Substrate processing method and substrate processing apparatus

Abstract

A substrate processing method includes: a hydrophilic film forming liquid supplying step of supplying, toward a main surface of a substrate, a hydrophilic film forming liquid that forms a hydrophilic film on the main surface of the substrate; a film thickness reducing liquid supplying step of supplying, toward the main surface of the substrate, a film thickness reducing liquid that reduces a thickness of the hydrophilic film by dissolving the hydrophilic film; a treatment film forming liquid supplying step of supplying, toward the main surface of the substrate after the thickness of the hydrophilic film is reduced by the film thickness reducing liquid supplying step, a treatment film forming liquid that forms, on a surface of the hydrophilic film, a treatment film for holding a removal target existing on the main surface of the substrate; and a peeling liquid supplying step of supplying, toward the main surface of the substrate, a peeling liquid that peels the treatment film from the hydrophilic film.

Description

Technical Field

[0001] This invention relates to a substrate processing method and a substrate processing apparatus.

[0002] The substrates that are processed include substrates for FPD (Flat Panel Display) such as semiconductor wafers, liquid crystal display devices and organic EL (Electroluminescence) display devices, substrates for optical discs, substrates for magnetic disks, substrates for optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, etc. Background Technology

[0003] Patent Document 1 below discloses a substrate processing method in which a processing liquid supplied to the main surface of the substrate is solidified or hardened to form a processing film, and the processing film is peeled off from the main surface of the substrate by a stripping liquid, thereby removing the object to be removed along with the processing film.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: US Patent Publication No. 2019 / 366394 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The processing film in Patent Document 1 contains a first component and a second component (polymer) with lower solubility in the stripping liquid than the first component. When the main surface of the substrate is a hydrophobic surface, there is a concern that the interaction between the hydrophobic surface and the hydrophobic groups of the polymer contained in the processing film may hinder the stripping liquid from penetrating between the substrate and the processing film. Therefore, there is a concern that the processing film may not be able to peel off well from the substrate, and that the object to be removed may not be able to be sufficiently removed from the main surface of the substrate.

[0009] Therefore, one of the objectives of this invention is to provide a substrate processing method and a substrate processing apparatus that can effectively remove the object to be removed from the main surface of the substrate regardless of the state of the main surface.

[0010] means for solving problems

[0011] An embodiment of the present invention provides a substrate processing method, comprising: a hydrophilic film forming liquid supply step, wherein a hydrophilic film forming liquid for forming a hydrophilic film on a main surface of a substrate is supplied toward the main surface of the substrate; a film thickness reduction liquid supply step, wherein a film thickness reduction liquid for reducing the thickness of the hydrophilic film by dissolving the hydrophilic film is supplied toward the main surface of the substrate; a processing film forming liquid supply step, wherein after the thickness of the hydrophilic film is reduced by the film thickness reduction liquid supply step, a processing film forming liquid is supplied toward the main surface of the substrate, wherein the processing film forming liquid forms a processing film on the surface of the hydrophilic film for retaining a removal target object present on the main surface of the substrate; and a stripping liquid supply step, wherein a stripping liquid for peeling the processing film from the hydrophilic film is supplied toward the main surface of the substrate.

[0012] According to this substrate processing method, a hydrophilic film can be formed on the main surface of the substrate by supplying a hydrophilic film forming solution to the main surface of the substrate. With the hydrophilic film already formed on the main surface of the substrate, a film thickness reducing solution is supplied to the main surface of the substrate to dissolve the hydrophilic film, thereby reducing the thickness of the hydrophilic film on the main surface of the substrate. After the thickness of the hydrophilic film is reduced, a treatment film forming solution is supplied to the main surface of the substrate, thereby forming a treatment film on the surface of the hydrophilic film with reduced thickness. With the treatment film already formed on the surface of the hydrophilic film, a stripping solution is supplied to the main surface of the substrate, thereby peeling the treatment film off from the hydrophilic film. The stripping solution can be an alkaline liquid.

[0013] Even when the main surface of the substrate is hydrophobic, forming a hydrophilic film on the main surface can make it appear pseudo-hydrophilic. Strictly speaking, the properties of the main surface of the substrate itself do not change. When the hydrophilicity of the portion forming the contact interface with the processing film is increased by forming a hydrophilic film between the processing film and the main surface of the substrate, this is described as "pseudo-hydrophilizing the main surface of the substrate." Hydrophobic surfaces are, for example, surfaces exposing one or more of amorphous carbon, silicon carbide, and ruthenium.

