JP7596089B2 - SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS - Google Patents

Description

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

The following Patent Document 1 discloses a substrate processing method in which a processing film that holds objects to be removed, such as particles, present on the surface of the substrate is formed on the surface of the substrate, and the processing film that holds the objects to be removed is peeled off and removed.
In this substrate processing method, a part of the processing film is dissolved in a stripping solution, and the remaining part is maintained in a solid state, thereby forming through holes in the processing film. By continuing to supply the stripping solution, the stripping solution acts on the interface between the substrate and the processing film through the through holes, and the processing film is stripped from the substrate.

JP 2019-212889 A

In the substrate processing method described in Patent Document 1, it is necessary to maintain most of the processing film in a solid state while dissolving a part of the processing film with a stripping solution to form through holes, and therefore the processing film needs to be composed of two components (a low solubility component and a high solubility component) that have different solubilities in the stripping solution.
Therefore, one object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can break up a processing film without supplying liquid to the processing film in a configuration in which a processing film is removed from a surface of a substrate using a processing film removal liquid.

One embodiment of the present invention provides a substrate processing method including a process film forming step of supplying a process liquid to a surface of a substrate and solidifying or curing the process liquid on the surface of the substrate to form a process film on the surface of the substrate, a light irradiation step of irradiating the process film with light to split the process film on the surface of the substrate, and a process film removal step of supplying a process film removal liquid to the surface of the substrate after the light irradiation step and removing the split process film from the surface of the substrate with the process film removal liquid.

According to this method, the treatment film is split by irradiating the treatment film with light before supplying the treatment film removal liquid to the treatment film. The split treatment film is removed from the surface of the substrate by the treatment film removal liquid. Since the treatment film can be split before supplying the treatment film removal liquid, there is no need to split the treatment film by the treatment film removal liquid. In this way, the treatment film can be split without supplying liquid to the treatment film.

In one embodiment of the present invention, the processing film formed in the processing film forming step holds the object to be removed present on the surface of the substrate, and the light irradiating step includes a step of splitting the processing film to form processing film pieces larger than the object to be removed.
According to this method, since the treated film pieces are larger than the object to be removed, it is possible to prevent the object to be removed from falling off the treated film pieces even after the treated film is split, and therefore it is possible to effectively remove the object to be removed from the surface of the substrate.

In one embodiment of the present invention, the substrate processing method further includes an irradiation peeling step, after the light irradiation step and before the processing film removal step, of peeling the processing film from the surface of the substrate by irradiating the processing film with light.
According to this method, the light irradiation can not only split the treatment film, but also peel the treatment film from the surface of the substrate. Therefore, it is not necessary to split the treatment film or peel the treatment film by the treatment film removal solution. Therefore, the treatment film can be removed from the upper surface of the substrate using the treatment film removal solution that has almost no property of dissolving the treatment film. This improves the selectivity of the combination of the treatment solution and the treatment film removal solution.

In one embodiment of the present invention, the treatment film removing step includes a liquid removing step of removing the treatment film from the surface of the substrate by the treatment film removing liquid. According to this method, even if the treatment film is not removed by light irradiation, it can be removed from the surface of the substrate by the treatment film removing liquid.
In one embodiment of the present invention, the treated film contains a first polymer having a solid-state main chain and a side chain bonded to the main chain and configured to be liquefied by irradiation with light, and the light irradiation step includes a step of splitting the treated film by liquefying the side chain of the first polymer.

According to this method, a part (side chain) of the first polymer is liquefied by irradiation with light. Therefore, a part of the treated film is liquefied while a large part of the treated film is kept in a solid state by irradiation with light. Therefore, the treated film can be split before the treatment film removal solution is supplied.
In one embodiment of the present invention, the treatment film contains a second polymer that is decomposed by irradiation with light, and the light irradiation step includes a step of decomposing the second polymer to thereby split the treatment film.

According to this method, the second polymer is decomposed by irradiation with light. Therefore, the treated film, which was held together by the presence of the second polymer, is no longer able to maintain its shape due to the decomposition of the second polymer and is split. Therefore, the treated film can be split before the supply of the treated film removal solution.
In one embodiment of the present invention, the second polymer has a plurality of hydrocarbon groups and C-O bonds connecting the hydrocarbon groups together, and the light irradiation step cuts the C-O bonds by irradiation with light to form decomposition products made of hydrocarbon compounds.

There are cases where hydrophobic objects to be removed are attached to the surface of the substrate. Therefore, the objects to be removed are held in the treatment film by being surrounded by the hydrocarbon groups of the second polymer in the treatment film. If a decomposition product consisting of a hydrocarbon compound is formed after the decomposition of the second polymer, the objects to be removed are maintained in a state surrounded by the hydrocarbon groups in the decomposition product even after the second polymer is decomposed. Therefore, even after the treatment film is split, the objects to be removed can be firmly held by the split treatment film.

In one embodiment of the present invention, the treatment liquid contains the second polymer and a crosslinking agent that crosslinks the second polymers together by irradiation with light, and the treatment film forming step includes a photocrosslinking step of crosslinking the polymers together with the crosslinking agent to harden the polymers.
According to this method, the second polymers are crosslinked with each other by the crosslinking agent. This makes it possible to increase the hardness of the treatment film compared to when the second polymer is not crosslinked. By increasing the hardness of the treatment film, the treatment film can firmly hold the object to be removed. Therefore, the treatment film removal solution can remove the object to be removed together with the split treatment film outside the substrate. Therefore, the object to be removed can be successfully removed from the surface of the substrate.

In one embodiment of the present invention, the light irradiation step includes a step of irradiating light toward the surface of the substrate through a photomask. Therefore, the treatment film is exposed according to the pattern of the photomask, so that light can be irradiated only to a portion of the treatment film. For example, this is useful when there are portions of the substrate surface that need to be avoided from exposure, or when it is desired to leave part of the treatment film on the substrate. Unlike this method, if a liquid is supplied to split the treatment film, it is difficult to split only a portion of the treatment film.

Another embodiment of the present invention provides a substrate processing apparatus including a processing liquid supply unit that supplies a processing liquid toward a surface of a substrate, a processing film forming unit that solidifies or hardens the processing liquid on the surface of the substrate to form a processing film on the surface of the substrate, a light irradiation unit that irradiates the surface of the substrate with light, a processing film removal liquid supply unit that supplies a processing film removal liquid that removes the processing film formed on the substrate toward the surface of the substrate, and a controller that controls the processing liquid supply unit, the processing film formation unit, the light irradiation unit, and the processing film removal liquid supply unit.

The controller is programmed to execute a process of forming a treatment film on the surface of the substrate by supplying a treatment liquid from the treatment liquid supply unit and forming a treatment film on the surface of the substrate by the treatment film formation unit, a process of irradiating the treatment film with light from the light irradiation unit to split the treatment film on the surface of the substrate, and a process of removing a treatment film from the treatment film removal liquid supply unit after the light irradiation process, in which a treatment film removal liquid is supplied to the surface of the substrate from the treatment film removal liquid supply unit and the split treatment film is removed from the surface of the substrate by the treatment film removal liquid.

This device achieves the same effects as the substrate processing method.

