Substrate processing method and substrate processing apparatus

Abstract

A substrate processing method includes: a treatment film forming step of supplying a treatment liquid to a surface of a substrate to solidify or harden the treatment liquid on the surface of the substrate, thereby forming a treatment film on the surface of the substrate; a light irradiation step of irradiating light to the treatment film to split the treatment film on the surface of the substrate; and a treatment film removing step of supplying a treatment film removing liquid 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 liquid.

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing method and a substrate processing apparatus that process a substrate. As the substrate to be processed, for example, a semiconductor wafer, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and a substrate for an FPD (Flat Panel Display) such as a liquid crystal display device, a plasma display, and an organic EL (Electroluminescence) display device, and the like are included. BACKGROUND

[0002] A substrate processing method is disclosed in Patent Document 1 below, which forms a processing film that holds a removal target such as a particle present on the surface of a substrate on the surface of the substrate, and peels off and removes the processing film in a state where the removal target is held.

[0003] In this substrate processing method, a through-hole is formed in the processing film by dissolving a part of the processing film in a peeling liquid and maintaining the remaining part in a solid state. By continuously supplying the peeling liquid, the peeling liquid acts on the interface between the substrate and the processing film via the through-hole, and the processing film is peeled off from the substrate.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENTS

[0006] Patent Document 1: U.S. Patent Application Publication No. 2019 / 366394 Specification SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] With the substrate processing method described in Patent Document 1, a part of the processing film needs to be dissolved by the peeling liquid to form a through-hole, and most of the processing film needs to be maintained in a solid state. Therefore, the processing film needs to be composed of two components (a low-solubility component and a high-solubility component) whose solubilities in the peeling liquid are different from each other.

[0009] Therefore, an object of the present application is to provide a substrate processing method and a substrate processing apparatus that can split a processing film without supplying a liquid to the processing film in a configuration where the processing film is removed from the surface of a substrate by a processing film removal liquid.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] One embodiment of the present application provides a substrate processing method including: a treatment film forming step of supplying a treatment liquid to a surface of a substrate, and solidifying or hardening the treatment liquid on the surface of the substrate, thereby forming a treatment film on the surface of the substrate; a light irradiation step of irradiating light to the treatment film, and splitting the treatment film on the surface of the substrate; and a treatment film removing step of supplying a treatment film removing liquid 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 liquid.

[0012] According to this method, the treatment film is split by light irradiation to the treatment film before the treatment film removing liquid is supplied to the treatment film. The split treatment film is removed from the surface of the substrate by the treatment film removing liquid. Since the treatment film can be split before the treatment film removing liquid is supplied, the treatment film does not need to be split with the treatment film removing liquid. Thus, the treatment film can be split without supplying a liquid to the treatment film.

[0013] In one embodiment of the present application, the treatment film formed in the treatment film forming step holds a removal target existing on the surface of the substrate. The light irradiation step includes a step of forming a treatment film piece larger than the removal target by splitting the treatment film.

[0014] According to this method, the treatment film piece is larger than the removal target, so that the removal target can be prevented from falling off from the treatment film piece even after the treatment film is split. Thus, the removal target can be removed from the surface of the substrate favorably.

[0015] In one embodiment of the present application, the substrate processing method further includes a light irradiation peeling step of irradiating light to the treatment film to peel the treatment film from the surface of the substrate after the light irradiation step and before the treatment film removing step.

[0016] According to this method, the light irradiation can split the treatment film and can also peel the treatment film from the surface of the substrate. Thus, the treatment film does not need to be split with the treatment film removing liquid, and the treatment film does not need to be peeled with the treatment film removing liquid. Thus, the treatment film removing liquid having substantially no property of dissolving the treatment film can be used to remove the treatment film from the surface of the substrate. As a result, the selectivity of the combination of the treatment liquid and the treatment film removing liquid is improved.

[0017] In one embodiment of the present application, the treatment film removing step includes a liquid peeling step of peeling the treatment film from the surface of the substrate with the treatment film removing liquid. According to this method, the treatment film can be peeled from the surface of the substrate with the treatment film removing liquid even when the treatment film cannot be peeled by light irradiation.

[0018] In one embodiment of the present invention, the aforementioned treatment film contains a first polymer, the aforementioned first polymer having: a main chain in a solid state; and a side chain bonded to the aforementioned main chain and configured to be liquefied by irradiation of light. Also, the aforementioned light irradiation process includes a process of splitting the aforementioned treatment film by liquefying the side chain of the aforementioned first polymer.

[0019] According to this method, a part (side chain) of the first polymer is liquefied by irradiation of light. Therefore, by irradiation of light, a part of the treatment film is liquefied while the majority of the treatment film is maintained in a solid state. Thus, it is possible to split the treatment film before the supply of the liquid for removing the treatment film.

[0020] In one embodiment of the present invention, the aforementioned treatment film contains a second polymer that is decomposed by irradiation of light. Also, the aforementioned light irradiation process includes a process of splitting the aforementioned treatment film by decomposing the aforementioned second polymer.

[0021] According to this method, the second polymer is decomposed by irradiation of light. Therefore, the treatment film that is integrated due to the presence of the second polymer cannot maintain its shape due to the decomposition of the second polymer, and splitting occurs. Thus, it is possible to split the treatment film before the supply of the liquid for removing the treatment film.

[0022] In one embodiment of the present invention, the aforementioned second polymer has a plurality of hydrocarbon groups, and a C-O bond that links the aforementioned hydrocarbon groups to each other. Also, the aforementioned light irradiation process cuts the aforementioned C-O bond by irradiation of light, thereby forming a decomposition product containing a hydrocarbon compound.

[0023] On the surface of the substrate, a hydrophobic removal target is sometimes attached. Therefore, the removal target is held on the treatment film by being surrounded by the hydrocarbon groups of the second polymer in the treatment film. As long as the configuration is such that a decomposition product containing a hydrocarbon compound is formed after the decomposition of the second polymer, even after the decomposition of the second polymer, the removal target is maintained in a state of being surrounded by the hydrocarbon groups in the decomposition product. Thus, even after the treatment film is split, it is possible to firmly hold the removal target by the split treatment film.

[0024] In one embodiment of the present invention, the aforementioned treatment liquid contains: the aforementioned second polymer; and a crosslinking agent that crosslinks the aforementioned second polymers to each other by irradiation of light. Also, the aforementioned treatment film forming process includes a photocrosslinking process that crosslinks the aforementioned polymers to each other with the aforementioned crosslinking agent, thereby hardening the aforementioned polymers.

[0025] According to the method, the second polymers are crosslinked with each other using a crosslinking agent. Thereby, the hardness of the treatment film can be increased compared to a case where the second polymers are not crosslinked. By increasing the hardness of the treatment film, the removal target can be firmly held by the treatment film. Therefore, the removal target can be removed from the surface of the substrate together with the split treatment film by the treatment film removal liquid. Therefore, the removal target can be favorably removed from the surface of the substrate.

[0026] In one embodiment of the present application, the aforementioned light irradiation process includes a process of irradiating light toward the surface of the aforementioned substrate through a photomask. Therefore, the treatment film is exposed according to the pattern of the photomask, and thus light can be irradiated only to a part of the treatment film. This is useful, for example, in a case where a part of the surface of the substrate is desired to be avoided from being exposed, or in a case where the treatment film is desired to be partially left on the substrate. If a method different from this method is used in which a liquid is supplied in order to split the treatment film, it is difficult to split only a part of the treatment film.

[0027] Another embodiment of the present application provides a substrate processing apparatus including: a treatment liquid supply unit that supplies a treatment liquid toward a surface of a substrate; a treatment film forming unit that solidifies or hardens the treatment liquid on the surface of the aforementioned substrate to form a treatment film on the surface of the aforementioned substrate; a light irradiation unit that irradiates light toward the surface of the aforementioned substrate; a treatment film removal liquid supply unit that supplies a treatment film removal liquid that removes the treatment film formed on the aforementioned substrate toward the surface of the aforementioned substrate; and a controller that controls the aforementioned treatment liquid supply unit, the aforementioned treatment film forming unit, the aforementioned light irradiation unit, and the aforementioned treatment film removal liquid supply unit.

[0028] The aforementioned controller is programmed to execute the following processes: a treatment film forming process of supplying a treatment liquid toward a surface of a substrate by the aforementioned treatment liquid supply unit, and forming a treatment film on the surface of the aforementioned substrate by the aforementioned treatment film forming unit; a light irradiation process of irradiating light toward the aforementioned treatment film by the aforementioned light irradiation unit to split the aforementioned treatment film on the surface of the aforementioned substrate; and a treatment film removal process of supplying a treatment film removal liquid toward the surface of the aforementioned substrate by the aforementioned treatment film removal liquid supply unit after the aforementioned light irradiation process, and removing the aforementioned split treatment film from the surface of the aforementioned substrate by the aforementioned treatment film removal liquid.

[0029] According to the apparatus, the same effects as the aforementioned substrate processing method are exerted.

[0030] The above and other objects, features and effects of the present application will become clearer from the following description of the embodiments thereof, taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0031] [ Figure 1 ] Figure 1Fig. 1 is a schematic plan view showing the arrangement of a substrate processing apparatus according to a first embodiment of the present application.

[0032] [ Figure 2 ] Figure 2 Fig. 2 is a schematic partial sectional view showing the outline configuration of a processing unit provided in the substrate processing apparatus.

[0033] [ Figure 3 ] Figure 3 Fig. 3 is a schematic view for explaining the properties of a first polymer contained in a processing film.