[0014] By forming a hydrophilic film, the main surface of the substrate is pseudo-hydrophilized, allowing the stripping liquid to easily penetrate between the main surface of the substrate and the treatment film, or more specifically, the interface between the treatment film and the hydrophilic film. Therefore, the treatment film, which retains the object to be removed on the main surface of the substrate, can be easily peeled off from the main surface of the substrate.

[0015] In this substrate processing method, the thickness of the hydrophilic film is reduced by a film thickness reduction liquid before the treatment film is peeled off from the hydrophilic film. Therefore, the object to be removed, present on the main surface of the substrate, can be well exposed from the hydrophilic film. Thus, if the treatment film is formed on the surface of the hydrophilic film with reduced thickness, the object to be removed can be firmly held to the treatment film. Therefore, by subsequently supplying a stripping liquid, the object to be removed can be effectively removed along with the treatment film.

[0016] As described above, even when the main surface of the substrate is hydrophobic, i.e., regardless of the condition of the main surface of the substrate, the object to be removed can be effectively removed from the main surface of the substrate. The film thickness reduction solution can also be water. Preferably, the film thickness reduction solution is a liquid with the same solvent as that contained in the hydrophilic film-forming solution.

[0017] In one embodiment of the present invention, the substrate processing method further includes a hydrophilic film removal liquid supply step, wherein after the stripping liquid supply step, the hydrophilic film removal liquid that removes the hydrophilic film from the main surface of the substrate is supplied toward the main surface of the substrate.

[0018] According to this substrate processing method, after the processing film is peeled off using a stripping solution to remove the object to be removed from the main surface of the substrate, the hydrophilic film can be removed from the main surface of the substrate using a hydrophilic film removal solution. Therefore, after the object to be removed is removed, the main surface of the substrate can be restored to its state before the formation of the hydrophilic film. The hydrophilic film removal solution can also be an acidic liquid.

[0019] In one embodiment of the present invention, the hydrophilic film-forming liquid contains a hydrophilic component having both hydrophobic and hydrophilic groups, with the hydrophilic group being more numerous than the hydrophobic group.

[0020] According to this substrate processing method, the hydrophilic component contained in the hydrophilic film forming solution has both hydrophobic and hydrophilic groups. Because the hydrophilic component has more hydrophilic groups than hydrophobic groups, the highly hydrophilic surface (hydrophilic film surface) can be fully exposed regardless of whether the main surface of the substrate is hydrophobic. Furthermore, because the hydrophilic component has hydrophobic groups, an interaction can occur between the hydrophobic groups and the hydrophobic surface when the main surface of the substrate is hydrophobic. The hydrophilic component can be, for example, a nitrogen-containing polymer, a nitrogen-containing compound, a saturated nitrogen-containing hydrocarbon ring, or a salt thereof.

[0021] In one embodiment of the present invention, the above-mentioned treatment film forming liquid contains: a highly soluble component; and a low-soluble component that is more difficult to dissolve in the above-mentioned stripping liquid than the highly soluble component.

[0022] Therefore, by supplying a stripping solution to the main surface of the substrate, highly soluble components in the treated film can be selectively dissolved in the stripping solution. While selectively dissolving the highly soluble components, the stripping solution moves towards the interface between the treated film and the hydrophilic film. Thus, the stripping solution can form pathways within the treated film. After forming pathways through the dissolution of the highly soluble components, the stripping solution efficiently reaches the interface between the treated film and the hydrophilic film via these pathways. This allows the stripping solution to effectively act on the interface between the treated film and the hydrophilic film.

[0023] When the highly soluble component is dissolved, most of the less soluble component remains undissolved in the stripping liquid. Therefore, the treatment film can be split into larger sheets, and the object to be removed can be held within these sheets, which are primarily composed of the less soluble component. As a result, the treatment film can be rapidly peeled off from the main surface of the substrate, and the object to be removed, along with the treatment film, can be efficiently pushed to the outside of the main surface of the substrate by the flow of the stripping liquid.

[0024] Furthermore, the so-called "selective dissolution of highly soluble components" does not mean that only highly soluble components are dissolved, but rather that less soluble components are also slightly dissolved, while most of the highly soluble components are dissolved.

[0025] The aforementioned low-soluble components may contain at least one of phenolic varnish, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers thereof.

[0026] In addition, the aforementioned highly soluble components are crack-promoting components, which may contain hydrocarbons, hydroxyl groups and / or carbonyl groups.

[0027] The aforementioned highly soluble component may be a substance represented by at least any one of (B-1), (B-2) and (B-3) below.