FIG. 1 is a schematic plan view showing a layout of a substrate processing apparatus according to a first embodiment of the present invention. FIG. 2 is a schematic partial cross-sectional view showing a schematic configuration of a processing unit provided in the substrate processing apparatus. FIG. 3 is a schematic diagram for explaining the properties of the first polymer contained in the treatment film. FIG. 4 is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus. FIG. 5 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus. FIG. 6A is a schematic diagram for explaining the processing liquid supply step (step S1) of the substrate processing. FIG. 6B is a schematic diagram for explaining the processing film forming step (step S2) of the substrate processing. FIG. 6C is a schematic diagram for explaining the processing film forming step (step S2) of the substrate processing. FIG. 6D is a schematic diagram for explaining the light irradiation step (step S3) of the substrate processing. FIG. 6E is a schematic diagram for explaining the processing film removing step (step S4) of the substrate processing. FIG. 6F is a schematic diagram for explaining the processing film removing step (step S4) of the substrate processing. FIG. 6G is a schematic diagram for explaining the residue dissolving step (step S5) of the substrate processing. FIG. 7A is a schematic diagram for explaining the state near the surface of the substrate during the substrate processing. FIG. 7B is a schematic diagram for explaining the state near the surface of the substrate during the substrate processing. FIG. 7C is a schematic diagram for explaining the state near the surface of the substrate during the substrate processing. FIG. 7D is a schematic diagram for explaining the state near the surface of the substrate during the substrate processing. FIG. 8 is a schematic diagram for explaining the state near the surface of the substrate during the substrate processing, showing how the processing film is peeled off from the surface of the substrate by irradiation with light. FIG. 9A is a schematic diagram for explaining an example of a second polymer contained in the treatment film. FIG. 9B is a schematic diagram for explaining the decomposition mechanism of the second polymer. FIG. 9C is a schematic diagram for explaining how the treatment film containing the second polymer holds the object to be removed. FIG. 10A is a schematic diagram for explaining the processing film forming step (step S2) in the modified example of the substrate processing. FIG. 10B is a schematic diagram for explaining the processing film forming step (step S2) in the modified substrate processing method. FIG. 11 is a schematic diagram for explaining a first modified example of the light irradiation unit provided in the processing unit. FIG. 12 is a schematic diagram for explaining a second modified example of the light irradiation unit. FIG. 13 is a schematic view for explaining the configuration of a wet processing unit provided in the substrate processing apparatus according to the second embodiment. FIG. 14 is a schematic view for explaining the configuration of a dry processing unit provided in the substrate processing apparatus according to the second embodiment. FIG. 15A is a schematic view for explaining a state near the surface of a substrate during substrate processing by the substrate processing apparatus according to the second embodiment. FIG. 15B is a schematic view for explaining the state near the surface of the substrate during substrate processing by the substrate processing apparatus according to the second embodiment. FIG. 15C is a schematic view for explaining the state near the surface of the substrate during substrate processing by the substrate processing apparatus according to the second embodiment. FIG. 15D is a schematic view for explaining the state near the surface of the substrate during substrate processing by the substrate processing apparatus according to the second embodiment. FIG. 16 is a schematic diagram for explaining a state near a surface of a substrate during substrate processing by the substrate processing apparatus according to the second embodiment; FIG. 17 is a schematic view for explaining the configuration of a substrate processing apparatus according to the third embodiment.

Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.
First Embodiment
FIG. 1 is a schematic plan view showing a layout of a substrate processing apparatus 1 according to one embodiment of the present invention.
The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a disk-shaped substrate. As the substrate W, a substrate having an etchable component exposed on the surface can be used. As the substrate W, a substrate having at least one of SiO ₂ (silicon oxide), TiN (titanium nitride), Cu (copper), and Ru (ruthenium) exposed on the surface is preferably used. Only one of the above-mentioned substances may be exposed on the surface of the substrate W, or a plurality of the above-mentioned substances may be exposed on the surface of the substrate W. An etchable substance other than the above-mentioned substances may be exposed on the surface of the substrate W.

The substrate processing apparatus 1 includes a plurality of processing units 2 that process substrates W with a fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W to be processed in the processing units 2 is placed, 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 the substrate W between the carrier C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing units 2. The processing units 2 have, for example, the same configuration. Although described in detail below, fluids supplied to the substrate W in the processing units 2 include a processing liquid, a processing film removing liquid, a residue dissolving liquid, etc.

FIG. 2 is a schematic diagram for explaining an example of the configuration of the processing unit 2. As shown in FIG.
The processing unit 2 includes a chamber 4 , a spin chuck 5 , a processing cup 7 , a light irradiation unit 8 , a first moving nozzle 9 , a second moving nozzle 10 , and a third moving nozzle 11 .
The chamber 4 accommodates a spin chuck 5, a processing cup 7, a light irradiation unit 8, a first moving nozzle 9, a second moving nozzle 10, and a third moving nozzle 11. The chamber 4 is formed with an entrance 4a through which the transport robot CR loads and unloads the substrate W. The chamber 4 is provided with a shutter unit 4b that opens and closes the entrance 4a.

The spin chuck 5 is an example of a substrate holding and rotating unit that rotates the substrate W about a rotation axis A1 (vertical axis) while holding the substrate W horizontally. The rotation axis A1 is a vertical line passing through the center of the substrate W. The spin chuck 5 includes a plurality of chuck pins 20, a spin base 21, a rotation shaft 22, and a spin motor 23.
The spin base 21 has a horizontally extending disk shape. A plurality of chuck pins 20 for gripping the peripheral edge of the substrate W are arranged at intervals in the circumferential direction of the spin base 21 on the upper surface of the spin base 21.

The spin base 21 and the plurality of chuck pins 20 constitute a substrate holding unit that horizontally holds the substrate W. The substrate holding unit is also called a substrate holder.
The rotation shaft 22 extends vertically along the rotation axis A1. The upper end of the rotation shaft 22 is coupled to the center of the lower surface of the spin base 21. The spin motor 23 applies a rotational force to the rotation shaft 22. The rotation shaft 22 is rotated by the spin motor 23, thereby rotating the spin base 21. As a result, the substrate W is rotated about the rotation axis A1. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W about the rotation axis A1.

The light irradiation unit 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 as light sources attached to the facing surface 6a.
The facing member 6 is formed in a disk shape having a diameter substantially equal to or greater than that of the substrate W. The facing surface 6a is disposed above the spin chuck 5 and along a substantially horizontal plane.

A rotating shaft 60 is fixed to the opposing member 6 on the side opposite to the opposing 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 the space. For this reason, the facing member 6 is also called a blocking plate.
The lamps 80 are disposed at equal intervals across the entire area of the facing surface 6a. The processing unit 2 further includes a lamp energizing unit 85 configured to energize the lamps 80 or stop energizing the lamps 80. The lamps 80 emit light when energized. Examples of the light emitted from each lamp 80 include infrared light, ultraviolet light, and visible light.

The processing unit 2 further includes a counter member lifting unit 61 that lifts and lowers the counter member 6, and a counter member rotating unit 62 that rotates the counter member 6 about the rotation axis A1.
The opposing member lifting unit 61 can position the opposing member 6 in the vertical direction at any position (height) between the lower position and the upper position. The lower position is a position where the opposing surface 6a is closest to the substrate W within the movable range of the opposing member 6. The upper position is a position where the opposing surface 6a is farthest from the substrate W within the movable range of the opposing member 6. When the opposing member 6 is located at the upper position, the transport robot CR can access the spin chuck 5 to load and unload the substrate W.

The opposing member lifting unit 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 a driving force to the ball screw mechanism. The opposing member lifting unit 61 is also called an opposing member lifter (shield lifter). The opposing member rotating unit 62 includes, for example, a motor (not shown) that rotates the rotating shaft 60.

The opposing member lifting unit 61 lifts and lowers the plurality of lamps 80 together with the opposing member 6. The opposing member lifting unit 61 is an example of a lamp lifting unit (lamp lifter). The opposing member rotating unit 62 rotates the plurality of lamps 80 together with the opposing member 6. The opposing member rotating unit 62 is an example of a lamp rotating unit (lamp motor).
The processing cup 7 includes a plurality of guards 71 for receiving liquid that splashes outward from the substrate W held on the spin chuck 5, a plurality of cups 72 for receiving liquid guided downward by the multiple guards 71, and a cylindrical outer wall member 73 that surrounds the multiple guards 71 and the multiple cups 72.

In this embodiment, an example is shown in which two guards 71 (a first guard 71A and a second guard 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided.
Each of the first cup 72A and the second cup 72B has the form of an upwardly opening annular groove.

The first guard 71A is disposed so as to surround the spin base 21. The second guard 71B is disposed so as to surround the spin base 21 on the outer side of the first guard 71A.
The first guard 71A and the second guard 71B each have a substantially cylindrical shape. The upper end of each guard 71 is inclined inward toward the spin base 21.

The first cup 72A receives the liquid guided downward by the first guard 71 A. The second cup 72B is formed integrally with the first guard 71 A, and receives the liquid guided downward by the second guard 71B.
The processing unit 2 includes a guard lifting unit 74 that vertically raises and lowers the first guard 71A and the second guard 71B separately. The guard lifting unit 74 raises and lowers the first guard 71A between a lower position and an upper position. The guard lifting unit 74 raises and lowers the second guard 71B between a lower position and an upper position.

When the first guard 71A and the second guard 71B are both in the upper position, liquid splashed from the substrate W is received by the first guard 71A. When the first guard 71A is in the lower position and the second guard 71B is in the upper position, liquid splashed from the substrate W is received by the second guard 71B. When the first guard 71A and the second guard 71B are both in the lower position, the transport robot CR can access the spin chuck 5 to load and unload the substrate W.