[0034] [ Figure 4 ] Figure 4 Fig. 4 is a block diagram showing the electrical configuration of main parts of the substrate processing apparatus.

[0035] [ Figure 5 ] Figure 5 Fig. 5 is a flowchart for explaining an example of substrate processing using the substrate processing apparatus.

[0036] [ Figure 6A ] Figure 6A Fig. 6 is a schematic view for explaining the condition of a processing liquid supply process (step S1) of the substrate processing.

[0037] [ Figure 6B ] Figure 6B Fig. 7 is a schematic view for explaining the condition of a processing film formation process (step S2) of the substrate processing.

[0038] [ Figure 6C ] Figure 6C Fig. 8 is a schematic view for explaining the condition of a processing film formation process (step S2) of the substrate processing.

[0039] [ Figure 6D ] Figure 6D Fig. 9 is a schematic view for explaining the condition of a light irradiation process (step S3) of the substrate processing.

[0040] [ Figure 6E ] Figure 6E Fig. 10 is a schematic view for explaining the condition of a processing film removal process (step S4) of the substrate processing.

[0041] [ Figure 6F ] Figure 6F Fig. 11 is a schematic view for explaining the condition of a processing film removal process (step S4) of the substrate processing.

[0042] [ Figure 6G ] Figure 6G Fig. 12 is a schematic view for explaining the condition of a residue dissolution process (step S5) of the substrate processing.

[0043] [ Figure 7A ] Figure 7A is a schematic view for explaining a state of a surface vicinity of a substrate in the aforementioned substrate processing.

[0044] [ Figure 7B ] Figure 7B is a schematic view for explaining a state of a surface vicinity of a substrate in the aforementioned substrate processing.

[0045] [ Figure 7C ] Figure 7C is a schematic view for explaining a state of a surface vicinity of a substrate in the aforementioned substrate processing.

[0046] [ Figure 7D ] Figure 7D is a schematic view for explaining a state of a surface vicinity of a substrate in the aforementioned substrate processing.

[0047] [ Figure 8 ] Figure 8 is a schematic view for explaining a state of a surface vicinity of a substrate in the aforementioned substrate processing, showing a state in which a processing film is peeled from a surface of a substrate by irradiation of light.

[0048] [ Figure 9A ] Figure 9A is a schematic view for explaining an example of the second polymer contained in the processing film.

[0049] [ Figure 9B ] Figure 9B is a schematic view for explaining a decomposition mechanism of the aforementioned second polymer.

[0050] [ Figure 9C ] Figure 9C is a schematic view for explaining a state in which the processing film containing the aforementioned second polymer holds a removal object.

[0051] [ Figure 10A ] Figure 10A is a schematic view for explaining a state of the processing film forming step (step S2) in the aforementioned modified example of the substrate processing.

[0052] [ Figure 10B ] Figure 10B is a schematic view for explaining a state of the processing film forming step (step S2) in the aforementioned modified example of the substrate processing.

[0053] [ Figure 11 ] Figure 11 is a schematic view for explaining a first modified example of the light irradiation unit provided in the aforementioned processing unit.

[0054] Figure 12 ] Figure 12 FIG. 2 is a schematic view for explaining a first modification example of the light irradiation unit described above.

[0055] [ Figure 13 ] Figure 13 FIG. 4 is a schematic view for explaining a configuration of a wet processing unit included in the substrate processing apparatus according to the second embodiment.

[0056] [ Figure 14 ] Figure 14 FIG. 5 is a schematic view for explaining a configuration of a dry processing unit included in the substrate processing apparatus according to the second embodiment.

[0057] [ Figure 15A ] Figure 15A FIG. 6 is a schematic view for explaining a state of a surface vicinity of a substrate in substrate processing performed by the substrate processing apparatus according to the second embodiment.

[0058] [ Figure 15B ] Figure 15B FIG. 7 is a schematic view for explaining a state of a surface vicinity of a substrate in substrate processing performed by the substrate processing apparatus according to the second embodiment.

[0059] [ Figure 15C ] Figure 15C FIG. 8 is a schematic view for explaining a state of a surface vicinity of a substrate in substrate processing performed by the substrate processing apparatus according to the second embodiment.

[0060] [ Figure 15D ] Figure 16 FIG. 9 is a schematic view for explaining a state of a surface vicinity of a substrate in substrate processing performed by the substrate processing apparatus according to the second embodiment.

[0061] [ Figure 17 ] Figure 1 FIG. 10 is a schematic view for explaining a state of a surface vicinity of a substrate in substrate processing performed by the substrate processing apparatus according to the second embodiment.

[0062] [ Figure 2 ] Figure 3 FIG. 12 is a schematic view for explaining a configuration of a substrate processing apparatus according to the third embodiment. DETAILED DESCRIPTION

[0063] Figure 3 FIG. 1 is a schematic plan view showing an arrangement of a substrate processing apparatus 1 according to one embodiment of the present application.

[0064] ​​​​​​​​​The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a circular plate-shaped substrate. As the substrate W, a substrate in which an etchable component is exposed on a surface can be used. As the substrate W, a substrate in which at least any one of SiO2 (silicon oxide), TiN (titanium nitride), Cu (copper), and Ru (ruthenium) is exposed on a surface is preferably used. On the surface of the substrate W, only one of the above-described substances can be exposed, or a plurality of the above-described substances can be exposed. On the surface of the substrate W, an etchable substance other than the above-described substances can be exposed.

[0065] The substrate processing apparatus 1 includes a plurality of processing units 2 that process the substrate W with a fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W processed by the processing units 2 is placed, a transfer robot IR and a CR that transfer the substrate W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.

[0066] The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing units 2. The plurality of processing units 2 have, for example, the same configuration. Among the fluids supplied to the substrate W in the processing units 2, there are processing liquids, processing film removing liquids, residue dissolving liquids, and the like, the details of which are described later.

[0067] Figure 2 A schematic view for explaining a configuration example of the processing unit 2.

[0068] The processing unit 2 includes a chamber 4, a spin chuck 5, a processing cup 7, a light irradiation unit 8, a first movable nozzle 9, a second movable nozzle 10, and a third movable nozzle 11.

[0069] The chamber 4 accommodates the spin chuck 5, the processing cup 7, the light irradiation unit 8, the first movable nozzle 9, the second movable nozzle 10, and the third movable nozzle 11. In the chamber 4, an entrance 4a for transferring the substrate W in or out by the transfer robot CR is formed. In the chamber 4, a shutter unit 4b that opens and closes the entrance 4a is provided.

[0070] The spin chuck 5 is an example of a substrate holding and rotating unit that holds the substrate W horizontally and rotates the substrate W around a rotation axis Al (a vertical axis). The rotation axis Al is a vertical straight line that passes through the center portion of the substrate W. The spin chuck 5 includes a plurality of chuck pins 20, a rotation base 21, a rotation shaft 22, and a rotation motor 23.

[0071] The rotary base 21 has a circular plate shape along a horizontal direction. On an upper surface of the rotary base 21, a plurality of chuck pins 20 that hold a periphery of the substrate W are arranged at intervals in a circumferential direction of the rotary base 21.

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

[0073] The rotary shaft 22 extends in a vertical direction along the rotary axis Al. An upper end portion of the rotary shaft 22 is coupled to a lower surface center of the rotary base 21. A rotary motor 23 supplies a rotary force to the rotary shaft 22. By rotating the rotary shaft 22 with the rotary motor 23, the rotary base 21 is rotated. Thus, the substrate W is rotated around the rotary axis Al. The rotary motor 23 is an example of a substrate rotating unit that rotates the substrate W around the rotary axis Al.

[0074] The light irradiation unit 8 includes: the opposing member 6 that opposes an upper surface (a surface on the upper side) of the substrate W held to the rotary chuck 5 from above; and a plurality of lamps 80 as light sources that are installed on the opposing surface 6a.

[0075] The opposing member 6 is formed in a circular plate shape having substantially the same diameter as or a larger diameter than the substrate W. The opposing surface 6a is arranged along a substantially horizontal plane further upward than the rotary chuck 5.

[0076] The rotary shaft 60 is fixed to a side opposite to the opposing surface 6a in the opposing member 6.

[0077] The opposing member 6 blocks an atmosphere in a space between the opposing surface 6a and the upper surface of the substrate W from an atmosphere outside the space. Thus, the opposing member 6 is also referred to as a blocking plate.

[0078] The plurality of lamps 80 are arranged at equal intervals in an entire region of the opposing surface 6a. The processing unit 2 also includes a lamp energization unit 85 configured to energize the plurality of lamps 80 or stop energization of the plurality of lamps 80. The lamps 80 emit light by being energized. The light emitted by each lamp 80 can be, for example, infrared rays, ultraviolet rays, visible light, or the like.

[0079] The processing unit 2 also includes: an opposing member elevating unit 61 that elevates the opposing member 6; and an opposing member rotating unit 62 that rotates the opposing member 6 around the rotary axis Al.

[0080] The opposing member elevating unit 61 is capable of positioning the opposing member 6 at any position (height) in the vertical direction from a lower position to an upper position. The lower position is a position at which 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 at which 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 positioned at the upper position, the transfer robot CR can access the rotary chuck 5 to carry in and carry out the substrate W.

