-1), this compound has three structural units of chemical formula 16, which are linked by a linker L ₁ (methylene). n _b1 =n _b1' =1, and R ₁ is methyl.

(B-2) is represented by the following chemical formula 19.

R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ each independently represent hydrogen or C _1-5 alkyl, preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

Linkers _L21 and _L22 are each independently a _{C1-20 alkylene, a C1-20} cycloalkylene, a _C2-4 alkenylene, _{a C2-4 alkynylene} , or a _C6-20 arylene. These groups may be substituted with a _C1-5 alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon group having one or more double bonds, and alkynylene means a divalent hydrocarbon group having one or more triple bonds. Linkers _L21 and _L22 are preferably a _C2-4 alkylene, acetylene ( _C2 alkynylene), or phenylene, more preferably a _C2-4 alkylene or acetylene, and even more preferably acetylene.

n _b2 is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

While not intending to limit the scope of the rights, suitable examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, suitable examples of (B-2) include 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.

(B-3) is a polymer containing a structural unit represented by the following chemical formula 20, and has a weight-average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

Here, R ₂₅ is —H, —CH ₃ , or —COOH, preferably —H or —COOH. It is also acceptable for one (B-3) polymer to contain two or more types of constitutional units each represented by Chemical Formula 20.

While not intending to limit the scope of the invention, suitable examples of the (B-3) polymer include polymers of acrylic acid, maleic acid, or combinations thereof. More suitable examples include polyacrylic acid and maleic-acrylic acid copolymers.

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

As an example, the maleic acid acrylic acid copolymer shown in the following chemical formula 21 will be described. This copolymer is included in (B-3) and has two types of structural units represented by chemical formula 20, with R ₂₅ being —H in one structural unit and _—COOH in the other structural unit.

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

(B) The 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, more preferably 100 to 3000.

<Other embodiments>
The present invention is not limited to the above-described embodiment, and can be embodied in other forms.

(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 (e.g., 10 rpm), and then, after the discharge of the polymer-containing liquid from the polymer-containing liquid nozzle 9 has stopped, the rotation of the substrate W may be accelerated to rotate the substrate W at a spin-off speed (e.g., 1500 rpm). This allows the polymer-containing liquid adhering to the central region of the upper surface of the substrate W to be spread thinly over the upper surface of the substrate W, forming a thin film of polymer-containing liquid on the upper surface of the substrate W.

(2) The polymer film removal process may be a dissolving liquid supply process in which, after the light irradiation process, a dissolving liquid that dissolves the polymer film 100 is supplied to the upper surface of the substrate W. Because at least a portion of the polymer film 100 has been peeled off from the upper surface of the substrate W by the light irradiation, even if the polymer film 100 is dissolved by supplying a dissolving liquid, the particles 150 that have been detached from the upper surface of the substrate W due to the peeling of the polymer film 100 caused by the light irradiation will be removed from the upper surface of the substrate W together with the dissolving liquid.

(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.

(4) The polymer film 100 does not necessarily have to become curved film pieces bent into a bow shape upon light irradiation; it is sufficient that at least a portion of the polymer film 100 is peeled off. For example, the polymer film 100 may be deformed into a hemispherical shape upon light irradiation, forming hemispherical film pieces. Furthermore, the polymer film 100 may be bent into a V shape upon light irradiation, or V-shaped film pieces may be formed. Furthermore, film pieces of various shapes may be mixed together.

(5) Unlike the above-described embodiments, a stripping liquid nozzle 10 and a suction nozzle 12 may be provided, and the polymer film 100 may be removed by both supplying the stripping liquid and suctioning the polymer film 100. For example, the polymer film 100 may be removed by suction, and then the stripping liquid may be supplied to the upper surface of the substrate W. Furthermore, suctioning the polymer film 100 and irradiating it with light may be performed in parallel.