The guard lifting unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first guard 71A, a first motor (not shown) that provides a driving force to the first ball screw mechanism, a second ball screw mechanism (not shown) coupled to the second guard 71B, and a second motor (not shown) that provides a driving force to the second ball screw mechanism. The guard lifting unit 74 is also called a guard lifter.

The first movable nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (discharges) a processing liquid toward the top surface (upper surface) of the substrate W held by the spin chuck 5 .
The first movable nozzle 9 is moved in the horizontal and vertical directions by the first nozzle movement unit 35. The first movable nozzle 9 can move in the horizontal direction between a central position and a home position (retracted position). When the first movable nozzle 9 is located at the central position, it faces a central region of the upper surface of the substrate W.

When the first moving nozzle 9 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 first moving nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.
The first nozzle moving unit 35 may include an arm (not shown) connected to the first moving nozzle 9 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending vertically, and a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

The pivot drive unit rotates the pivot about a vertical axis to swing the arm. The pivot drive unit raises and lowers the pivot in the vertical direction to raise and lower the arm. The first moving nozzle 9 moves in the horizontal and vertical directions in response to the swing and raising and lowering of the arm.
The first moving nozzle 9 is connected to a processing liquid pipe 40 that guides the processing liquid. When a processing liquid valve 50 disposed in the processing liquid pipe 40 is opened, the processing liquid is discharged downward in a continuous flow from the first moving nozzle 9. When the processing liquid valve 50 is opened while the first moving nozzle 9 is located at the central position, the processing liquid is supplied to a central region of the upper surface of the substrate W.

The processing liquid contains a solute and a solvent. The processing liquid solidifies or hardens when at least a portion of the solvent contained in the processing liquid volatilizes (evaporates). The processing liquid solidifies or hardens on the substrate W to form a solid processing film. When the processing liquid solidifies or hardens, the processing film captures and holds within itself the objects to be removed that are present on the substrate W. The objects to be removed are, for example, foreign matter such as particles adhering to the surface of the substrate W.

Here, "solidification" refers to the solidification of a solute due to forces acting between molecules or atoms as a solvent evaporates, for example. "Hardening" refers to the solidification of a solute due to chemical changes such as polymerization or crosslinking, for example. Therefore, "solidification or hardening" refers to the "solidification" of a solute due to various factors.
In addition, the treatment film does not have to be composed of only solid components. The treatment film may be semi-solid, composed of both solid and liquid components, as long as it maintains a constant shape as a whole. In other words, it is not necessary to completely remove the solvent from the treatment liquid, and the solvent may remain in the treatment film.

The treatment liquid contains a polymer as a solute. The polymer contained in the treatment liquid is, for example, a first polymer having a main chain in a solid state and a side chain bonded to the main chain and liquefied by irradiation with light from the light irradiation unit 8.
The main chain of the first polymer remains in a solid state even after the light irradiation. Therefore, the entire treated film is in a solid state before the light irradiation from the light irradiation unit 8. On the other hand, when the treated film is irradiated with light from the light irradiation unit 8, a part of the treated film is liquefied and the treated film is split.

As shown in Fig. 3, the first polymer may be a polymer 200 having a main chain 201 composed of a hydrocarbon group and a side chain 202 having an azobenzene group in the molecule. The azobenzene group is reversibly photoisomerized into a trans isomer and a cis isomer when irradiated with light.
Specifically, an azobenzene group in a trans form is changed to a cis form by ultraviolet light, and an azobenzene group in a cis form is changed to a trans form by visible light or heat. When the azobenzene group is in a trans form, the side chain 202 is in a solid state. When the azobenzene group is in a cis form, the side chain is in a liquid state. For example, ultraviolet light of 365 nm is used as the ultraviolet light that changes the azobenzene group to a cis form. The wavelength of the ultraviolet light that changes the azobenzene group to a cis form is not limited to 365 nm.

Therefore, before the treatment film is irradiated with ultraviolet light, the azobenzene group is in the trans form, and the entire treatment film is maintained in a solid state. On the other hand, when the treatment film is irradiated with ultraviolet light, the azobenzene group changes to the cis form, and a part of the treatment film is liquefied. This causes the treatment film to split.
The first polymer is not limited to the polymer 200 shown in Fig. 3, but may have a main chain in a solid state and a side chain that is bonded to the main chain and liquefied by irradiation with light. For example, the first polymer may have an azobenzene derivative as the side chain.

2 again, the second moving nozzle 10 is an example of a processing film removing liquid nozzle (processing film removing liquid supply unit) that supplies (discharges) a processing film removing liquid such as pure water in a continuous flow toward the upper surface of the substrate W held by the spin chuck 5. The processing film removing liquid is a liquid for removing a processing film formed on the substrate W by pushing it out of the substrate W without dissolving it.
The second movable nozzle 10 is moved in the horizontal and vertical directions by the second nozzle movement unit 36. The second movable nozzle 10 can move in the horizontal direction between a central position and a home position (retracted position).

When the second moving nozzle 10 is located at the central position, it faces a central region of the upper surface of the substrate W. When the second moving nozzle 10 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 second moving nozzle 10 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.
The second nozzle moving unit 36 has a configuration similar to that of the first nozzle moving unit 35. That is, the second nozzle moving unit 36 may include an arm (not shown) connected to the second moving nozzle 10 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending along the vertical direction, and a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

The second moving nozzle 10 is connected to a processing film removal liquid pipe 41 that guides the processing film removal liquid to the second moving nozzle 10. When a processing film removal liquid valve 51 interposed in the processing film removal liquid pipe 41 is opened, the processing film removal liquid is discharged downward in a continuous flow from the discharge port of the second moving nozzle 10. When the processing film removal liquid valve 51 is opened while the second moving nozzle 10 is located at the central position, the processing film removal liquid is supplied to the central region of the upper surface of the substrate W.

Examples of the treatment film removal liquid discharged from the second moving nozzle 10 include pure water such as DIW, carbonated water, electrolytic ion water, hydrochloric acid water with a diluted concentration (e.g., about 1 ppm to 100 ppm), ammonia water with a diluted concentration (e.g., about 1 ppm to 100 ppm), reduced water (hydrogen water), and the like.
The third movable nozzle 11 is an example of a residue dissolving liquid nozzle (residue dissolving liquid supply unit) that supplies (discharges) a residue dissolving liquid such as an organic solvent in a continuous flow toward the upper surface of the substrate W held by the spin chuck 5 .

The third movable nozzle 11 is moved in the horizontal and vertical directions by the third nozzle movement unit 37. The third movable nozzle 11 can move in the horizontal direction between a central position and a home position (retracted position).
When the third moving nozzle 11 is located at the central position, it faces a central region of the upper surface of the substrate W. When the third moving nozzle 11 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 third moving nozzle 11 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

The third nozzle moving unit 37 has a similar configuration to the first nozzle moving unit 35. That is, the third nozzle moving unit 37 may include an arm (not shown) connected to the third moving nozzle 11 and extending horizontally, a rotating shaft (not shown) connected to the arm and extending vertically, and a rotating shaft drive unit (not shown) that raises and lowers and rotates the rotating shaft.

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

The residue dissolving liquid is a liquid for dissolving a small amount of residue of the processing film remaining on the substrate W after the processing film removing liquid is supplied to the substrate W, and removing the residue of the processing film from the upper surface of the substrate W. For this reason, it is preferable that the residue dissolving liquid is compatible with the processing film removing liquid. Compatibility refers to the property of two types of liquids dissolving and mixing with each other.
The residue dissolving liquid is preferably a low surface tension liquid having a surface tension lower than that of the treatment film removing liquid. In the substrate processing described below, the upper surface of the substrate W is not dried by shaking off the treatment film removing liquid on the substrate W, but the treatment film removing liquid on the substrate W is replaced with the residue dissolving liquid, and then the residue dissolving liquid on the substrate W is shaken off to dry the upper surface of the substrate W. Therefore, if the residue dissolving liquid is a low surface tension liquid, the surface tension acting on the upper surface of the substrate W when the upper surface of the substrate W is dried can be reduced.

Examples of organic solvents that function as residue dissolving liquids and low surface tension liquids include liquids containing at least one of IPA ( isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene.
The organic solvent functioning as the residue dissolving liquid and the low surface tension liquid does not need to be composed of a single component, but may be a liquid mixed with other components, for example, a mixture of IPA and DIW, or a mixture of IPA and HFE.