[0081] The opposing member elevating unit 61 includes, for example, a ball screw mechanism (not shown) in conjunction with a support member (not shown) that supports the rotary shaft 60, and an electric motor (not shown) that supplies driving force to the ball screw mechanism. The opposing member elevating unit 61 is also referred to as an opposing member lifter (shutter lifter). The opposing member rotating unit 62 includes, for example, a motor (not shown) that rotates the rotary shaft 60.

[0082] The opposing member elevating unit 61 elevates the plurality of lamps 80 together with the opposing member 6. The opposing member elevating unit 61 is an example of a lamp elevating 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).

[0083] The processing cup 7 includes a plurality of shields 71 that receive liquid scattered outward from the substrate W held by the rotary chuck 5, a plurality of cups 72 that receive liquid guided downward by the plurality of shields 71, and a cylindrical outer wall member 73 that surrounds the plurality of shields 71 and the plurality of cups 72.

[0084] In this embodiment, an example in which two shields 71 (a first shield 71A and a second shield 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided is shown.

[0085] The first cup 72A and the second cup 72B each have a form of a ring-shaped groove that is open upward.

[0086] The first shield 71A is disposed so as to surround the rotary base 21. The second shield 71B is disposed so as to surround the rotary base 21 at a position farther outward than the first shield 71A.

[0087] The first shield 71A and the second shield 71B each have a substantially cylindrical shape. The upper end portion of each shield 71 is inclined inward toward the rotary base 21.

[0088] The first cup 72A receives liquid guided downward by the first shield 71A. The second cup 72B is formed integrally with the first shield 71A and receives liquid guided downward by the second shield 71B.

[0089] The processing unit 2 includes a shield lifting unit 74 that lifts the first shield 71A and the second shield 71B in the vertical direction, respectively. The shield lifting unit 74 lifts the first shield 71A between a lower position and an upper position. The shield lifting unit 74 lifts the second shield 71B between a lower position and an upper position.

[0090] When both the first shield 71A and the second shield 71B are in the upper position, liquid scattered from the substrate W is caught by the first shield 71A. When the first shield 71A is in the lower position and the second shield 71B is in the upper position, liquid scattered from the substrate W is caught by the second shield 71B. When both the first shield 71A and the second shield 71B are in the lower position, the transfer robot CR can reach the rotary chuck 5 to carry in and carry out the substrate W.

[0091] The shield lifting unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first shield 71A, a first motor (not shown) that provides driving force to the first ball screw mechanism, a second ball screw mechanism (not shown) coupled to the second shield 71B, and a second motor (not shown) that provides driving force to the second ball screw mechanism. The shield lifting unit 74 is also referred to as a shield lifter.

[0092] The first movable nozzle 9 is an example of a processing liquid nozzle (processing liquid supply unit) that supplies (sprays) a processing liquid toward the upper surface (the surface on the upper side) of the substrate W held on the rotary chuck 5.

[0093] The first movable nozzle 9 is moved in the horizontal direction and the vertical direction by the first nozzle moving unit 35. The first movable nozzle 9 is movable in the horizontal direction between a center position and a home position (a retreat position). When the first movable nozzle 9 is in the center position, it opposes the central region of the upper surface of the substrate W.

[0094] When the first movable nozzle 9 is in the home position, it does not oppose the upper surface of the substrate W and is located outside the processing cup 7 in plan view. The first movable nozzle 9 is able to 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.

[0095] The first nozzle moving unit 35 can include an arm (not shown) coupled to the first movable nozzle 9 and extending horizontally, a turning shaft (not shown) coupled to the arm and extending in the vertical direction, and a turning shaft driving unit (not shown) that lifts or turns the turning shaft.

[0096] The turning shaft driving unit turns the arm by turning the turning shaft around a vertical turning shaft axis. In addition, the turning shaft driving unit lifts the arm by lifting the turning shaft in the vertical direction. In correspondence with the turning and lifting of the arm, the first movable nozzle 9 is moved in the horizontal direction and the vertical direction.

[0097] The first moving nozzle 9 is connected to a processing liquid pipe 40 that guides a processing liquid. If a processing liquid valve 50 installed in the processing liquid pipe 40 is opened, the processing liquid is sprayed downward from the first moving nozzle 9 in a continuous flow. If the processing liquid valve 50 is opened when the first moving nozzle 9 is positioned at the center, the processing liquid is supplied to the central region of the upper surface of the substrate W.

[0098] The processing liquid contains a solute and a solvent. By volatilizing (evaporating) at least a part of the solvent contained in the processing liquid, the processing liquid is solidified or hardened. The processing liquid is solidified or hardened on the substrate W, thereby forming a processing film in a solid state. When the processing liquid is solidified or hardened, the processing film takes in and holds a removal target object present on the substrate W. The removal target object is, for example, a foreign matter such as a particle attached to the surface of the substrate W.

[0099] Here, the "solidification" refers to, for example, the solute becoming hard due to forces acting between molecules and atoms and the like accompanying volatilization of the solvent. The "hardening" refers to, for example, the solute becoming hard due to chemical changes such as polymerization and cross-linking. Thus, the "solidification or hardening" indicates that the solute "becomes hard" due to various main reasons.

[0100] In addition, the processing film need not be composed only of solid components. The processing film can also be in a semi-solid state composed of both solid components and liquid components as long as it maintains a certain shape as a whole. That is, the solvent can remain in the processing film without being completely removed from the processing liquid.

[0101] In the processing liquid, a polymer is contained as a solute. The polymer contained in the processing 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 of light from the light irradiation unit 8.

[0102] The main chain of the first polymer remains in a solid state even after light irradiation. Thus, the entire processing film is in a solid state before light is irradiated from the light irradiation unit 8. On the other hand, if light is irradiated from the light irradiation unit 8 to the processing film, a part of the processing film is liquefied, and the processing film is split.

[0103] As the first polymer, as shown in Figure 4 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 reversibly undergoes photoisomerization between the trans form and the cis form by irradiation of light.

[0104] In detail, the azobenzene group of the trans form is converted to the cis form by ultraviolet light, and the azobenzene group of the cis form is converted to the trans form by visible light or heat. When the azobenzene group is in the trans form, the side chain 202 is in a solid state. When the azobenzene group is in the cis form, the side chain is in a liquid state. As the ultraviolet light for converting the azobenzene group to the cis form, for example, ultraviolet light of 365 nm can be used. The wavelength of the ultraviolet light for converting the azobenzene group to the cis form is not limited to 365 nm.

[0105] Therefore, before the ultraviolet light is irradiated to the treatment film, the azobenzene group is in the trans form, and the entire treatment film is maintained in a solid state. On the other hand, by irradiating the ultraviolet light to the treatment film, the azobenzene group is converted to the cis form, and a part of the treatment film is liquefied. Thus, the treatment film is split.

[0106] The first polymer is not limited to Figure 5 The polymer 200 shown is only required to have a main chain in a solid state, and a side chain bonded to the main chain and liquefied by irradiation of light. For example, the first polymer can have an azobenzene derivative as the side chain.

[0107] Referring again to Figure 5 The second movable nozzle 10 is an example of a treatment film removing liquid nozzle (treatment film removing liquid supply unit) that supplies (sprays) a treatment film removing liquid such as pure water to the upper surface of the substrate W held to the rotary chuck 5 in a continuous flow. The treatment film removing liquid is a liquid for removing the treatment film formed on the substrate W without dissolving the treatment film to the outside of the substrate W.

[0108] The second nozzle moving unit 36 moves the second movable nozzle 10 in the horizontal direction and the vertical direction. The second movable nozzle 10 is movable in the horizontal direction between a center position and an initial position (retracted position).

[0109] The second movable nozzle 10 opposes the central region of the upper surface of the substrate W when the second movable nozzle 10 is positioned at the center position. The second movable nozzle 10 does not oppose the upper surface of the substrate W when the second movable nozzle 10 is positioned at the initial position, and is positioned outside the treatment cup 7 in plan view. The second movable nozzle 10 is capable of approaching the upper surface of the substrate W or retracting upward from the upper surface of the substrate W by moving in the vertical direction.

[0110] The second nozzle moving unit 36 has the same configuration as the first nozzle moving unit 35. That is, the second nozzle moving unit 36 can include an arm (not shown) coupled to the second movable nozzle 10 and extending horizontally, a rotation shaft (not shown) coupled to the arm and extending in the vertical direction, and a rotation shaft driving unit (not shown) that raises and lowers or rotates the rotation shaft.

[0111] The second movable nozzle 10 is connected to a processing film removal liquid pipe 41 that guides the processing film removal liquid to the second movable nozzle 10. If a processing film removal liquid valve 51 installed in the processing film removal liquid pipe 41 is opened, the processing film removal liquid is sprayed in a continuous flow downward from the nozzle outlet of the second movable nozzle 10. If the processing film removal liquid valve 51 is opened when the second movable nozzle 10 is positioned at the central position, the processing film removal liquid is supplied to the central region of the upper surface of the substrate W.

[0112] The processing film removal liquid sprayed from the second movable nozzle 10 can be, for example, pure water such as DIW, carbonated water, electrolytic ion water, hydrochloric acid water of a dilute concentration (e.g., about 1 ppm to 100 ppm), ammonia water of a dilute concentration (e.g., about 1 ppm to 100 ppm), reduced water (hydrogen-rich water), or the like.

[0113] The third movable nozzle 11 is an example of a residue dissolving liquid nozzle (residue dissolving liquid supply unit) that supplies (sprays) a residue dissolving liquid such as an organic solvent to the upper surface of the substrate W held by the rotary chuck 5 in a continuous flow.