[0028] (B-1) is a compound containing 1 to 6 chemical formulas 1 as constituent units, with each of the constituent units being bonded together by a linker L1.

[0029] [Chemistry 1]

[0030] Here, L1 is selected from single bonds and C. 1~6 At least one of the alkyl groups, Cy1 is C 5~30 The hydrocarbon ring, R1 is independently C 1~5 alkyl, n b1 n is 1, 2, or 3. b1’ It can be 0, 1, 2, 3, or 4.

[0031] (B-2) is the compound represented by chemical formula 2.

[0032] [Chemistry 2]

[0033] Here, R 21 R 22 R 23 and R 24 Each can be independently hydrogen or C 1~5 alkyl, L 21 and L 22 Each is independently C1~20 alkyl groups, C 1~20 cycloalkyl, C 2~4 enylene, C 2~4 The acetylenic group, or C 6~20 The aryl groups; these groups can also be derived from C 1~5 Alkyl or hydroxyl substitution, n b2 It can be 0, 1, or 2.

[0034] (B-3) is a polymer containing the constituent units shown in chemical formula 3 and having a weight average molecular weight (Mw) of 500 to 10,000.

[0035] [Chemistry 3]

[0036] R 25 It can be -H, -CH3, or -COOH.

[0037] In one embodiment of the present invention, during the above-mentioned film thickness reduction liquid supply step, the hydrophilic membrane is dissolved by the above-mentioned film thickness reduction liquid, such that the thickness of the hydrophilic membrane is less than the particle size of the object to be removed.

[0038] Therefore, the object to be removed can be more effectively exposed from the hydrophilic membrane surface. This allows the object to be retained more firmly within the treatment membrane. Consequently, with the subsequent supply of a stripping solution, the object can be effectively removed along with the treatment membrane. For convenience, the particle size of the object to be removed, assuming it to be a perfect sphere, is equivalent to its diameter.

[0039] Another embodiment of the present invention provides a substrate processing method, comprising: a hydrophilic film forming liquid supply step, wherein a hydrophilic film forming liquid for forming a hydrophilic film on a main surface of a substrate is supplied to the main surface of the substrate, the hydrophilic film forming liquid containing a hydrophilic component having both hydrophobic and hydrophilic groups, wherein the hydrophilic groups are more numerous than the hydrophobic groups; a processing film forming liquid supply step, wherein a processing film forming liquid is supplied to the main surface of the substrate, the processing film forming liquid forming a processing film on the surface of the hydrophilic film for retaining a removal target object present on the main surface of the substrate; and a stripping liquid supply step, wherein a stripping liquid for peeling the processing film from the hydrophilic film is supplied to the main surface of the substrate.

[0040] According to this substrate processing method, a hydrophilic film can be formed on the main surface of the substrate by supplying a hydrophilic film-forming solution to the main surface of the substrate. With the hydrophilic film already formed on the main surface of the substrate, a treatment film-forming solution is supplied to the main surface of the substrate, forming a treatment film on the surface of the hydrophilic film. With the treatment film already formed on the surface of the hydrophilic film, a stripping solution is supplied to the main surface of the substrate, thereby peeling the treatment film off from the hydrophilic film. The stripping solution can be an alkaline liquid.

[0041] Even when the main surface of the substrate is hydrophobic, it can be pseudo-hydrophilized by forming a hydrophilic film on the main surface of the substrate. For example, a hydrophobic surface is a surface exposing one or more of amorphous carbon, silicon carbide, and ruthenium.

[0042] According to this substrate processing method, the hydrophilic component contained in the hydrophilic film forming solution has both hydrophobic and hydrophilic groups. Since the hydrophilic component has more hydrophilic groups than hydrophobic groups, the highly hydrophilic surface (hydrophilic film surface) can be fully exposed regardless of whether the main surface of the substrate is a hydrophobic surface.

[0043] By forming a hydrophilic film, the main surface of the substrate is made hydrophilic, allowing the stripping liquid to easily penetrate between the main surface of the substrate and the treatment film, or more specifically, the interface between the treatment film and the hydrophilic film. Therefore, the treatment film, which retains the object to be removed on the main surface of the substrate, can be easily peeled off from the main surface of the substrate.

[0044] As a result, even if the main surface of the substrate is hydrophobic, the object to be removed can still be effectively removed from the main surface of the substrate.