4 is a block diagram showing an electrical configuration of the main parts of the substrate processing apparatus 1. The controller 3 includes a microcomputer, and controls the controlled objects provided in the substrate processing apparatus 1 according to a predetermined control program.
Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B in which a control program is stored. The controller 3 is configured to perform various controls for substrate processing by the processor 3A executing the control program.

In particular, the controller 3 is programmed to control the transport robots IR and CR, the spin motor 23, the pin opening and closing unit 24, the first nozzle moving unit 35, the second nozzle moving unit 36, the third nozzle moving unit 37, the guard lifting unit 74, the lamp power unit 85, the opposing member lifting unit 61, the opposing member rotating unit 62, the processing liquid valve 50, the processing film removal liquid valve 51, and the residue dissolving liquid valve 52. By controlling the valves with the controller 3, the presence or absence of ejection of processing fluid from the corresponding nozzle and the ejection flow rate of the processing fluid from the corresponding nozzle are controlled.

Fig. 5 is a flow chart for explaining an example of substrate processing by the substrate processing apparatus 1. Fig. 5 mainly shows processing that is realized by the controller 3 executing a program. Figs. 6A to 6G are schematic diagrams for explaining the state of each step of the substrate processing.
In substrate processing by the substrate processing apparatus 1, for example, as shown in FIG. 5, a processing liquid supply step (step S1), a processing film formation step (step S2), a light irradiation step (step S3), a processing film removal step (step S4), a residue dissolving step (step S5), and a spin drying step (step S6) are performed in this order.

In the following, reference will be made mainly to Figures 2 and 5. Reference will also be made to Figures 6A to 6G as appropriate.
First, an unprocessed substrate W is carried from the carrier C into the processing unit 2 by the transport robots IR, CR (see FIG. 1) and handed over to the spin chuck 5. Thereby, the substrate W is held horizontally by the spin chuck 5 (substrate holding step).
When the substrate W is carried in, the facing member 6 is placed in the retracted position and current is cut off to the plurality of lamps 80. The retracted position of the facing member 6 is, for example, the upper position, and may be any position that allows each moving nozzle to pass between the facing member 6 and the substrate W.

The spin chuck 5 continues to hold the substrate W until the spin dry process (step S6) is completed. From the start of the substrate holding process until the end of the spin dry process (step S6), the guard lifting unit 74 adjusts the height positions of the first guard 71A and the second guard 71B so that at least one guard 71 is located in the upper position. With the substrate W held by the spin chuck 5, the spin motor 23 rotates the spin base 21. This starts the rotation of the substrate W held horizontally (substrate rotation process).

Next, after the transport robot CR retreats to the outside of the processing unit 2, a processing liquid supply step (step S1) is performed in which a processing liquid is supplied to the upper surface of the substrate W. Specifically, the first nozzle moving unit 35 moves the first moving nozzle 9 to a processing position. The processing position of the first moving nozzle 9 is, for example, a central position.
With the first moving nozzle 9 in the processing position, the processing liquid valve 50 is opened. As a result, as shown in Fig. 6A, the processing liquid is supplied (discharged) from the first moving nozzle 9 toward the central region of the upper surface of the substrate W in the rotating state (processing liquid supply step, processing liquid discharge step). The processing liquid supplied to the upper surface of the substrate W spreads over the entire substrate W by centrifugal force. As a result, a liquid film 101 of the processing liquid (processing liquid film) is formed on the substrate W (processing liquid film formation step).

The supply of the processing liquid from the first moving nozzle 9 continues for a predetermined time, for example, 2 to 4 seconds. In the processing liquid supplying step, the substrate W is rotated at a predetermined processing liquid rotation speed, for example, 10 rpm to 1500 rpm.
6B and 6C, a treatment film forming step (step S2) is performed. In the treatment film forming step, the treatment liquid on the substrate W is solidified or hardened to form a treatment film 100 (see FIG. 6C) on the upper surface of the substrate W.

In the treatment film forming step, the thickness of the liquid film 101 of the treatment liquid on the substrate W is thinned (treatment liquid thinning step, treatment liquid spin-off step). Specifically, the treatment liquid valve 50 is closed. This stops the supply of the treatment liquid to the substrate W, as shown in Fig. 6B. Then, the first nozzle movement unit 35 moves the first moving nozzle 9 to the home position.
6B , in the treatment liquid thinning step, the substrate W is rotated in a state where the supply of the treatment liquid to the upper surface of the substrate W is stopped, so that a part of the treatment liquid is removed from the upper surface of the substrate W. As a result, the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness.

The centrifugal force caused by the rotation of the substrate W not only expels the processing liquid from the upper surface of the substrate W, but also acts on the gas in contact with the liquid film 101. The centrifugal force creates an airflow in which the gas flows from the center of the substrate W to the periphery. This airflow expels the gaseous solvent in contact with the liquid film 101 from the atmosphere in contact with the substrate W. This promotes the evaporation (volatilization) of the solvent from the processing liquid on the substrate W, and as shown in FIG. 6C, a processing film 100 is formed (solvent evaporation process, processing film formation process). In the processing film formation process, the spin motor 23 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the processing liquid. The spin motor 23 is an example of a processing film formation unit.

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

Unlike this substrate processing, in the processing film forming step, the processing liquid does not need to be removed by centrifugal force, and the processing film 100 may be formed only by evaporation of the solvent. In this case, the consumption of the processing liquid can be suppressed.
Next, a light irradiation step (step S3) is performed in which the treatment film 100 on the substrate W is irradiated with light.

Specifically, the opposing member lifting unit 61 positions the light irradiation unit 8 at the irradiation position. The irradiation position is, for example, a position where the light emitted from the light irradiation unit 8 is evenly irradiated onto the entire upper surface of the substrate W. Then, the lamp energizing unit 85 energizes the multiple lamps 80 of the light irradiation unit 8. As a result, as shown in FIG. 6D, the light irradiation unit 8 irradiates the entire treatment film 100 with light (light irradiation process). The treatment film 100 is split on the substrate W by the light irradiation (treatment film splitting process). The treatment film 100 is split to form film pieces of the treatment film 100 (treatment film piece formation process).

In the light irradiation process, the spin motor 23 changes the rotation speed of the substrate W to a predetermined processing film splitting speed. The processing film splitting speed is, for example, 300 rpm. The light irradiation is performed for, for example, 30 seconds.
Next, a processed film removing step (step S4) is performed in which the processed film 100 is removed from the upper surface of the substrate W by supplying a processed film removing liquid to the upper surface of the substrate W (strictly speaking, the surface of the processed film 100).

Specifically, the facing member lifting unit 61 moves the facing member 6 to the retracted position, and the lamp energizing unit 85 cuts off the energization of the plurality of lamps 80. With the facing member 6 in the retracted position, the second nozzle moving unit 36 moves the second moving nozzle 10 to the processing position. The processing position of the second moving nozzle 10 is, for example, the central position.
With the second moving nozzle 10 positioned at the processing position, the processing film removing liquid valve 51 is opened. As a result, as shown in Fig. 6E, the processing film removing liquid is supplied (discharged) from the second moving nozzle 10 toward the central region of the upper surface of the rotating substrate W (processing film removing liquid supplying step, processing film removing liquid discharging step).

The treatment film removal liquid supplied to the upper surface of the substrate W spreads over the entire substrate W due to centrifugal force. The treatment film removal liquid that has landed on the treatment film 100 passes through the gaps between the pieces of the treatment film 100 and enters between the substrate W and the treatment film 100, and peels the treatment film 100 from the substrate W (treatment film peeling process). As shown in FIG. 6F, by continuing to supply the treatment film removal liquid, the treatment film 100 is pushed out from the upper surface of the substrate W by the flow of the treatment film removal liquid and removed (treatment film removal process). The treatment film 100 is removed from the upper surface of the substrate W while holding the object to be removed. The second moving nozzle 10 is an example of a treatment film removal unit.

In the processing film removing step (step S4), the substrate W is rotated at a predetermined removal rotation speed, for example, 800 rpm. The processing film removing liquid is supplied for, for example, 30 seconds.
Next, a residue dissolving step (step S5) is performed in which a residue dissolving liquid such as an organic solvent is supplied to remove residues of the processing film 100 from the upper surface of the substrate W.
Specifically, the processing film removal liquid valve 51 is closed, and the second nozzle movement unit 36 moves the second moving nozzle 10 to the retracted position. Then, the third nozzle movement unit 37 moves the third moving nozzle 11 to the processing position. The processing position of the third moving nozzle 11 is, for example, the central position.