[0114] The third nozzle moving unit 37 moves the third movable nozzle 11 in the horizontal direction and the vertical direction. The third movable nozzle 11 is movable in the horizontal direction between the central position and the initial position (retracted position).

[0115] The third movable nozzle 11 opposes the central region of the upper surface of the substrate W when positioned at the central position. The third movable nozzle 11 does not oppose the upper surface of the substrate W when positioned at the initial position and is positioned outside the process cup 7 in plan view. The third movable nozzle 11 is capable of approaching the upper surface of the substrate W or retreating upward from the upper surface of the substrate W by moving in the vertical direction.

[0116] The third nozzle moving unit 37 has the same configuration as the first nozzle moving unit 35. That is, the third nozzle moving unit 37 can include an arm (not shown) coupled to the third movable nozzle 11 and extending horizontally, a rotation shaft (not shown) coupled to the arm and extending in the vertical direction, and a rotation shaft driving unit (not shown) that raises and lowers or rotates the rotation shaft.

[0117] The third movable nozzle 11 is connected to a residue dissolving liquid pipe 42 that guides the residue dissolving liquid to the third movable nozzle 11. If a residue dissolving liquid valve 52 installed in the residue dissolving liquid pipe 42 is opened, the residue dissolving liquid is sprayed in a continuous flow downward from the nozzle outlet of the third movable nozzle 11. If the residue dissolving liquid valve 52 is opened when the third movable 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.

[0118] The residue dissolving solution is a liquid for dissolving the residue of the treatment film slightly remaining on the substrate W after the treatment film removing liquid is supplied to the substrate W, and thereby removing the residue of the treatment film from the upper surface of the substrate W. Therefore, the residue dissolving solution preferably has compatibility with the treatment film removing liquid. The compatibility means a property in which two liquids are dissolved and mixed with each other.

[0119] The residue dissolving solution is preferably a low surface tension liquid having a lower surface tension than the treatment film removing liquid. In the substrate processing described later, the upper surface of the substrate W is not dried by flinging off the treatment film removing liquid on the substrate W, but is dried by flinging off the residue dissolving solution on the substrate W after the residue dissolving solution is substituted for the treatment film removing liquid on the substrate W. Therefore, if the residue dissolving solution is a low surface tension liquid, the surface tension acting on the upper surface of the substrate W can be reduced when the upper surface of the substrate W is dried.

[0120] As the organic solvent functioning as the residue dissolving solution and the low surface tension liquid, a liquid containing at least one of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, PGEE (propylene glycol monoethyl ether), and trans-1,2-dichloroethylene, and the like can be given.

[0121] The organic solvent functioning as the residue dissolving solution and the low surface tension liquid need not contain only a monomer component, but can be a liquid obtained by mixing with other components. For example, it can be a mixed liquid of IPA and DIW, or a mixed liquid of IPA and HFE.

[0122] Figures 6A-6G A block diagram showing the electrical configuration of the main part of the substrate processing apparatus 1. The controller 3 is provided with a microcomputer, and controls the control objects provided in the substrate processing apparatus 1 in accordance with a prescribed control program.

[0123] 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 execute various controls for substrate processing by the processor 3A executing the control program.

[0124] In particular, the controller 3 is programmed to control the transfer robot IR, the CR, the rotation 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 shield lifting unit 74, the lamp energization unit 85, the opposing member lifting unit 61, the opposing member rotating unit 62, the processing liquid valve 50, the treatment film removing liquid valve 51, and the residue dissolving solution valve 52. By controlling the valves using the controller 3, the presence or absence of ejection of the processing fluid from the corresponding nozzle, and the ejection flow rate of the processing fluid from the corresponding nozzle are controlled.

[0125] Figure 5A flowchart for explaining an example of substrate processing by the substrate processing apparatus 1. Figure 2 The processing realized by the controller 3 executing the program is mainly shown. Figure 5 A schematic diagram for explaining the conditions of each process of substrate processing.

[0126] In the substrate processing by the substrate processing apparatus 1, for example as shown in Figures 6A-6G , a treatment liquid supply process (step S1), a treatment film formation process (step S2), a light irradiation process (step S3), a treatment film removal process (step S4), a residue dissolution process (step S5), and a spin-drying process (step S6) are sequentially executed.

[0127] Hereinafter, mainly referring to Figure 1 and Figure 6A , the substrate processing will be explained. Appropriate reference will be made to Figure 6B .

[0128] First, an unprocessed substrate W is carried into the processing unit 2 from the carrier C by the carrying robot IR, CR (see Figure 6C ), and is delivered to the spin chuck 5. By this, the substrate W is horizontally held by the spin chuck 5 (substrate holding process).

[0129] At the time of carrying in the substrate W, the opposing member 6 is disposed at a retracted position, and the energization of the plurality of lamps 80 is blocked. The retracted position of the opposing member 6 is, for example, an upper position, as long as the position where each of the moving nozzles can pass through between the opposing member 6 and the substrate W.

[0130] The holding of the substrate W by the spin chuck 5 continues until the end of the spin-drying process (step S6). During the period from the start of the substrate holding process until the end of the spin-drying process (step S6), the height positions of the first and second shields 71A and 71B are adjusted by the shield lifting unit 74 so that at least one of the shields 71 is located at the upper position. With the substrate W held by the spin chuck 5, the rotation base 21 is rotated by the rotation motor 23. By this, the rotation of the horizontally held substrate W is started (substrate rotation process).

[0131] Next, after the carrying robot CR is retracted outside the processing unit 2, the treatment liquid supply process (step S1) of supplying a treatment liquid to the upper surface of the substrate W is executed. Specifically, the first nozzle moving unit 35 moves the first moving nozzle 9 to a treatment position. The treatment position of the first moving nozzle 9 is, for example, a central position.

[0132] With the first moving nozzle 9 located at the treatment position, the treatment liquid valve 50 is opened. By this, as shown in Figure 6CAs shown, the processing liquid is supplied (ejected) from the first moving nozzle 9 toward a central region of the upper surface of the substrate W in the rotating state (processing liquid supply process, processing liquid ejection process). The processing liquid supplied to the upper surface of the substrate W spreads over the entire substrate W due to centrifugal force. Thus, a liquid film 101 (processing liquid film) of the processing liquid is formed on the substrate W (processing liquid film formation process).

[0133] The supply of the processing liquid from the first moving nozzle 9 is continued for a prescribed time, for example, a time of 2 seconds to 4 seconds. In the processing liquid supply process, the substrate W is rotated at a prescribed processing liquid rotation speed, for example, 10 rpm to 1500 rpm.

[0134] Next, the processing film formation process (step S2) shown in FIG. 2 is executed. Figure 6B and Figure 6B In the processing film formation process, the processing liquid on the substrate W is solidified or hardened, and a processing film 100 is formed on the upper surface of the substrate W (see FIG. 3). Figure 6C ).

[0135] In the processing film formation process, the thickness of the liquid film 101 of the processing liquid on the substrate W is thinned (processing liquid thinning process, processing liquid spin off process). Specifically, the processing liquid valve 50 is closed. Thus, as shown in FIG. 4, the supply of the processing liquid to the substrate W is stopped. Then, the first moving nozzle 9 is moved to the initial position by the first nozzle moving unit 35. Figure 6D

[0136] As shown in FIG. 5, in the processing liquid thinning process, the substrate W is rotated in a state where the supply of the processing liquid to the upper surface of the substrate W is stopped, and thus a part of the processing liquid is discharged from the upper surface of the substrate W. Thus, the thickness of the liquid film 101 on the substrate W becomes an appropriate thickness. Figure 6E

[0137] The centrifugal force caused by the rotation of the substrate W not only discharges the processing liquid from the upper surface of the substrate W, but also acts on the gas in contact with the liquid film 101. By the action of the centrifugal force, a gas flow is formed in which the gas is directed from the center side of the substrate W toward the peripheral edge side. By this gas flow, the solvent in the state of the gas in contact with the liquid film 101 is discharged from the atmosphere in contact with the substrate W. Thus, the evaporation (volatilization) of the solvent from the processing liquid on the substrate W is promoted, and as shown in FIG. 6, the processing film 100 is formed (solvent evaporation process, processing film formation process). In the processing film formation process, the rotation motor 23 functions as an evaporation unit (evaporation promoting unit) that evaporates the solvent in the processing liquid. The rotation motor 23 is an example of a processing film formation unit. Figure 6F

[0138] ​​​In the treatment film forming process, the rotation motor 23 changes the rotation speed of the substrate W to a prescribed treatment film forming speed. The treatment film forming speed is, for example, 300 rpm to 1500 rpm. The rotation speed of the substrate W can be kept constant in the range of 300 rpm to 1500 rpm, or can be changed appropriately in the range of 300 rpm to 1500 rpm in the middle of the treatment film forming process. The treatment film forming process is performed for a prescribed time, for example, 30 seconds.

[0139] Unlike the substrate processing, in the treatment film forming process, the exclusion of the treatment liquid based on the centrifugal force can not be performed, and the treatment film 100 can be formed only by the evaporation of the solvent. In this case, the consumption amount of the treatment liquid can be suppressed.

[0140] Next, a light irradiation process of irradiating the treatment film 100 on the substrate W with light is performed (step S3).