(6) In each of the above-described embodiments, substrate processing is performed on the upper surface of the substrate W. However, substrate processing may also be performed on the lower surface of the substrate W.

(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 suctions the substrate W to the spin base 20.
(8) The spin chuck 5 does not necessarily need to horizontally hold the substrate W. That is, the spin chuck 5 may hold the substrate W vertically, or may hold the substrate W so that the top surface of the substrate W is inclined relative to the horizontal plane.

(9) In each of the above-described embodiments, multiple fluids are ejected from multiple nozzles. However, the manner in which each fluid is ejected is not limited to the above-described embodiments.

(10) In each of the above-described embodiments, illustrations of pipes, pumps, valves, actuators, etc. are omitted, but this does not mean that these components do not exist; in reality, these components are provided in appropriate positions. For example, each pipe may be provided with a flow rate adjustment valve (not shown) that adjusts the flow rate of the processing liquid ejected from the corresponding processing liquid nozzle.

(11) In each of the above-described embodiments, the controller 3 controls the entire substrate processing apparatus 1. However, the controllers controlling each component of the substrate processing apparatus 1 may be distributed across multiple locations. Furthermore, the controller 3 does not need to directly control each component, and signals output from the controller 3 may be received by a slave controller that controls each component of the substrate processing apparatus 1.

(12) In the above-described embodiment, the substrate processing apparatus 1 includes transport robots IR and CR, multiple processing units 2, and a controller 3. However, the substrate processing apparatus 1 may be configured with a single processing unit 2 and a controller 3 and may not include a transport robot. Alternatively, the substrate processing apparatus 1 may be configured with only a single processing unit 2. In other words, the processing unit 2 may be an example of a substrate processing apparatus.

Various other modifications may be made within the scope of the claims.

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: Stripping liquid nozzle (stripping liquid supply member, polymer film removal member)
12: Suction nozzle (suction member, polymer film removal member)
100: Polymer film 101: Polymer component 102: Highly soluble substance 103: Photoreactive compound 201: Mounting table (substrate holding member)
202: Light emitting member W: Substrate

Claims (10)

a substrate holding member for holding the substrate at a holding position;
a polymer film forming member that forms a polymer film containing a photoreactive compound including a diarylethene compound and a polymer component on a main surface of the substrate held at the holding position;
a light-emitting member that emits light including ultraviolet light toward a main surface of the substrate held at the holding position to isomerize the diarylethene compound from an open-ring form to a closed-ring form ;
a polymer film removal member that performs a polymer film removal process to remove a polymer film from a main surface of the substrate held at the holding position. 2 . The substrate processing apparatus according to claim 1 , wherein the polymer film removal member includes a stripping liquid supply member that performs, as the polymer film removal process, a stripping liquid supply process that supplies a stripping liquid that strips the polymer film onto the main surface of the substrate. The substrate processing apparatus according to claim 2 , wherein the polymer film forming member forms the polymer film further containing a highly soluble substance that is more soluble in the stripping liquid than the polymer component. 4. The substrate processing apparatus according to claim 1 , wherein the polymer film removal member includes a suction member that performs a suction removal process to remove the polymer film from the main surface of the substrate by sucking the polymer film as the polymer film removal process. 5. The substrate processing apparatus according to claim 1 , wherein in the polymer film removal process, at least a portion of the polymer film is detached from the main surface of the substrate. a polymer film forming step of forming a polymer film containing a photoreactive compound including a diarylethene 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 diarylethene compound from an open-ring form to a closed-ring form ;
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 supplying step of supplying a stripping liquid for stripping the polymer film onto 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 the step of forming the polymer film further containing a highly soluble substance that is more soluble in the stripping solution than the polymer component. The substrate processing method according to claim 6 , wherein the polymer film removing step includes a suction removing step of removing the polymer film from the main surface of the substrate by suction. The substrate processing method according to claim 6 , wherein the polymer film removing step includes the step of peeling the polymer film off the main surface of the substrate.