With the third moving nozzle 11 positioned at the processing position, the residue dissolving liquid valve 52 is opened, whereby, as shown in Fig. 6G, the residue dissolving liquid is supplied (discharged) from the third moving nozzle 11 toward the central region of the upper surface of the rotating substrate W (residue dissolving liquid supplying step, residue dissolving liquid discharging step).
The residue dissolving liquid supplied to the upper surface of the substrate W spreads radially due to the centrifugal force, and spreads over the entire upper surface of the substrate W. Even after the processing film is peeled off from the substrate W by the processing film removal liquid and removed from the substrate W, residue of the processing film may remain on the upper surface of the substrate W. The residue dissolving liquid supplied to the upper surface of the substrate W dissolves such residue. The residue dissolving liquid that has dissolved the residue is discharged from the periphery of the upper surface of the substrate W by the centrifugal force. This dissolves the residue of the processing film on the substrate W (residue dissolving process).

In the residue dissolving liquid supplying step, the discharge of the residue dissolving liquid from the fourth moving nozzle 12 is continued for a predetermined time, for example, 30 seconds. In the residue dissolving step (step S5), the substrate W is rotated at a predetermined residue dissolving rotation speed, for example, 300 rpm.
Next, a spin dry process (step S6) is performed in which the substrate W is rotated at high speed to dry the upper surface of the substrate W. Specifically, the residue dissolving liquid valve 52 is closed. This stops the supply of the residue dissolving liquid to the upper surface of the substrate W. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to the home position.

Then, the spin motor 23 accelerates the rotation of the substrate W, rotating it at high speed. In the spin dry process, the substrate W is rotated at a drying speed, for example, 1500 rpm. The spin dry process is performed for a predetermined time, for example, 30 seconds. As a result, 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 spin motor 23 stops the rotation of the substrate W. The guard lifting unit 74 moves the first guard 71A and the second guard 71B to the lower position.
The transport robot CR enters the processing unit 2, scoops up the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2. The substrate W is handed over from the transport robot CR to the transport robot IR, and stored in the carrier C by the transport robot IR.

Next, the state of the upper surface of the substrate W during substrate processing will be described in detail with reference to Figures 7A to 7D. Figures 7A to 7D are schematic diagrams for explaining the state near the upper surface of the substrate W during substrate processing. For convenience of explanation, in Figure 7B, the size relationship between the light irradiation units 8 and the substrate W is changed from that in Figure 2 (the same applies to Figures 8 and 15B described later).
7A , the processed film 100 formed in the processed film formation step (step S2) holds objects to be removed 105, such as particles, adhering to a surface layer 150 of the substrate W. The processed film 100 is mainly made of a polymer. The processed film 100 is in a solid state as at least a part of the solvent evaporates.

Next, referring to Fig. 7B, the treated film 100 is split by irradiating the treated film 100 with light (treated film splitting step, light irradiation step). In other words, cracks are generated in the treated film 100 (crack generation step). The treated film 100 becomes film fragments by being split. That is, film fragments of the treated film 100 (treated film fragments 110) are formed (treated film fragment splitting step).
The processing membrane piece 110 is larger than the removal target 105. The removal target 105 is approximately spherical, and has a diameter of, for example, 10 nm. Assuming that the processing membrane piece 110 is a cube, it is preferable that the length of one side of the processing membrane piece 110 is 20 nm or more and several μm or less.

7C , after the treatment film 100 is split, a treatment film removal liquid is supplied to the upper surface of the substrate W. The treatment film removal liquid that has landed on the surface of the treatment film 100 reaches the interface between the treatment film pieces 110 and the substrate W through the gaps G1 between the treatment film pieces 110.
The processing film removal liquid that has reached the vicinity of the upper surface of the substrate W slightly dissolves the portion of the processing film piece 110 near the upper surface of the substrate W. As a result, as shown in the enlarged view of Fig. 7C, the processing film removal liquid gradually dissolves the solid processing film piece 110 near the upper surface of the substrate W, and enters the gap G2 between the processing film piece 110 and the upper surface of the substrate W (removal liquid entry step). As a result, as shown in Fig. 7D, the processing film piece 110 is peeled off from the upper surface of the substrate W (liquid peeling step, processing film peeling step, film piece peeling step).

By continuing to supply the processing film removal liquid, the processing film pieces 110 are washed away by the processing film removal liquid while still holding the object to be removed 105. In other words, the processing film pieces 110 holding the object to be removed 105 are pushed out of the substrate W and removed from the top surface of the substrate W (processing film removal process, removal object removal process). This allows the top surface of the substrate W to be cleaned well.

The treated film pieces 110 are peeled off and removed from the upper surface of the substrate W while maintaining a mass state, without dropping off the object to be removed 105. Removal of the treated film 100 from the upper surface of the substrate W is promoted by the centrifugal force of the substrate W.
According to the first embodiment, the following effects are achieved.
According to the first embodiment, the processing film 100 is split by light irradiation before the processing film removal liquid is supplied to the processing film 100. By being split, the processing film 100 becomes more susceptible to physical force (energy) by the processing film removal liquid. Therefore, the split processing film 100 is pushed out from the upper surface of the substrate W by the processing film removal liquid and removed from the substrate W. Therefore, since the processing film 100 can be split before the processing film removal liquid is supplied, there is no need to split the processing film 100 by the processing film removal liquid. In this way, the processing film 100 can be split without supplying a liquid to the processing film 100, i.e., by dry processing.

Furthermore, according to the first embodiment, the processing film 100 is split to form processing film pieces 110 larger than the object to be removed 105. Therefore, even after the processing film 100 is split, it is possible to prevent the object to be removed 105 from falling off from the processing film pieces 110. Therefore, it is possible to satisfactorily remove the object to be removed 105 from the upper surface of the substrate W.
Moreover, according to the first embodiment, the treatment film 100 is peeled off from the upper surface of the substrate W by the treatment film removal liquid. According to this method, even if the treatment film 100 is not peeled off by light irradiation, it can be peeled off from the upper surface of the substrate W by the treatment film removal liquid.

According to the first embodiment, the treated film 100 contains a polymer 200 having a main chain 201 in a solid state and a side chain 202 bonded to the main chain 201 and configured to be liquefied by light irradiation (see FIG. 3). Therefore, a part of the polymer 200 (the side chain 202) is liquefied by light irradiation, and the treated film 100 is split. Therefore, a part of the treated film 100 is liquefied by light irradiation while most of the treated film 100 is maintained in a solid state. Therefore, the treated film 100 can be split before the treatment film removal solution is supplied.

In the substrate processing described above (FIGS. 7A to 7D), the processing film 100 is split by irradiation with light. However, the light irradiation may not only split the processing film 100, but may also peel the processing film 100 from the top surface of the substrate W. FIG. 8 is a schematic diagram for explaining the state near the top surface of the substrate W during substrate processing, and shows how the processing film 100 is peeled off from the top surface of the substrate W by irradiation with light.

More specifically, in the light irradiation process (step S3), as shown in FIG. 8, it is also possible to split the treated film 100 while peeling it off from the upper surface of the substrate W (treated film splitting process, irradiation peeling process). In this case, in the subsequent treated film removal process (step S4), there is no need to split the treated film 100 using a treated film removal solution, nor is it necessary to peel the treated film 100 off. Therefore, the treated film 100 can be removed from the upper surface of the substrate W using a treated film removal solution that has almost no ability to dissolve the treated film 100. This improves the selectivity of the combination of the treated liquid and the treated film removal solution.

Because the treatment film 100 has already been peeled off by light irradiation, there is no need to apply a large amount of energy to the treatment film 100 that would cause the treatment film removal liquid flowing along the upper surface of the substrate W to peel off the treatment film 100. Therefore, the treatment film removal liquid can effectively wash away the treatment film fragments 110 from the upper surface of the substrate W. This in turn reduces the residue of the treatment film 100. Therefore, the residue dissolution process can be omitted.

Furthermore, when removing the treated film 100, the time during which the treated film 100 is exposed to the treated film removal liquid can be shortened. For this reason, it is possible to use, as the treated film removal liquid, an organic solvent such as IPA that dissolves the treated film 100 to some extent, or a mixed liquid of water and an organic solvent.
As described above, the splitting and peeling of the processing film 100 may proceed simultaneously, or, differently from the above, after the processing film 100 splits, the processing film pieces 110 may be peeled off from the substrate W by continuing to irradiate light.

Unlike the above-described embodiment, the polymer contained as a solute in the treatment liquid may be a second polymer that is decomposed by irradiation with light. In this case, the treatment film 100 that was held together by the presence of the second polymer is no longer able to maintain its shape due to the decomposition of the second polymer, and is split. Therefore, the treatment film 100 can be split before the treatment film removal liquid is supplied.