[0141] Specifically, the opposing member lifting unit 61 configures the light irradiation unit 8 at the irradiation position. The irradiation position is, for example, a position at which light emitted from the light irradiation unit 8 is uniformly irradiated to the entire upper surface of the substrate W. Then, the lamp energization unit 85 energizes the plurality of lamps 80 of the light irradiation unit 8. Thus, as shown in FIG. 6, the light irradiation unit 8 irradiates the entire treatment film 100 with light (light irradiation process). By the light irradiation, the treatment film 100 is split on the substrate W (treatment film splitting process). The treatment film 100 is split to form pieces of the treatment film (treatment film pieces) (treatment film piece forming process). Figure 6G

[0142] In the light irradiation process, the rotation motor 23 changes the rotation speed of the substrate W to a prescribed treatment film splitting speed. The treatment film splitting speed is, for example, 300 rpm. The light irradiation is performed, for example, for 30 seconds.

[0143] Next, a treatment film removing process of removing the treatment film 100 from the upper surface of the substrate W by supplying a treatment film removing liquid to the upper surface (strictly speaking, the surface of the treatment film 100) of the substrate W is performed (step S4).

[0144] Specifically, the opposing member lifting unit 61 moves the opposing member 6 to the retreat position, and the lamp energization unit 85 interrupts the energization of the plurality of lamps 80. In the state in which the opposing member 6 is positioned at the retreat position, the 2nd nozzle moving unit 36 moves the 2nd moving nozzle 10 to the treatment position. The treatment position of the 2nd moving nozzle 10 is, for example, the central position.

[0145] In the state in which the 2nd moving nozzle 10 is positioned at the treatment position, the treatment film removing liquid valve 51 is opened. Thus, as shown in FIG. 8, the 2nd moving nozzle 10 supplies the treatment film removing liquid to the entire treatment film 100 (treatment film removing process). Figures 7A-7D ​As shown, the processing film removing liquid is supplied (ejected) from the second moving nozzle 10 toward the central region of the upper surface of the substrate W in the rotating state (processing film removing liquid supply process, processing film removing liquid ejection process).

[0146] The processing film removing liquid supplied to the upper surface of the substrate W spreads over the entire substrate W by the centrifugal force. The processing film removing liquid landed on the processing film 100 passes through the gaps between the pieces of the processing film 100 to enter between the substrate W and the processing film 100, and peels the processing film 100 from the substrate W (processing film peeling process). As shown, Figures 7A-7D by the continued supply of the processing film removing liquid, the processing film 100 is pushed out from the upper surface of the substrate W by the flow of the processing film removing liquid and is removed (processing film removing process). The processing 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 processing film removing unit.

[0147] In the processing film removing process (step S4), the substrate W is rotated at a prescribed removing rotation speed, for example, 800 rpm. The supply of the processing film removing liquid is performed for, for example, 30 seconds.

[0148] Next, a residue dissolving process (step S5) of supplying a residue dissolving liquid such as an organic solvent to the substrate W to remove the residue of the processing film 100 from the upper surface of the substrate W is performed.

[0149] Specifically, the processing film removing liquid valve 51 is closed, and the second nozzle moving unit 36 moves the second moving nozzle 10 to the retreat position. Then, the third nozzle moving unit 37 moves the third moving nozzle 11 to the processing position. The processing position of the third moving nozzle 11 is, for example, the central position.

[0150] In the state where the third moving nozzle 11 is positioned at the processing position, the residue dissolving liquid valve 52 is opened. Thus, as shown, Figure 7B the residue dissolving liquid is supplied (ejected) from the third moving nozzle 11 toward the central region of the upper surface of the substrate W in the rotating state (residue dissolving liquid supply process, residue dissolving liquid ejection process).

[0151] The residue dissolving liquid supplied to the upper surface of the substrate W spreads radially by the centrifugal force and spreads over the entire upper surface of the substrate W. There is a case where the residue of the processing film remains on the upper surface of the substrate W even after the processing film is peeled from the substrate W by the processing film removing liquid and is removed from the substrate W. The residue dissolving liquid supplied to the upper surface of the substrate W dissolves such residue. The residue dissolving liquid in which the residue is dissolved is discharged from the periphery of the upper surface of the substrate W by the centrifugal force. Thus, the residue of the processing film on the substrate W is dissolved (residue dissolving process).

[0152] In the residue dissolving liquid supplying step, the residue dissolving liquid is ejected from the fourth movable nozzle 12 for a prescribed time, for example, 30 seconds. In the residue dissolving step (step S5), the substrate W is rotated at a prescribed residue dissolving rotation speed, for example, 300 rpm.

[0153] Next, a rotation drying step (step S6) of rotating the substrate W at high speed to dry the upper surface of the substrate W is executed. Specifically, the residue dissolving liquid valve 52 is closed. Thereby, the supply of the residue dissolving liquid to the upper surface of the substrate W is stopped. Then, the third nozzle moving unit 37 moves the third movable nozzle 11 to the initial position.

[0154] Then, the rotation motor 23 accelerates the rotation of the substrate W to rotate the substrate W at high speed. The substrate W in the rotation drying step is rotated at a drying speed, for example, 1500 rpm. The rotation drying step is executed for a prescribed time, for example, 30 seconds. Thereby, a large centrifugal force acts on the residue dissolving liquid on the substrate W, and the residue dissolving liquid on the substrate W is flung to the periphery of the substrate W.

[0155] Then, the rotation motor 23 stops the rotation of the substrate W. The shield lifting unit 74 moves the first shield 71A and the second shield 71B to the lower position.

[0156] The transfer robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pin 20 of the rotation chuck 5, and carries out the substrate W outside the processing unit 2. The substrate W is transferred from the transfer robot CR to the transfer robot IR, and is stored in the carrier C by the transfer robot IR.

[0157] Next, the use of the light irradiation unit 8 will be described. Figure 2 The condition of the upper surface of the substrate W in the substrate processing will be described in detail. Figure 8 is a schematic view for explaining the condition of the vicinity of the upper surface of the substrate W in the substrate processing. Figure 15B In the following description, the size relationship between the light irradiation unit 8 and the substrate W is illustrated by Figure 7A is changed (in the following description Figure 7B and Figure 7C as well).

[0158] As shown in Figure 7C , the processing film 100 formed in the processing film forming step (step S2) holds the removal object 105 such as particles and the like attached to the surface layer portion 150 of the substrate W. The processing film 100 is mainly formed of a polymer. The processing film 100 becomes a solid state by evaporating at least a part of the solvent.

[0159] Next, referring to Figure 7DThe processing film 100 is split by irradiating light to the processing film 100 (processing film splitting step, light irradiation step). In other words, a crack is generated in the processing film 100 (crack generation step). The processing film 100 becomes a film sheet by the splitting. That is, a film sheet (processing film sheet 110) is formed from the processing film 100 (processing film sheet splitting step).

[0160] The processing film sheet 110 is larger than the removal target object 105. The removal target object 105 is a substantially spherical body, and has a diameter of, for example, 10 nm. In a case where the processing film sheet 110 is assumed to be a cubic body, it is preferable that the length of one side of the processing film sheet 110 be 20 nm or more and several μm or less.

[0161] Next, referring to Figure 3 After the processing film 100 is split, the processing film removal liquid is supplied to the upper surface of the substrate W. The processing film removal liquid landed on the surface of the processing film 100 reaches the interface between the processing film sheet 110 and the substrate W via the gap G1 between the processing film sheets 110.

[0162] The processing film removal liquid reaching the vicinity of the upper surface of the substrate W slightly dissolves the portion of the processing film sheet 110 in the vicinity of the upper surface of the substrate W. Thus, as shown in an enlarged view of Figures 7A-7D the processing film removal liquid gradually dissolves the processing film sheet 110 in a solid state in the vicinity of the upper surface of the substrate W, and enters the gap G2 between the processing film sheet 110 and the upper surface of the substrate W (removal liquid entering step). Thus, as shown in Figure 8 the processing film sheet 110 is peeled from the upper surface of the substrate W (liquid peeling step, processing film peeling step, film sheet peeling step).

[0163] By continuously supplying the processing film removal liquid, the processing film sheet 110 is washed by the processing film removal liquid while holding the removal target object 105. In other words, the processing film sheet 110 holding the removal target object 105 is pushed out to the outside of the substrate W and is excluded from the upper surface of the substrate W (processing film exclusion step, removal target object exclusion step). Thus, the upper surface of the substrate W can be well cleaned.

[0164] The processing film sheet 110 is removed from the upper surface of the substrate W in a state of maintaining the block state without falling off the removal target object 105. The removal of the processing film 100 from the upper surface of the substrate W is promoted by the centrifugal force of the substrate W.

[0165] According to the first embodiment, the following effects are obtained.

[0166] According to the first embodiment, the treatment film 100 is split by light irradiation before the treatment film removing liquid is supplied to the treatment film 100. The treatment film 100 becomes susceptible to physical force (energy) by the treatment film removing liquid due to the splitting. Therefore, the split treatment film 100 is pushed out from the upper surface of the substrate W by the treatment film removing liquid and is removed from the substrate W. Thus, the treatment film 100 can be split before the supply of the treatment film removing liquid, and therefore, the treatment film 100 does not need to be split by the treatment film removing liquid. Thus, the treatment film 100 can be split by dry processing without supplying a liquid to the treatment film 100.

[0167] Further, according to the first embodiment, the treatment film 100 is split, and therefore, the treatment film piece 110 larger than the removal target 105 is formed. Therefore, even after the treatment film 100 is split, the removal target 105 can be prevented from falling off from the treatment film piece 110. Thus, the removal target 105 can be favorably removed from the upper surface of the substrate W.