[0045] In other embodiments of the present invention, the processing film forming liquid contains a hydrophobic component with lower hydrophilicity than the aforementioned hydrophilic component. In a method different from this substrate processing method, where a processing film is formed on the main surface of the substrate without forming a hydrophilic film, when the main surface of the substrate is a hydrophobic surface, a hydrophobic interaction occurs between the hydrophobic component in the processing film and the main surface of the substrate. On the other hand, in this substrate processing method, the processing film is formed on the surface of a hydrophilic film. That is, the processing film is formed on the surface of a hydrophilic film located between the processing film and the main surface of the substrate. Therefore, the hydrophobic interaction between the processing film and the main surface of the substrate can be suppressed. Consequently, the stripping liquid can act effectively on the interface between the processing film and the hydrophilic film, thus effectively stripping the processing film.

[0046] In one embodiment of the present invention, the above-mentioned treatment film forming liquid contains a highly soluble component that is more soluble in the above-mentioned stripping liquid than the above-mentioned hydrophobic component.

[0047] Therefore, by supplying a stripping solution to the main surface of the substrate, highly soluble components in the treated film can be selectively dissolved in the stripping solution. While selectively dissolving the highly soluble components, the stripping solution moves towards the interface between the treated film and the hydrophilic film. Thus, the stripping solution can form pathways within the treated film. After forming pathways through the dissolution of the highly soluble components, the stripping solution efficiently reaches the interface between the treated film and the hydrophilic film via these pathways. This allows the stripping solution to effectively act on the interface between the treated film and the hydrophilic film.

[0048] When the highly soluble components are dissolved, most of the hydrophobic components remain undissolved in the stripping liquid. Therefore, the treatment film can be split into larger sheets, and the material to be removed can be held within these sheets, which are primarily composed of hydrophobic components. As a result, the treatment film can be rapidly peeled off from the main surface of the substrate, and the material to be removed, along with the treatment film, is efficiently pushed to the outside of the main surface of the substrate by the flow of the stripping liquid.

[0049] Furthermore, the term "selectively dissolving highly soluble components" does not mean that only highly soluble components are dissolved, but rather that hydrophobic components are also slightly dissolved, while most of the highly soluble components are dissolved. As hydrophobic components, the same components as the aforementioned low-soluble components can be used.

[0050] In other embodiments of the present invention, the affinity of the stripping liquid for the interface between the hydrophilic film and the treatment film is higher than that of the stripping liquid for the interface between the substrate and the hydrophilic film. Therefore, by using the stripping liquid, the hydrophilic film can be prevented from peeling off from the main surface of the substrate and the hydrophilic film can be maintained on the main surface of the substrate, while the treatment film can be peeled off from the hydrophilic film.

[0051] In other embodiments of the present invention, the substrate processing method further includes a hydrophilic film removal step, wherein after the stripping liquid supply step, a hydrophilic film removal liquid is supplied to the main surface of the substrate to remove the hydrophilic film from the main surface of the substrate.

[0052] According to this substrate processing method, after the processing film is peeled off using a stripping solution to remove the object to be removed from the main surface of the substrate, a hydrophilic film removal solution can be used to remove the hydrophilic film from the main surface of the substrate. Therefore, after the object to be removed is removed, the main surface of the substrate can be restored to its state before the formation of the hydrophilic film. The hydrophilic film removal solution can also be an acidic liquid.

[0053] Further embodiments of the present invention provide a substrate processing apparatus, comprising: a hydrophilic film forming liquid supply member for supplying a hydrophilic film forming liquid for forming a hydrophilic film onto the main surface of a substrate; a film thickness reducing liquid supply member for supplying a film thickness reducing liquid that dissolves the hydrophilic film and reduces its thickness onto the main surface of the substrate; a processing film forming liquid supply member for supplying a processing film forming liquid for forming a processing film onto the main surface of the substrate; and a stripping liquid supply member for supplying a stripping liquid that peels the processing film from the hydrophilic film onto the main surface of the substrate. According to this substrate processing apparatus, the same effects as the aforementioned substrate processing method can be achieved.

[0054] Further embodiments of the present invention provide a substrate processing apparatus, comprising: a hydrophilic film forming liquid supply member for supplying a hydrophilic film forming liquid, which forms a hydrophilic film on a main surface of a substrate, to the main surface of the substrate, the hydrophilic film forming liquid containing a hydrophilic component having both hydrophobic and hydrophilic groups, with the hydrophilic groups being more numerous than the hydrophobic groups; a processing film forming liquid supply member for supplying a processing film forming liquid to the main surface of the substrate, the processing film forming liquid forming a processing film on the surface of the hydrophilic film for retaining a removal target object present on the main surface of the substrate; and a stripping liquid supply member for supplying a stripping liquid, which peels the processing film from the hydrophilic film, to the main surface of the substrate. According to this substrate processing apparatus, the same effects as the aforementioned substrate processing method can be achieved.