Specifically, the second polymer is decomposed by breaking a part of the covalent bonds (for example, C-O bonds or C-C bonds) in the molecule of the second polymer. The second polymer is polyisoprene, PMMA (polymethyl methacrylate), polyethylene terephthalate, etc.
In addition to these polymers, for example, a polymer 250 having a C-O bond in the molecule as shown in Fig. 9A can be used as the second polymer. Fig. 9A is a schematic diagram for explaining polymer 250. In polymer 250, ^R1 and ^R2 are hydrocarbon groups. Hereinafter, ^R1 and ^R2 may be collectively referred to as a hydrocarbon group R.

The C-O bond of the polymer 250 is broken by ultraviolet light. The wavelength of the ultraviolet light irradiated to the polymer 250 is preferably greater than 339 nm and equal to or less than 374 nm. In this case, the C-O bond can be selectively broken. It is even more preferable that the wavelength of the ultraviolet light is 374 nm.
9B is a schematic diagram for explaining the mechanism of decomposition of the polymer 250. As shown in FIG. 9B, when the C-O bond is cut by ultraviolet light, the hydrocarbon group (RH) in the polymer 250 changes to a radical (R.). Then, the radical (R.) reacts with oxygen in the atmosphere to form an oxy radical (ROO.). Then, the oxy radical (ROO.) pulls out a hydrogen atom from a new hydrocarbon group (RH), and a radical (R.) and a hydroperoxide (ROOH) are formed. In this way, the cutting of the C-O bond of the polymer 250 forms a decomposition product (R-COOH) having a hydrophilic group (-COOH) at the end, thereby improving the hydrophilicity of the treatment film.

Figure 9C is a schematic diagram for explaining how the treatment film 100 containing the second polymer holds the object to be removed 105. The object to be removed 105 attached to the upper surface of the substrate W is hydrophobic. Therefore, as shown in Figure 9C, the polymer 250 holds the object to be removed 105 attached to the upper surface of the substrate W by surrounding the object to be removed 105 with a hydrocarbon group R. When the treatment film 100 is irradiated with light, the C-O bond is cut only outside the hydrocarbon group R, while the object to be removed 105 remains surrounded by the hydrocarbon group R. For example, the polymer 250 is cut at the cutting position CP shown in Figure 9C.

The decomposition of the polymer 250 forms a decomposition product 251 made of a hydrocarbon compound with a hydrophilic group (-COOH) bonded to the end. Even after the decomposition product 251 is formed, the hydrocarbon group R maintains a state in which it surrounds the object to be removed 105 adhering to the upper surface of the substrate W. This makes it possible to form a processing film piece 110 that is larger than the object to be removed 105. This allows the processing film piece 110 to firmly hold the object to be removed 105.

In addition, since hydrophilic groups are bonded to the ends of the decomposition products 251, the treated membrane pieces 110 are easily washed away with a treated membrane removal solution that contains water.
If polymer 250 is designed so that hydrocarbon group R is longer than the expected size of object 105 to be removed (for example, 10 nm), object 105 to be removed can be firmly held by decomposition product 251 .

By adjusting the intensity and duration of the irradiated light, the degree of cleavage of the covalent bond to be cleaved can be controlled.
The substrate processing shown in FIG. 5 can also be carried out when the second polymer is used as the solute contained in the processing liquid.
In the case where the treatment liquid contains a cross-linking agent that cross-links the second polymers together by the light emitted from the light irradiation unit 8, the liquid film 101 of the treatment liquid can be hardened by the light irradiation emitted from the light irradiation unit 8, as shown in Figures 10A and 10B.

10A and 10B are schematic diagrams for explaining the state of the treatment film forming step (step S2) in a modified example of substrate processing. In this substrate processing, after the supply of the treatment liquid to the substrate W is stopped, the opposing member 6 is placed at the treatment position, and the multiple lamps 80 are energized. As a result, light is irradiated onto the liquid film 101 as shown in FIG. 10A. The light irradiation causes the second polymer in the liquid film 101 to react with the crosslinking agent, and the second polymers are crosslinked together (photocrosslinking step). For example, pyrene or anthracene can be used as the crosslinking agent. By crosslinking the second polymers together, the second polymer is hardened, as shown in FIG. 10B, and the liquid film 101 on the substrate W changes into a solid treatment film 100. In this case, the light irradiation unit 8 functions as a treatment film forming unit.

According to this method, the second polymer is hardened by crosslinking the second polymers with each other using a crosslinking agent. This makes it possible to increase the hardness of the treatment film 100 compared to a case in which the second polymer is not crosslinked. By increasing the hardness of the treatment film 100, the treatment film 100 can firmly hold the object to be removed 105. Therefore, the object to be removed 105 can be removed from the substrate W together with the treatment film pieces 110. Therefore, the object to be removed 105 can be successfully removed from the upper surface of the substrate W.

Next, modified examples of the light irradiation unit 8 will be described with reference to Fig. 11 and Fig. 12. Fig. 11 is a schematic diagram for describing a first modified example of the light irradiation unit 8. Fig. 12 is a schematic diagram for describing a second modified example of the light irradiation unit 8.
For example, as in a first modified example shown in FIG. 11 , the light irradiation unit 8 may be configured to be moved between an irradiation position and a home position (retracted position) by a lamp moving unit 86 provided in the chamber 4.

The irradiation position is a position where the light irradiation unit 8 faces the upper surface of the substrate W. The irradiation position is a position where the light irradiation unit 8 can irradiate the upper surface of the substrate W with light. The retracted position is a position where the light irradiation unit 8 does not irradiate the upper surface of the substrate W with light. When the light irradiation unit 8 is located at the irradiation position, the light irradiation unit 8 faces the upper surface of the substrate W. When the light irradiation unit 8 is located at the home position, the light irradiation unit 8 does not face the upper surface of the substrate W and is located outside the processing cup 7 in a planar view.

In the configuration shown in FIG. 11, the light irradiation unit 8 includes a lamp 80 and a lamp holder 81 that houses the lamp 80. The lamp movement unit 86 includes an arm 87 that supports the lamp holder 81, a rotating shaft 89 that is connected to the arm 87 and extends vertically, and an arm movement unit 88 that moves the arm 87 via the rotating shaft 89. The arm movement unit 88 includes, for example, a motor that rotates the rotating 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 rotating shaft 89.

In the first modified example, the upper surface of the substrate W can be irradiated with light while the light irradiation unit 8 is moved in a direction parallel to the upper surface of the substrate W.
In the second modification shown in Fig. 12, the lamp 80 is rod-shaped and disposed within a linearly extending arm 87. In this case, it is possible to irradiate light over a wider range than in the first modification shown in Fig. 11.

Second Embodiment
The main difference between the substrate processing apparatus 1P according to the second embodiment and the substrate processing apparatus 1 according to the first embodiment is that the substrate processing apparatus 1P is configured to perform liquid processing using liquid and light irradiation in separate processing units.
Fig. 13 is a schematic diagram for explaining the configuration of a wet processing unit 2W provided in the substrate processing apparatus 1P according to the second embodiment. Fig. 14 is a schematic diagram for explaining the configuration of a dry processing unit 2D provided in the substrate processing apparatus 1P according to the second embodiment. As shown in Fig. 13, the wet processing unit 2W differs from the processing unit 2 according to the first embodiment in that a light irradiation unit 8 is not provided.

14, the dry processing unit 2D includes a chamber 300, a substrate holding table 301, a light irradiation unit 8P, and a mask placement unit 302.
The chamber 300 houses a substrate holder 301 and a light irradiation unit 8P. An entrance 300a is formed in the chamber 300 for loading and unloading a substrate W by a transport robot CR. The chamber 300 is provided with a shutter unit 300b for opening and closing the entrance 300a. A substrate W having a treatment film 100 formed on an upper surface thereof is loaded into the chamber 300.

The substrate holding table 301 has a horizontal stage surface 301a (upper surface) and holds the substrate W placed on the stage surface 301a.
The light irradiation unit 8P includes a light generating section 310, a light path adjusting section 311, and a light scanning section 312. The light generating section 310 has a light source such as a semiconductor laser or a gas laser, and emits a light beam L. As the light beam L, for example, ultraviolet light is used.