[0168] Further, according to the first embodiment, the treatment film 100 is peeled from the upper surface of the substrate W by the treatment film removing liquid. According to this method, even when the treatment film 100 cannot be peeled by light irradiation, the treatment film 100 can be peeled from the upper surface of the substrate W by the treatment film removing liquid.

[0169] Further, according to the first embodiment, the treatment 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 irradiation of light (see Figure 8 ). Therefore, by irradiation of light, a part (the side chain 202) of the polymer 200 is liquefied, and the treatment film 100 is split. Thus, by irradiation of light, a part of the treatment film 100 is liquefied while a large part of the treatment film 100 is maintained in a solid state. Therefore, the treatment film 100 can be split before the supply of the treatment film removing liquid.

[0170] In the above-described substrate processing Figure 9A ), the treatment film 100 is split by irradiation of light. However, the light irradiation not only splits the treatment film 100 but also peels the treatment film 100 from the upper surface of the substrate W. Figure 9A is a schematic view for explaining a state of the vicinity of the upper surface of the substrate W in substrate processing, and shows a state in which the treatment film 100 is peeled from the upper surface of the substrate W by irradiation of light.

[0171] In detail, in the light irradiation process (step S3), as shown in Figure 9BAs shown, the treatment film 100 can be split while being peeled from the upper surface of the substrate W (treatment film splitting process, irradiation peeling process). In this case, in the treatment film removing process (step S4), it is not necessary to split the treatment film 100 with the treatment film removing liquid, nor is it necessary to peel the treatment film 100 with the treatment film removing liquid. Therefore, the treatment film 100 can be removed from the upper surface of the substrate W using a treatment film removing liquid that has substantially no property of dissolving the treatment film 100. As a result, the selectivity of the combination of the treatment liquid and the treatment film removing liquid is improved.

[0172] Since the treatment film 100 has been peeled by the light irradiation, it is not necessary to impart the treatment film 100 with energy as great as that of the treatment film removing liquid flowing along the upper surface of the substrate W peeling the treatment film 100. Therefore, the treatment film pieces 110 can be washed from the upper surface of the substrate W with the treatment film removing liquid. Furthermore, the residue of the treatment film 100 can be reduced. Therefore, the residue dissolving process can be omitted.

[0173] Furthermore, when the treatment film 100 is removed, the time during which the treatment film 100 is exposed to the treatment film removing liquid can be shortened. Therefore, as the treatment film removing liquid, an organic solvent such as IPA that slightly dissolves the treatment film 100, a mixed liquid of water and an organic solvent can be used.

[0174] As described above, the splitting and peeling of the treatment film 100 can be performed simultaneously, or, differently from the above, the light can be continuously irradiated after the splitting of the treatment film 100, thereby peeling the treatment film pieces 110 from the substrate W.

[0175] Differently from the above embodiment, the polymer contained as a solute in the treatment liquid can be a second polymer that is decomposed by the irradiation of light. In this case, the treatment film 100 that is integrated by the presence of the second polymer cannot maintain its shape due to the decomposition of the second polymer, and is split. Therefore, the treatment film 100 can be split before the supply of the treatment film removing liquid.

[0176] Specifically, a part of the covalent bond (for example, C-O bond, C-C bond) in the molecule of the second polymer is cut, thereby decomposing the second polymer. The second polymer is polyisoprene, PMMA (polymethyl methacrylate), polyethylene terephthalate, or the like.

[0177] As the second polymer, in addition to the above-described polymers, for example, as shown in Figure 9B , a polymer 250 having a C-O bond in the molecule can be used. Figure 9C is a schematic view for explaining the polymer 250. In the polymer 250, R 1 and R 2 are hydrocarbon groups. Hereinafter, R 1 and R2 R is a hydrocarbon group.

[0178] The C-O bond of the polymer 250 is cleaved by ultraviolet light. The wavelength of the ultraviolet light irradiated to the polymer 250 is preferably longer than 339 nm and is 374 nm or less. In this way, the C-O bond can be selectively cleaved. The wavelength of the ultraviolet light is more preferably 374 nm.

[0179] Figure 9C is a schematic diagram for explaining the decomposition mechanism of the polymer 250. As shown in Figure 9C the C-O bond is cleaved by ultraviolet light, the hydrocarbon group (RH) in the polymer 250 is converted into a radical (R·). Then, the radical (R·) reacts with oxygen in the atmosphere to form an oxygen radical (ROO·). Then, the oxygen radical (ROO·) abstracts a hydrogen atom from a new hydrocarbon group (RH) to form a radical (R·) and a hydroperoxide (ROOH). In this way, by cleavage of the C-O bond of the polymer 250, a decomposed product (R-COOH) having a hydrophilic group (-COOH) at the terminal end is formed, and thus the hydrophilicity of the treatment film is improved.

[0180] Figure 5 is a schematic diagram for explaining the state in which the treatment film 100 containing the second polymer holds the removal object 105. The removal object 105 attached to the upper surface of the substrate W is hydrophobic. Therefore, as shown in Figure 10A the polymer 250 holds the removal object 105 by surrounding the periphery of the removal object 105 attached to the upper surface of the substrate W with the hydrocarbon group R. By irradiating light to the treatment film 100, the C-O bond is cleaved only at a position farther outside than the hydrocarbon group R in the state in which the removal object 105 is surrounded with the hydrocarbon group R. For example, at the cleavage position CP shown in Figure 10B the polymer 250 is cleaved.

[0181] By decomposition of the polymer 250, a decomposed product 251 containing a hydrocarbon compound having a hydrophilic group (-COOH) bonded at the terminal end is formed. Even after the decomposed product 251 is formed, the hydrocarbon group R maintains the state of surrounding the removal object 105 attached to the upper surface of the substrate W. Therefore, a treatment film piece 110 larger than the removal object 105 can be formed. Thus, the removal object 105 can be firmly held by the treatment film piece 110.

[0182] In addition, since the hydrophilic group is bonded at the terminal end in the decomposed product 251, the treatment film piece 110 is easily washed away by a treatment film removal liquid containing water.

[0183] If the polymer 250 is designed so that the hydrocarbon group R is longer than the size (for example, 10 nm) of the removal object 105 assumed, the removal object 105 can be firmly held by the decomposed product 251.

[0184] By adjusting the intensity and time of the irradiated light, the degree of cleavage of the covalent bond that is the cleavage target can be controlled.

[0185] In the case where the second polymer is used as a solute contained in the treatment liquid, the substrate treatment illustrated in Figure 10A can also be performed.

[0186] In the case where the treatment liquid contains a cross-linking agent that cross-links the second polymers with each other by light emitted from the light irradiation unit 8, as illustrated in Figure 10B and Figure 10A , the liquid film 101 of the treatment liquid can be hardened by light irradiation from the light irradiation unit 8.

[0187] Figure 10B and Figure 11 is a schematic view for explaining a state of a treatment film formation process (step S2) in a modified example of the substrate treatment. In this substrate treatment, after the supply of the treatment liquid to the substrate W is stopped, the opposing member 6 is arranged at the treatment position, and the plurality of lamps 80 is energized. Thereby, as illustrated in Figure 12 , light is irradiated to the liquid film 101. By the light irradiation, the second polymers in the liquid film 101 react with the cross-linking agent, and the second polymers cross-link with each other (photo-crosslinking process). As the cross-linking agent, for example, pyrene, anthracene can be used. By cross-linking the second polymers with each other, as illustrated in Figure 11 , the second polymers are hardened, and the liquid film 101 on the substrate W is changed to the solid treatment film 100. In this case, the light irradiation unit 8 functions as a treatment film formation unit.

[0188] According to this method, by cross-linking the second polymers with each other with the cross-linking agent, the second polymers are hardened. Thereby, compared to the case where the second polymers are not cross-linked, the hardness of the treatment film 100 can be improved. By improving the hardness of the treatment film 100, the removal target 105 can be firmly held by the treatment film 100. Therefore, the removal target 105 can be excluded to the outside of the substrate W together with the treatment film piece 110. Therefore, the removal target 105 can be favorably removed from the upper surface of the substrate W.

[0189] Next, a modified example of the light irradiation unit 8 will be described using Figure 12 and Figure 11 . Figure 11 is a schematic view for explaining a first modified example of the light irradiation unit 8. Figure 11 is a schematic view for explaining a second modified example of the light irradiation unit 8.

[0190] For example, as illustrated in Figure 11In the first modification example shown, the light irradiation unit 8 is configured to move between the irradiation position and the initial position (retracted position) by a lamp moving unit 86 provided inside the chamber 4.

[0191] The irradiation position is a position at which the light irradiation unit 8 opposes the upper surface of the substrate W (indicated by a two-dot chain line in the figure). The irradiation position is a position from which light can be irradiated from the light irradiation unit 8 to the upper surface of the substrate W. The retracted position is a position from which light cannot be irradiated from the light irradiation unit 8 to the upper surface of the substrate W (indicated by a solid line in the figure). When the light irradiation unit 8 is positioned at the irradiation position, the light irradiation unit 8 opposes the upper surface of the substrate W. When the light irradiation unit 8 is positioned at the initial position, the light irradiation unit 8 does not oppose the upper surface of the substrate W and is positioned outside the process cup 7 in plan view. Figure 12 Figure 11

[0192] Figure 13 In the configuration shown, the light irradiation unit 8 includes a lamp 80 and a lamp support 81 that houses the lamp 80. The lamp moving unit 86 includes an arm 87 that supports the lamp support 81, a rotation shaft 89 that is connected to the arm 87 and extends vertically, and an arm moving unit 88 that moves the arm 87 via the rotation shaft 89. The arm moving unit 88 includes, for example, a motor that rotates the rotation shaft 89 about its central axis (rotation axis A2) in order to move the arm 87 horizontally, and a ball screw mechanism that raises and lowers the arm 87 together with the rotation shaft 89.