[0055] The above, or other, objects, features, and effects of the present invention will be further explained with reference to the accompanying drawings and the following description of the embodiments. Attached Figure Description

[0056] Figure 1 This is a top view illustrating the configuration of a substrate processing apparatus according to an embodiment of the present invention.

[0057] Figure 2 This is a schematic diagram illustrating an example of the configuration of the processing unit included in the aforementioned substrate processing apparatus.

[0058] Figure 3 This is a block diagram illustrating an example of the configuration of the control of the aforementioned substrate processing apparatus.

[0059] Figure 4 This is a flowchart illustrating an example of the substrate processing performed by the aforementioned substrate processing apparatus.

[0060] Figure 5A This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0061] Figure 5B This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0062] Figure 5C This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0063] Figure 5D This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0064] Figure 5E This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0065] Figure 5FThis is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0066] Figure 5G This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0067] Figure 5H This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0068] Figure 5I This is a schematic diagram illustrating the substrate condition during the above-described substrate processing.

[0069] Figure 6A This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0070] Figure 6B This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0071] Figure 6C This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0072] Figure 6D This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0073] Figure 6E This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0074] Figure 6F This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0075] Figure 6G This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0076] Figure 6H This is a schematic diagram illustrating the situation near the upper surface of the substrate during the above substrate processing.

[0077] Figure 7A This is a schematic diagram illustrating the composition near the upper surface of a substrate in which a hydrophilic film and a treatment film have been formed during the above substrate processing.

[0078] Figure 7B This is a schematic diagram illustrating the composition near the upper surface of the substrate during substrate processing in a reference example where a hydrophilic film has not been formed.

[0079] Figure 8 This table shows the results of a treatment film peeling experiment in which the treatment film was peeled off from the main surface of a substrate from which a hydrophilic film had been formed using a peeling solution.

[0080] Figure 9 This table shows the results of a particle removal experiment in which the treated film was peeled off from the main surface of the substrate and the particle removal rate after peeling was measured. Detailed Implementation

[0081] <Composition of the substrate processing device>

[0082] Figure 1 This is a top view illustrating the configuration of a substrate processing apparatus 1 according to an embodiment of the present invention.

[0083] The substrate processing apparatus 1 is a monolithic apparatus for processing substrates W, such as silicon wafers, one by one. In this embodiment, the substrate W is a circular substrate. The substrate W has a pair of main surfaces, which are processed with either main surface facing upwards. At least one of the pair of main surfaces is a device surface with a raised or recessed pattern formed on it. One of the pair of main surfaces may be a non-device surface without a raised or recessed pattern formed on it.

[0084] The main surface of substrate W is a hydrophobic surface exposing a hydrophobic material. The hydrophobic material may be, for example, amorphous carbon (aC), silicon carbide (SiCN), or ruthenium (Ru). The hydrophobic surface is a surface exposing one or more of amorphous carbon, silicon carbide, and ruthenium.

[0085] The contact angle of the hydrophobic surface, which is deionized water (DIW), is 40°. The above surfaces. For example, when the hydrophobic material is ruthenium, the contact angle of DIW on the hydrophobic surface is 60°. When the hydrophobic material is silicon carbide, the contact angle of DIW with the hydrophobic surface is 60°. When the hydrophobic material is amorphous carbon, the contact angle of DIW with the hydrophobic surface is 50°. If the contact angle is 40° Therefore, hydrophobic substances can also be substances mentioned above.

[0086] Hydrophilicity refers to a high affinity for water, while hydrophobicity refers to a low affinity for water. The contact angle is an indicator of hydrophilicity and hydrophobicity. The contact angle is a numerical value representing the expansion (height of the liquid) of a droplet when a liquid is dropped onto a solid. Specifically, the contact angle is the angle formed between the liquid surface and the solid surface when viewed laterally. A larger contact angle indicates lower hydrophilicity of the solid surface, while a smaller contact angle indicates higher hydrophilicity.

[0087] The substrate processing apparatus 1 includes: multiple processing units 2 that process substrates W using fluid; a loading port LP for holding a conveyor C for accommodating multiple substrates W processed by the processing units 2; a transport robot IR and CR for transporting substrates W between the loading port LP and the processing units 2; and a controller 3 for controlling the substrate processing apparatus 1.