The light path adjustment unit 311 guides the light emitted from the light generation unit 310 to the light scanning unit 312. The light path adjustment unit 311 includes, for example, a reflecting mirror. The light scanning unit 312 changes the light path of the light beam L incident from the light generation unit 310 via the light path adjustment unit 311. The light scanning unit 312 momentarily changes the incident position of the light beam L on the substrate W held by the substrate holding table 301. As a result, the entire treatment film 100 on the substrate W is irradiated with light.

The mask placement unit 302 is disposed between the optical scanning unit 312 and the substrate holding table 301. A photomask 303 corresponding to the uneven pattern formed on the upper surface of the substrate W is placed on the mask placement unit 302. When the photomask 303 is placed on the mask placement unit 302 and light is irradiated from the light irradiation unit 8P, the light beam L traveling from the optical scanning unit 312 to the substrate W is partially blocked, and the processing film on the substrate W is exposed according to the mask pattern from the photomask 303. Note that instead of scanning the light beam L such as a laser beam, light from a light source that emits a light beam having a wider cross-sectional area may be incident on the entire photomask 303 to expose the processing film 100 all at once.

The substrate processing according to the second embodiment is similar to the substrate processing according to the first embodiment (see FIG. 5). In the substrate processing according to the second embodiment, a processing liquid supplying step (step S1) and a processing film forming step (step S2) are performed in the wet processing unit 2W, and then the substrate W on which the processing film 100 has been formed is transported to the dry processing unit 2D. After a light irradiation step (step S3) is performed in the dry processing unit 2D, the substrate W is transported to the wet processing unit 2W. Then, the processing film removing step (step S4) to the spin drying step (step S6) are performed in the wet processing unit 2W.

15A to 15D are schematic views for explaining the state near the upper surface of the substrate W during substrate processing according to the second embodiment.
15A , a fine uneven pattern 160 may be formed on the surface layer of a substrate W used in substrate processing according to the second embodiment. The uneven pattern 160 includes fine protruding structures 161 formed on the surface of the substrate W, and recesses (grooves) 162 formed between adjacent structures 161.

The surface of the uneven pattern 160, i.e., the surfaces of the structures 161 (protrusions) and recesses 162, form an uneven pattern surface 165. The pattern surface 165 is included in the surface of the substrate W. The surface 161a of the structure 161 is composed of a tip surface 161b (top) and a side surface 161c, and the surface of the recesses 162 is composed of a bottom surface 162a (bottom). If the structure 161 is cylindrical, a recess will be formed inside it.

The structure 161 may include an insulating film or a conductive film. Also, the structure 161 may be a laminated film in which a plurality of films are laminated.
15A , the processed film 100 formed in the processed film formation step (step S2) holds the removal target 105 adhering to the surface layer 150 of the substrate W. The processed film 100 is mainly made of a polymer. The processed film 100 is in a solid state as at least a part of the solvent evaporates.

Next, referring to FIG. 15B, the processing film 100 is irradiated with light through a photomask 303. In FIG. 15B, the portion of the processing film 100 formed on the tip surface 161b of the structure 161 is shielded by the photomask 303. That is, the portion of the processing film 100 formed on the tip surface 161b of the structure 161 is the non-exposed portion 100A. Therefore, only the portions of the processing film 100 located between the structures 161 are exposed. The portions of the processing film 100 located between the structures 161 are the exposed portions 100B.

By light irradiation using a photomask 303, only the exposed portion 100B of the treated film 100 is split (treated film splitting step, light irradiation step). The exposed portion 100B of the treated film 100 is split into film pieces. That is, film pieces of the treated film 100 (treated film pieces 110) are formed in the exposed portion 100B (treated film piece splitting step).
15C , after the treatment film 100 is split, a treatment film removal liquid is supplied to the upper surface of the substrate W. The treatment film removal liquid that has landed on the surface of the treatment film 100 reaches the interface between the treatment film pieces 110 and the substrate W through the gaps G1 between the treatment film pieces 110.

The processing film removal liquid that has reached the vicinity of the upper surface of the substrate W slightly dissolves the portion of the processing film piece 110 near the upper surface of the substrate W. As a result, as shown in the enlarged view of FIG. 15C, the processing film removal liquid gradually dissolves the solid processing film piece 110 near the upper surface of the substrate W, while entering the gap G2 between the processing film piece 110 and the upper surface of the substrate W (removal liquid entry process). As a result, as shown in FIG. 15D, the processing film piece 110 is peeled off from the upper surface of the substrate W (processing film peeling process, film piece peeling process).

By continuing to supply the processing film removal liquid, only the exposed portion 100B of the processing film 100 is removed. The exposed portion 100B is washed away by the processing film removal liquid while still holding the object to be removed 105. In other words, the processing film pieces 110 holding the object to be removed 105 are pushed out of the substrate W and removed from the top surface of the substrate W (processing film removal process, removal object removal process). This allows the top surface of the substrate W to be cleaned well.

On the other hand, the non-exposed portion 100A of the treatment film 100 is not split by the light irradiation and is therefore not peeled off by the treatment film removal solution. The non-exposed portion 100A remains on the pattern surface 165 as a protective film. Therefore, oxidation of the portion of the pattern surface 165 that is covered by the protective film can be suppressed.
It may be possible to conceive of a case where it is desired to avoid exposure to light on the upper surface of the substrate W, but subsequent processing is to be performed on the entire upper surface of the substrate W. In such a case, as shown in Fig. 16, after light irradiation using a photomask 303, both the non-exposed portion 100A and the exposed portion 100B may be removed by a processing film removal liquid.

Unlike the second embodiment, if a liquid is supplied to break up the treatment film, it is difficult to break up only a part of the treatment film.
According to the second embodiment, the light irradiation step includes a step of irradiating the upper surface of the substrate W with light through the photomask 303. Therefore, the treatment film 100 is exposed according to the mask pattern of the photomask 303, so that only a part of the treatment film 100 can be irradiated with light. For example, this is useful when there is a part on the upper surface of the substrate W that needs to be avoided from being exposed to light, or when it is desired to leave the treatment film 100 partially on the substrate W as a protective film.
In the second embodiment, irradiation of the treated film 100 with light may also cause not only division of the treated film 100 but also peeling of the treated film 100 .
The second embodiment also provides the same effects as the first embodiment.

Third Embodiment
17 is a schematic diagram for explaining the configuration of a substrate processing apparatus 1Q according to a third embodiment. The substrate processing apparatus 1Q according to the third embodiment is mainly different from the substrate processing apparatus 1 according to the first embodiment in that the substrate processing apparatus 1Q is configured to perform formation of a processing film 100 and removal of the processing film 100 in separate chambers 4A and 4B.

The substrate processing apparatus 1Q includes a film formation processing unit 2A for forming a treatment film 100 and a film removal processing unit 2B for removing the treatment film 100.
The film formation processing unit 2A includes a spin chuck 5A that rotates the substrate W while holding the substrate W horizontally, a first moving nozzle 9 that supplies a processing liquid to the upper surface of the substrate W, and a chamber 4A that accommodates the spin chuck 5A and the first moving nozzle 9. The spin chuck 5A has a similar configuration to the spin chuck 5.

The chamber 4A is formed with an entrance 4Aa through which the transport robot CR loads and unloads the substrate W. The chamber 4A is provided with a shutter unit 4Ab for opening and closing the entrance 4Aa .
The film formation processing unit 2A further includes a light irradiation unit 8 that irradiates light onto the substrate W passing through the entrance/exit 4Aa of the chamber 4A. The light irradiation unit 8 includes a lamp (light source) that emits, for example, infrared light, ultraviolet light, visible light, etc. The light irradiation unit 8 is attached to the side wall of the chamber 4A.

The film removal processing unit 2B includes a spin chuck 5B that rotates the substrate W while holding it horizontally, a second moving nozzle 10 that supplies a stripping liquid to the top surface of the substrate W, a third moving nozzle 11 that supplies a rinsing liquid to the top surface of the substrate W, and a chamber 4B that houses the spin chuck 5B, the second moving nozzle 10, and the third moving nozzle 11. The spin chuck 5B has the same configuration as the spin chuck 5.

The chamber 4B is formed with an entrance 4Ba through which the transport robot CR loads and unloads the substrate W. The chamber 4B is provided with a shutter unit 4Bb that opens and closes the entrance 4Ba .
In the substrate processing by the substrate processing apparatus 1Q according to the third embodiment, after the substrate W is loaded into the chamber 4A of the film forming processing unit 2A by the transport robot CR, a processing liquid supplying step (step S1) and a processing film forming step (step S2) shown in Fig. 5 are performed in the chamber 4A. During the processing liquid supplying step and the processing film forming step, the substrate W is held by the spin chuck 5A in the chamber 4A (first substrate holding step).