[0193] In the first modification example, the light irradiation unit 8 can be moved in a direction parallel to the upper surface of the substrate W while irradiating light to the upper surface of the substrate W.

[0194] In the second modification example shown, the lamp 80 is a rod shape that is disposed inside the arm 87 extending in a straight line. In this case, light can be irradiated to a wider range than in the first modification example shown. Figure 14 Figure 13

[0195] <Second Embodiment>

[0196] The substrate processing apparatus IP related to the second embodiment differs from the substrate processing apparatus 1 related to the first embodiment mainly in that the substrate processing apparatus IP is configured to perform liquid processing using a liquid and irradiation of light by separate processing units.

[0197] Figure 14 is a schematic view for explaining the configuration of the wet processing unit 2W provided in the substrate processing apparatus IP related to the second embodiment. Figure 5 is a schematic view for explaining the configuration of the dry processing unit 2D provided in the substrate processing apparatus IP related to the second embodiment. As shown in the figure, the dry processing unit 2D includes a process chamber 4D, a substrate W, a light irradiation unit 8, and a lamp moving unit 86. Figures 15A-15D ​​​​As shown, the wet processing unit 2W differs from the processing unit 2 related to the first embodiment in that the light irradiation unit 8 is not provided.

[0198] Referring to Figure 15A The dry processing unit 2D includes a chamber 300, a substrate holding stage 301, a light irradiation unit 8P, and a mask placement unit 302.

[0199] The chamber 300 accommodates the substrate holding stage 301 and the light irradiation unit 8P. An entrance 300a for carrying in or out the substrate W by means of a carrying robot CR is formed in the chamber 300. The substrate W having the processing film 100 formed on the upper surface is carried into the chamber 300.

[0200] The substrate holding stage 301 has a horizontal stage surface 301a (upper surface). The substrate holding stage 301 holds the substrate W placed on the stage surface 301a.

[0201] 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, for example, a light source such as a semiconductor laser or a gas laser, which emits a light beam L. As the light beam L, for example, ultraviolet rays can be used.

[0202] The light path adjusting section 311 guides the light emitted from the light generating section 310 to the light scanning section 312. The light path adjusting section 311 includes, for example, a mirror. The light scanning section 312 changes the light path of the light beam L incident from the light generating section 310 via the light path adjusting section 311. The light scanning section 312 changes the incident position of the light beam L to the substrate W held on the substrate holding stage 301 every moment. Thus, the light is irradiated to the entire processing film 100 on the substrate W.

[0203] The mask placement unit 302 is disposed between the light scanning section 312 and the substrate holding stage 301. In the mask placement unit 302, a photomask 303 corresponding to the concave-convex pattern formed on the upper surface of the substrate W is placed. In a state where the photomask 303 is placed on the mask placement unit 302, the light is irradiated by the light irradiation unit 8P, whereby the light beam L from the light scanning section 312 toward the substrate W is partially shielded, and the processing film on the substrate W is exposed according to the mask pattern from the photomask 303. Note that, instead of the method of scanning the light beam L (e.g., a laser beam), a configuration can be made in which light from a light source that emits a light beam having a wider cross-sectional area is incident to the entire photomask 303, and the processing film 100 is exposed at once.

[0204] The substrate processing related to the second embodiment is the same as the substrate processing related to the first embodiment (see Figure 15AThe same applies. In the substrate processing according to the second embodiment, after the processing liquid supply process (step S1) and the processing film formation process (step S2) are performed in the wet processing unit 2W, the substrate W with the processing film 100 formed is transferred to the dry processing unit 2D. After the light irradiation process (step S3) is performed in the dry processing unit 2D, the substrate W is transferred to the wet processing unit 2W. Then, the processing film removal process (step S4) to the rotary drying process (step S6) are performed in the wet processing unit 2W.

[0205] Figure 15B This is a schematic diagram illustrating the condition near the upper surface of the substrate W during substrate processing according to the second embodiment.

[0206] like Figure 15B As shown, a fine convex-concave pattern 160 can be formed on the surface of the substrate W used in the substrate processing according to the second embodiment. The convex-concave pattern 160 includes: fine convex structures 161 formed on the surface of the substrate W; and recesses (grooves) 162 formed between adjacent structures 161.

[0207] The surfaces of the raised and recessed patterns 160, namely the structures 161 (convex portion) and the recessed portion 162, form a patterned surface 165 with raised and recessed areas. The patterned surface 165 is contained within the surface of the substrate W. The surface 161a of the structure 161 is formed by a front end surface 161b (top) and a side surface 161c, and the surface of the recessed portion 162 is formed by a bottom surface 162a (bottom). When the structure 161 is cylindrical, a recess is formed on its inner side.

[0208] Structure 161 may include an insulating film or a conductive film. Alternatively, structure 161 may be a laminated film composed of multiple films.

[0209] like Figure 15C As shown, the treatment film 100 formed in the treatment film formation process (step S2) retains the object to be removed 105 attached to the surface portion 150 of the substrate W. The treatment film 100 is mainly formed of a polymer. By evaporating at least a portion of the solvent, the treatment film 100 becomes a solid state.

[0210] Next, see Figure 15C The treatment film 100 is irradiated with light through the light mask 303. Figure 15D In the process film 100, the portion formed on the front end face 161b of the structure 161 is shielded by the photomask 303. That is, the portion of the process film 100 formed on the front end face 161b of the structure 161 is the non-exposed portion 100A. Therefore, only the portion of the process film 100 located between the structures 161 is exposed. The portion of the process film 100 located between the structures 161 is the exposed portion 100B.

[0211] By light irradiation using the photomask 303, only the exposed portion 100B of the processing film 100 is split (processing film splitting step, light irradiation step). The exposed portion 100B of the processing film 100 becomes a film piece by the splitting. That is, a film piece (processing film piece 110) of the processing film 100 is formed in the exposed portion 100B (processing film piece splitting step).

[0212] Next, referring to Figure 16 After the processing film 100 is split, the processing film removing liquid is supplied to the upper surface of the substrate W. The processing film removing liquid landed on the surface of the processing film 100 reaches the interface between the processing film piece 110 and the substrate W via the gap Gl between the processing film pieces 110.

[0213] The processing film removing liquid reaching the vicinity of the upper surface of the substrate W slightly dissolves the portion of the processing film piece 110 in the vicinity of the upper surface of the substrate W. Thus, as shown in the enlarged view of Figure 17 the processing film removing liquid gradually dissolves the processing film piece 110 in the solid state in the vicinity of 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 (removing liquid entering step). Thus, as shown in Figure 5 the processing film piece 110 is peeled from the upper surface of the substrate W (processing film peeling step, film piece peeling step).

[0214] By continuously supplying the processing film removing liquid, only the exposed portion 100B of the processing film 100 is removed. The exposed portion 100B is washed with the processing film removing liquid while the removing object 105 is held. In other words, the processing film piece 110 holding the removing object 105 is pushed out to the outside of the substrate W and is excluded from the upper surface of the substrate W (processing film exclusion step, removing object exclusion step). Thus, the upper surface of the substrate W can be well cleaned.

[0215] On the other hand, the non-exposed portion 100A of the processing film 100 is not split by the light irradiation and thus is not peeled by the processing film removing liquid. The non-exposed portion 100A remains as a protective film in the pattern surface 165. Thus, oxidation of the portion covered by the protective film in the pattern surface 165 can be suppressed.

[0216] Although it is intended to avoid exposure on the upper surface of the substrate W, a case where the entire upper surface of the substrate W is subjected to subsequent processing is also envisioned. In such a case, as shown in Figure 17 the non-exposed portion 100A and the exposed portion 100B can be removed by the processing film removing liquid after the light irradiation using the photomask 303.

[0217] If the method of supplying a liquid in order to split the processing film is different from the second embodiment, it is difficult to split only a portion of the processing film.

[0218] According to the second embodiment, the light irradiation process includes a process of irradiating light toward the upper surface of the substrate W through the photomask 303. Therefore, the treatment film 100 is exposed in accordance with the mask pattern of the photomask 303, and thus it is possible to irradiate light only to a part of the treatment film 100. This is useful, for example, in a case where there is a portion on the upper surface of the substrate W that is desired to avoid exposure, or in a case where it is desired to cause the treatment film 100 to remain as a protective film partially on the substrate W.

[0219] In the second embodiment, by the irradiation of light to the treatment film 100, not only splitting of the treatment film 100 is caused, but also peeling of the treatment film 100 can be caused.

[0220] In the second embodiment, the same effects as those of the first embodiment are also obtained.

[0221] <Third Embodiment>

[0222] Figure 17 A schematic view for explaining the configuration of a substrate processing apparatus IQ involved in the third embodiment will be described. The substrate processing apparatus IQ involved in the third embodiment differs from the substrate processing apparatus 1 involved in the first embodiment mainly in that the substrate processing apparatus IQ is configured to perform formation of the treatment film 100 and removal of the treatment film 100 in separate chambers 4A, 4B.

[0223] The substrate processing apparatus IQ includes a film formation processing unit 2A that forms the treatment film 100, and a film removal processing unit 2B that removes the treatment film 100.