[0088] A transport robot IR transports substrate W between transporter C and transport robot CR. Transport robot CR transports substrate W between transport robot IR and processing unit 2. Multiple processing units 2, for example, have the same configuration. The processing fluid supplied to substrate W within processing unit 2 includes, as described later, a hydrophilic film-forming liquid, a film thickness reduction liquid, a processed film-forming liquid, a stripping liquid, a rinsing liquid, a residue removal liquid, and a hydrophilic film removal liquid.

[0089] Each processing unit 2 includes: a chamber 4; and a processing cup 7 disposed within the chamber 4. Processing of the substrate W is performed within the processing cup 7. The chamber 4 has an entrance / exit (not shown) for a transfer robot CR to move the substrate W into or out of the chamber. The chamber 4 is equipped with a gate unit (not shown) for opening and closing this entrance / exit.

[0090] Figure 2 This is a schematic cross-sectional view used to illustrate an example of the configuration of processing unit 2.

[0091] The processing unit 2 further includes: a rotary chuck 5 that holds the substrate W in a predetermined holding position while rotating the substrate W around a rotation axis A1 (vertical axis); and a heating member 6 that heats the substrate W held in the rotary chuck 5. The rotation axis A1 is a vertical line passing through the center of the substrate W. The holding position is... Figure 2 The position of the substrate W shown is the position of the substrate W held in a horizontal posture.

[0092] The rotary chuck 5 includes: a rotary base 21 having a circular plate shape in the horizontal direction; a plurality of chuck pins 20 holding the substrate W above the rotary base 21 and holding the substrate W in a holding position; a rotary shaft 22 connected to the rotary base 21 at its upper end and extending in the vertical direction; and a rotary drive member 23 for rotating the rotary shaft 22 about its central axis (rotation axis A1).

[0093] Multiple chuck pins 20 are spaced apart on the upper surface of the rotating base 21 in the circumferential direction. The rotation drive member 23 is, for example, an actuator such as an electric motor. The rotation drive member 23 rotates the rotating base 21 and the multiple chuck pins 20 about the rotation axis A1 by rotating the rotation shaft 22. As a result, the substrate W rotates together with the rotating base 21 and the multiple chuck pins 20 about the rotation axis A1.

[0094] Multiple chuck pins 20 are movable between a closed position, in contact with the periphery of the substrate W and holding the substrate W, and an open position, retracting from the periphery of the substrate W. The multiple chuck pins 20 are moved by a switching mechanism (not shown). When the multiple chuck pins 20 are in the closed position, they hold the periphery of the substrate W horizontally. The switching mechanism includes, for example, a linkage mechanism and an actuator that applies a driving force to the linkage mechanism.

[0095] The heating element 6 has the shape of a circular heating plate. The heating element 6 is disposed between the upper surface of the rotating base 21 and the lower surface of the substrate W. The heating element 6 has a heating surface 6a that faces the lower surface of the substrate W from below.

[0096] The heating element 6 includes a plate body 61 and a heater 62. The upper surface of the plate body 61 forms a heating surface 6a. The heater 62 may also be a resistor built into the plate body 61. By energizing the heater 62, the heating surface 6a is heated. The heater 62 is connected to an energizing element 64, such as a power supply, via a power supply line 63. The temperature of the heater 62 is adjusted by adjusting the current supplied by the energizing element 64.

[0097] The heating element 6 is raised and lowered via a heater lifting drive mechanism 65. The plate body 61 is connected to the heater lifting drive mechanism 65 via a lifting shaft 66. The heater lifting drive mechanism 65 includes, for example, an actuator (not shown) such as an electric motor or cylinder that drives the lifting shaft 66 to move up and down. The heating element 6 can move up and down between the lower surface of the substrate W and the upper surface of the rotating base 21. The heating element 6 can also be used to exchange with the substrate W between multiple chuck pins 20 via the raising and lowering mechanism.

[0098] The processing cup 7 collects liquid that splashes from the substrate W held in the rotating chuck 5. The processing cup 7 comprises multiple containers for collecting liquid that splashes from the substrate W held in the rotating chuck 5 to the outside. Figure 2 (In the example, there are 2) baffles 30; multiple ( ) baffles 30 to receive the liquid guided downwards by the multiple baffles 30. Figure 2 (Two cups in the example) 31; a cylindrical outer wall member 32 surrounding the multiple baffles 30 and the multiple cups 31. The multiple baffles 30 are individually raised and lowered by a baffle raising and lowering drive mechanism (not shown). The baffle raising and lowering drive mechanism includes, for example, an actuator such as an electric motor or cylinder that drives the raising and lowering of each baffle 30.