Then, as shown in FIG. 17, the substrate W with the liquid film 101 of the processing liquid formed on its upper surface is transported out of the chamber 4A of the film formation processing unit 2A by the transport robot CR (transport process). When the substrate W passes through the entrance 4Aa of the chamber 4A, the light irradiation unit 8 irradiates the processing film 100 with light, causing the processing film 100 to split. That is, the light irradiation process (step S3) is performed during the transport process. The substrate W, with the processing film 100 now split, is transported into the chamber 4B of the film removal processing unit 2B (transport process). The transport robot CR is an example of a transport unit.

Then, the processing film removing step (step S4), the residue dissolving step (step S5), and the spin drying step (step S6) are performed in the chamber 4B. That is, from the start of the processing film removing step (step S4) to the end of the spin drying step (step S6), the substrate W is held by the spin chuck 5B in the chamber 4B (second substrate holding step).
According to the third embodiment, the same effects as those of the first embodiment are achieved. Furthermore, according to the third embodiment, in a configuration in which the formation of the treated film 100 and the removal of the treated film 100 are performed in separate chambers 4A and 4B, the treated film 100 can be split during the transportation of the substrate W (treated film splitting step). Therefore, the time required for substrate processing can be shortened.
Although not shown in FIG. 17, the film formation processing unit 2A and the film removal processing unit 2B may be provided with a processing cup 7 (see FIG. 2).

<Other embodiments>
The present invention is not limited to the above-described embodiment, and can be embodied in other forms.
For example, the treatment solution may contain both the first polymer and the second polymer as solutes. Even in this case, the treatment film can be decomposed by light irradiation.
In the above-described embodiment, each processing fluid is discharged from a moving nozzle. However, each processing fluid may be discharged from a fixed nozzle whose position with respect to the spin chuck 5 is fixed.

The spin chuck 5 is not limited to a clamping type chuck that brings multiple chuck pins 20 into contact with the peripheral edge surface of the substrate W, but may also be a vacuum type chuck that holds the substrate W horizontally by adsorbing the lower surface of the substrate W to the upper surface of the spin base 21.
In the above-described embodiment, the treatment film 100 is split by light irradiation on the substrate W. However, a substrate treatment may be performed in which the treatment film 100 is dissolved, melted, or decomposed by light irradiation.

In this specification, when numerical ranges are indicated using "to" or "-", they include both endpoints and have the same units, unless otherwise specified and limited.
In addition, various modifications can be made within the scope of the claims.

1: Substrate processing apparatus 1P: Substrate processing apparatus 1Q: Substrate processing apparatus 3: Controller 8: Light irradiation unit (treatment film forming unit)
8P: Light irradiation unit 9: First moving nozzle (treatment liquid supply unit)
10: Second moving nozzle (treated film removal solution supply unit)
23: Spin motor (treatment film forming unit)
100: Treatment film 105: Object to be removed 110: Treatment film piece 200: Polymer (first polymer)
201: Main chain 202: Side chain 250: Polymer (second polymer)
251: decomposition product 303: photomask W: substrate

Claims (11)

a treatment film forming step of supplying a treatment liquid onto a surface of the substrate and solidifying or curing the treatment liquid on the surface of the substrate to form a treatment film on the surface of the substrate;
a light irradiation step of irradiating the treated film with light to split the treated film on the surface of the substrate;
a treatment film removing step of supplying a treatment film removing solution to the surface of the substrate after the light irradiation step, and removing the split treatment film from the surface of the substrate with the treatment film removing solution ;
the treated film includes a first polymer having a solid-state backbone and a side chain attached to the backbone and configured to be liquefied upon irradiation with light;
The substrate processing method , wherein the light irradiation step includes a step of splitting the processing film by liquefying a side chain of the first polymer . the treated film contains a second polymer that is decomposed by irradiation with light,
The substrate processing method according to claim 1 , wherein the light irradiation step includes a step of decomposing the second polymer to thereby split the processing film. a treatment film forming step of supplying a treatment liquid onto a surface of the substrate and solidifying or curing the treatment liquid on the surface of the substrate to form a treatment film on the surface of the substrate;
a light irradiation step of irradiating the treated film with light to split the treated film on the surface of the substrate;
a treatment film removing step of supplying a treatment film removing solution to the surface of the substrate after the light irradiation step, and removing the split treatment film from the surface of the substrate with the treatment film removing solution;
the treated film contains a second polymer that is decomposed by irradiation with light,
The substrate processing method, wherein the light irradiation step includes a step of decomposing the second polymer to thereby split the processing film. the second polymer has a plurality of hydrocarbon groups and C—O bonds connecting the hydrocarbon groups together,
4. The substrate processing method according to claim 2 , wherein in the light irradiation step, decomposition products made of hydrocarbon compounds are formed by cleaving the C--O bonds by irradiation with light. the treatment liquid contains the second polymer and a crosslinking agent that crosslinks the second polymers together by irradiation with light,
The substrate processing method according to any one of claims 2 to 4, wherein the processing film forming step includes a photo-crosslinking step of irradiating the processing liquid on the surface of the substrate with light to cause the crosslinking agent to crosslink the second polymers to each other and harden the second polymers. the processing film formed in the processing film forming step holds a removal target present on a surface of the substrate,
The substrate processing method according to claim 1 , wherein the light irradiation step includes a step of splitting the processing film to form processing film pieces larger than the object to be removed. The substrate processing method according to claim 1 , further comprising an irradiation and peeling step of irradiating the processing film with light to peel the processing film from the surface of the substrate after the light irradiation step and before the processing film removal step. 8. The substrate processing method according to claim 1 , wherein the processing film removing step includes a liquid removing step of removing the processing film from the surface of the substrate by using the processing film removing liquid. The substrate processing method according to any one of claims 1 to 8, wherein the light irradiation step includes a step of irradiating light toward the surface of the substrate through a photomask. a processing liquid supply unit for supplying a processing liquid toward a surface of the substrate;
a treatment film forming unit for solidifying or curing the treatment liquid on the surface of the substrate to form a treatment film on the surface of the substrate;
a light irradiation unit that irradiates light onto a surface of the substrate;
a processing film removing liquid supplying unit that supplies a processing film removing liquid for removing the processing film formed on the substrate toward a surface of the substrate;
a controller for controlling the processing liquid supply unit, the processing film forming unit, the light irradiation unit, and the processing film removal liquid supply unit,
the controller is programmed to execute a treatment film forming step of supplying a treatment liquid from the treatment liquid supply unit onto the surface of the substrate and forming a treatment film on the surface of the substrate by the treatment film forming unit, a light irradiation step of irradiating the treatment film with light from the light irradiation unit to split the treatment film on the surface of the substrate, and a treatment film removal step of supplying a treatment film removal liquid from the treatment film removal liquid supply unit onto the surface of the substrate after the light irradiation step and removing the split treatment film from the surface of the substrate with the treatment film removal liquid ,
the treated film includes a first polymer having a solid-state backbone and a side chain attached to the backbone and configured to be liquefied upon irradiation with light;
The substrate processing apparatus , wherein the light irradiation step includes a step of splitting the processing film by liquefying a side chain of the first polymer . a processing liquid supply unit for supplying a processing liquid toward a surface of the substrate;
a treatment film forming unit for solidifying or curing the treatment liquid on the surface of the substrate to form a treatment film on the surface of the substrate;
a light irradiation unit that irradiates light onto a surface of the substrate;
a processing film removing liquid supplying unit that supplies a processing film removing liquid for removing the processing film formed on the substrate toward a surface of the substrate;
a controller for controlling the processing liquid supply unit, the processing film forming unit, the light irradiation unit, and the processing film removal liquid supply unit,
the controller is programmed to execute a treatment film forming step of supplying a treatment liquid from the treatment liquid supply unit onto the surface of the substrate and forming a treatment film on the surface of the substrate by the treatment film forming unit, a light irradiation step of irradiating the treatment film with light from the light irradiation unit to split the treatment film on the surface of the substrate, and a treatment film removal step of supplying a treatment film removal liquid from the treatment film removal liquid supply unit onto the surface of the substrate after the light irradiation step and removing the split treatment film from the surface of the substrate with the treatment film removal liquid,
the treated film contains a second polymer that is decomposed by irradiation with light,
The light irradiation step includes a step of decomposing the second polymer to thereby split the treatment film.

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