[0224] The film formation processing unit 2A includes a spin chuck 5A that rotates the substrate W in a state where the substrate W is held horizontally, a first moving nozzle 9 that supplies a treatment 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 is configured the same as the spin chuck 5.

[0225] The chamber 4A is formed with an entrance and exit 4Aa for carrying the substrate W in or out by a carrying robot CR. A shutter unit 4Ab that opens and closes the entrance and exit 4Aa is provided in the chamber 4A.

[0226] The film formation processing unit 2A further includes a light irradiation unit 8 that irradiates light to the substrate W passing through the entrance and exit 4Aa of the chamber 4A. The light irradiation unit 8 includes a lamp (a light source) that emits, for example, infrared rays, ultraviolet rays, visible light, or the like. The light irradiation unit 8 is installed to a side wall of the chamber 4A.

[0227] The film removing treatment unit 2B includes a rotary chuck 5B that rotates the substrate W while the substrate W is held horizontally, a second moving nozzle 10 that supplies a peeling liquid to the upper surface of the substrate W, a third moving nozzle 11 that supplies a rinsing liquid to the upper surface of the substrate W, and a chamber 4B that houses the rotary chuck 5B, the second moving nozzle 10, and the third moving nozzle 11. The rotary chuck 5B has the same configuration as the rotary chuck 5.

[0228] The chamber 4B has a door unit 4Bb that opens and closes the entrance 4Ba for carrying the substrate W into or out of the chamber 4B by the carrying robot CR.

[0229] In the substrate treatment performed by the substrate processing apparatus 1Q according to the third embodiment, after the substrate W is carried into the chamber 4A of the film forming treatment unit 2A by the carrying robot CR, the processing liquid supplying process (step S1) and the film forming process (step S2) shown in FIG. 6 are performed in the chamber 4A. During the execution of the processing liquid supplying process and the film forming process, the substrate W is held on the rotary chuck 5A in the chamber 4A (first substrate holding process). Figure 2

[0230] Then, as shown in FIG. 7, the substrate W on which the liquid film 101 of the processing liquid is formed on the upper surface is carried out of the chamber 4A of the film forming treatment unit 2A by the carrying robot CR (carrying-out 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, thereby splitting the processing film 100. That is, during the carrying-out process, the light irradiation process (step S3) is performed. The substrate W is carried into the chamber 4B of the film removing treatment unit 2B in a state where the processing film 100 has been split (carrying-in process). The carrying robot CR is an example of a carrying unit. ​

[0231] Then, in the chamber 4B, the processing film removing process (step S4), the residue dissolving process (step S5), and the spin-drying process (step S6) are performed. That is, during the period from the start of the processing film removing process (step S4) to the end of the spin-drying process (step S6), the substrate W is held on the rotary chuck 5B in the chamber 4B (second substrate holding process).

[0232] According to the third embodiment, the same effects as those of the first embodiment are exerted. In addition, according to the third embodiment, in the configuration in which the formation of the processing film 100 and the removal of the processing film 100 are performed in separate chambers 4A and 4B, the processing film 100 can be split during the carrying of the substrate W (processing film splitting process). Therefore, the time required for the substrate treatment can be shortened.

[0233] Although​​​ In the film formation processing unit 2A and the film removal processing unit 2B, a processing cup 7 (see FIG. 2) can also be provided, although not shown. ​

[0234] <Other Embodiments>

[0235] The present application is not limited to the embodiments described above, but can be implemented in other ways.

[0236] For example, both the first polymer and the second polymer can be contained as solutes in the processing liquid. In this case, the processing film can also be decomposed by light irradiation.

[0237] In the above-described embodiments, each processing fluid is ejected from a moving nozzle. However, each processing fluid can also be ejected from a fixed nozzle whose position relative to the rotary chuck 5 is fixed.

[0238] The rotary chuck 5 is not limited to a chuck-type chuck that brings the plurality of chuck pins 20 into contact with the peripheral end surface of the substrate W, but can 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 rotary base 21.

[0239] In the above-described embodiments, the processing film 100 is split on the substrate W by light irradiation. However, a substrate processing that dissolves, melts, or decomposes the processing film 100 by light irradiation can also be performed.

[0240] In this specification, in the case where "~" or "-" is used to indicate a numerical range, unless specifically limited, they include both ends, and the units are common.

[0241] Although the embodiments of the application have been described in detail, these are merely specific examples used to clarify the technical content of the present application, and the present application should not be interpreted by being limited to these specific examples, and the scope of the present application is only limited by the appended claims.

[0242] This application corresponds to Japanese Patent Application No. 2020-122304 filed on July 16, 2020 with the Japan Patent Office, the entire disclosure of which is incorporated herein by reference.

[0243] Explanation of Reference Signs

[0244] 1: Substrate processing apparatus

[0245] 1P: Substrate processing apparatus

[0246] 1Q: Substrate processing apparatus

[0247] 3: Controller

[0248] ​8: light irradiation unit (treatment film forming unit)

[0249] 8P: light irradiation unit

[0250] 9: 1st moving nozzle (treatment liquid supply unit)

[0251] 10: 2nd moving nozzle (treatment film removing liquid supply unit)

[0252] 23: rotary motor (treatment film forming unit)

[0253] 100: treatment film

[0254] 105: removal target object

[0255] 110: treatment film piece

[0256] 200: polymer (1st polymer)

[0257] 201: main chain

[0258] 202: side chain

[0259] 250: polymer (2nd polymer)

[0260] 251: decomposition product

[0261] 303: photomask

[0262] W: substrate

Claims

1. A substrate processing method, comprising: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate, causing the treatment liquid on the surface of the substrate to solidify or harden, thereby forming a treatment film on the surface of the substrate. In the light irradiation process, light is irradiated onto the treatment film, causing the treatment film to split on the surface of the substrate; and In the film removal process, after the light irradiation process, a film removal solution is supplied to the surface of the substrate, and the split film is removed from the surface of the substrate using the film removal solution. The treatment membrane contains a first polymer having: a solid main chain; and side chains bonded to the main chain to liquefy upon light irradiation. The light irradiation process includes a step of splitting the treatment membrane by liquefying the side chains of the first polymer.

2. A substrate processing method, comprising: In the process of forming a treatment film, a treatment liquid is supplied to the surface of a substrate, causing the treatment liquid on the surface of the substrate to solidify or harden, thereby forming a treatment film on the surface of the substrate. In the light irradiation process, light is irradiated onto the treatment film, causing the treatment film to split on the surface of the substrate; and In the film removal process, after the light irradiation process, a film removal solution is supplied to the surface of the substrate, and the split film is removed from the surface of the substrate using the film removal solution. The treated membrane contains a second polymer that decomposes upon light irradiation. The light irradiation process includes a step of causing the treatment membrane to split by decomposing the second polymer.

3. The substrate processing method as described in claim 2, wherein, The second polymer has multiple hydrocarbon groups and CO bonds linking the hydrocarbon groups together. The light irradiation process breaks the CO bonds by irradiating them with light, thereby forming a decomposition product containing hydrocarbon compounds.

4. The substrate processing method as described in claim 2, wherein, The treatment solution contains the second polymer and a crosslinking agent that causes the second polymer to crosslink with each other through light irradiation. The processing film formation process includes a photocrosslinking process, in which light is irradiated onto the processing liquid on the surface of the substrate, thereby causing the second polymer to crosslink with each other through the crosslinking agent, and thus hardening the second polymer.

5. The substrate processing method according to any one of claims 1 to 4, wherein, The processing film formed in the processing film formation process retains the object to be removed that is present on the surface of the substrate. The light irradiation process includes the step of forming a treatment film larger than the object to be removed by splitting the treatment film.

6. The substrate processing method according to any one of claims 1 to 4, further comprising an irradiation stripping step after the light irradiation step and before the processing film removal step, wherein the processing film is irradiated with light to peel the processing film off the surface of the substrate.

7. The substrate processing method according to any one of claims 1 to 4, wherein, The process for removing the treatment film includes a liquid stripping process that uses the treatment film removal liquid to peel the treatment film off the surface of the substrate.

8. The substrate processing method according to any one of claims 1 to 4, wherein, The light irradiation process includes the process of irradiating light onto the surface of the substrate through a light mask.

9. A substrate processing apparatus, comprising: A processing liquid supply unit supplies processing liquid to the surface of the substrate; A processing film forming unit that solidifies or hardens a processing liquid on the surface of the substrate, thereby forming a processing film on the surface of the substrate; A light irradiation unit that irradiates light onto the surface of the substrate; A membrane removal liquid supply unit supplies a membrane removal liquid for removing the membrane formed on the substrate to the surface of the substrate. and The controller controls the treatment liquid supply unit, the treatment membrane formation unit, the light irradiation unit, and the treatment membrane removal liquid supply unit. The controller is programmed to perform the following steps: The processing film formation process involves supplying processing liquid to the surface of a substrate by the processing liquid supply unit, and forming a processing film on the surface of the substrate by the processing film formation unit. The light irradiation process involves the light irradiation unit irradiating light onto the processing film, causing the processing film to split on the surface of the substrate; and In the film removal process, after the light irradiation process, a film removal solution supply unit supplies film removal solution to the surface of the substrate, and the film removal solution is used to remove the split film from the surface of the substrate. The treatment membrane contains a first polymer having: a solid main chain; and side chains bonded to the main chain to liquefy upon light irradiation. The light irradiation process includes a step of splitting the treatment membrane by liquefying the side chains of the first polymer.

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