[0099] The processing unit 2 further includes: a hydrophilic film forming liquid nozzle 10 for supplying a hydrophilic film forming liquid capable of forming a hydrophilic film to the upper surface (upper main surface) of the substrate W held by the rotary chuck 5; a hydrophilic film removing liquid nozzle 12 for supplying a hydrophilic film removing liquid that removes a hydrophilic film from the upper surface of the substrate W to the upper surface of the substrate W; and a rinsing liquid nozzle 11 for supplying a rinsing liquid that rinses the liquid on the upper surface of the substrate W to the upper surface of the substrate W.

[0100] A hydrophilic film-forming solution contains both a solute and a solvent. A solid or semi-solid hydrophilic film is formed through the evaporation (evaporation) of at least a portion of the solvent in the hydrophilic film-forming solution. A solid state refers to a state where all the solvent has evaporated, and only the solute forms the hydrophilic film. A semi-solid state refers to a state where some solvent remains in the hydrophilic film, and the film is formed by both the solvent and the solute.

[0101] The formation of a hydrophilic film can be confirmed, for example, by the disappearance of interference patterns. For instance, the disappearance of interference patterns can be confirmed by photographing the upper surface of substrate W (obtaining image data of the upper surface of substrate W) using a photographic component 80. The photographic component 80 includes a camera 81 and a light source (not shown). The camera 81 includes: a lens; a photographic element that converts the optical image formed by the lens into an electrical signal; and a component that generates an image signal based on the converted electrical signal, and transmits image data consisting of the image signal and timing information to a controller 3 (see reference 3). Figure 1 The imaging circuitry. Imaging elements include, for example, CCD (Charge Coupled Devices) sensors or CMOS (Complementary Metal Oxide Semiconductor) sensors.

[0102] The hydrophilic film-forming solution contains a hydrophilic component as a solute. The hydrophilic component is, for example, an organic compound having a main chain (backbone) and multiple side chains bonded to the main chain. These side chains include multiple hydrophobic side chains and multiple hydrophilic side chains. The hydrophobic side chains are composed of hydrophobic groups, and the hydrophilic side chains are composed of hydrophilic groups. As functional groups constituting the side chains, there are more hydrophilic groups than hydrophobic groups.

[0103] Hydrophilic components do not necessarily exist as the main chain; any organic compound with both hydrophilic and hydrophobic groups is acceptable.

[0104] Hydrophilic components possess hydrophobic groups (first hydrophobic groups), such as hydrocarbon groups. Examples of hydrocarbon groups include alkyl, vinyl, and phenyl groups. Hydrophilic components possess hydrophilic groups (first hydrophilic groups), such as hydroxyl, amino, thiol, aldehyde, amide (amide bond), and carbonyl groups. Carbonyl groups include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones. Multiple hydrophobic groups do not need to be of the same type, and a hydrophilic component can contain multiple types of hydrophobic groups. Similarly, multiple hydrophilic groups do not need to be of the same type, and a hydrophilic component can contain multiple types of hydrophilic groups. Hydrophilic components can have an amino group as a hydrophilic group and a pyridine skeleton as the main skeleton.

[0105] The hydrophilic component is particularly a nitrogen-containing polymer, a nitrogen-containing compound, or a saturated nitrogen-containing hydrocarbon ring, or a salt thereof. The hydrophilic component is preferably a nitrogen-containing polymer.

[0106] Examples of nitrogen-containing polymers include polyallylamine, polydiallylamine, polyvinylpyrrolidone, and copolymers thereof. Polyethyleneimine may also be a nitrogen-containing polymer. Polyallylamine and polydiallylamine are preferred nitrogen-containing polymers.

[0107] Examples of nitrogen-containing compounds include 1,4-diaminobutane, N,N'-bis(3-aminopropyl)ethylenediamine, N,N,N',N”,N”-pentamethylethylenediamine, N,N,N',N’-tetramethylethylenediamine, and 2,6,10-trimethyl-2,6,10-triazaundecane. Other nitrogen-containing compounds include diallylamine, triallylamine, 2-(2-aminoethylamino)ethanol, and diethanolamine.

[0108] Saturated nitrogen-containing hydrocarbon rings can have a cage-like three-dimensional structure or a planar ring structure. This invention is not intended to be particularly limited, but specific examples of saturated nitrogen-containing hydrocarbon rings with a cage-like three-dimensional structure include 1,4-diazabicyclo[2.2.2]octane and hexamethylenetetramine. Specific examples of saturated nitrogen-containing hydrocarbon groups with a planar ring structure include 1,4,7,10-tetraazacyclododecane.

[0109] The solvent in a hydrophilic film-forming solution is a liquid component that dissolves the hydrophilic components. The solvent contained in the hydrophilic film-forming solution is a liquid at room temperature, and it can be any substance that can dissolve the hydrophilic components and evaporate through the rotation or heating of the substrate W.

[0110] The solvent for hydrophilic film-forming solutions can be, for example, water such as DIW. Organic solvents may also be contained in the solvent of hydrophilic film-forming solutions.

[0111] Organic solvents used as solvents in hydrophilic film-forming solutions can include, for example, alcohols such as ethanol (EtOH) and isopropanol (IPA); ethylene glycol monomethyl ethers and ethylene glycol monoethyl ethers; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE); lactate esters such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as toluene and xylene; and ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone. Additionally, propylene glycol monomethyl ether acetate (PGMEA) can also be used as an organic solvent in hydrophilic film-forming solutions. These organic solvents can be used alone or in combination of two or more.

[0112] In addition to hydrophilic components, hydrophilic film-forming solutions may also contain surfactants as solutes. Surfactants can be used to improve coatability or solubility. Examples of surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants.

[0113] Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonic acids, and alkylbenzene sulfonates.

[0114] Examples of cationic surfactants include laurylpyridinium chloride and laurylmethylammonium chloride.

[0115] Examples of nonionic surfactants include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene ethynyl glycol ether, and fluorinated surfactants (such as Fluorad (3M), MEGAFAC (DIC), and Surflon (AGC SEIMICHEMICAL)).

[0116] These surfactants can be used alone or in combination of two or more.

[0117] The rinsing solution may be, for example, deionized water or other water. The rinsing solution is not limited to DIW; any liquid containing at least one of DIW, electrolyzed ionized water, or reduced water (hydrogen water) is acceptable. Preferably, the rinsing solution is the same liquid as the solvent for the hydrophilic film-forming solution. For example, when using DIW as the solvent for the hydrophilic film-forming solution, it is preferable to use DIW as the rinsing solution.

[0118] A hydrophilic membrane removal solution is a liquid with the property of dissolving hydrophilic components. Examples of hydrophilic membrane removal solutions include acidic liquids (acidic aqueous solutions) such as hydrochloric acid. The acidic solution used as a hydrophilic membrane removal solution is not limited to hydrochloric acid. The hydrophilic membrane removal solution contains at least one of hydrochloric acid, dilute sulfuric acid (aqueous sulfuric acid), dilute nitric acid (aqueous nitric acid), formic acid, acetic acid, citric acid, and oxalic acid. The hydrophilic membrane removal solution only needs to remove the hydrophilic membrane from the main surface of the substrate W; it does not need to be an aqueous solution, and can also be a liquid containing an organic solvent as a solvent.

[0119] The hydrophilic film-forming fluid nozzle 10, the rinsing fluid nozzle 11, and the hydrophilic film-removing fluid nozzle 12 are all movable nozzles that can move at least in the horizontal direction. The hydrophilic film-forming fluid nozzle 10, the rinsing fluid nozzle 11, and the hydrophilic film-removing fluid nozzle 12 are moved horizontally by a first nozzle moving mechanism 35. The first nozzle moving mechanism 35 includes: a first arm 35A that commonly supports the hydrophilic film-forming fluid nozzle 10, the rinsing fluid nozzle 11, and the hydrophilic film-removing fluid nozzle 12; and a first arm moving mechanism 35B that moves the first arm 35A horizontally. The first arm moving mechanism 35B includes actuators such as an electric motor and a cylinder.

[0120] Unlike this embodiment, the hydrophilic film-forming liquid nozzle 10, the rinsing liquid nozzle 11, and the hydrophilic film-removing liquid nozzle 12 can also move in the vertical direction. Unlike this embodiment, the hydrophilic film-forming liquid nozzle 10, the rinsing liquid nozzle 11, and the hydrophilic film-removing liquid nozzle 12 can also be fixed nozzles with their horizontal and vertical positions fixed. Alternatively, the hydrophilic film-forming liquid nozzle 10, the rinsing liquid nozzle 11, and the hydrophilic film-removing liquid nozzle 12 can be individually movable.

[0121] A hydrophilic film-forming liquid nozzle 10 is connected to one end of a hydrophilic film-forming liquid piping 40 that guides the hydrophilic film-forming liquid to the nozzle 10. The other end of the hydrophilic film-forming liquid piping 40 is connected to a hydrophilic film-forming liquid tank (not shown). The hydrophilic film-forming liquid piping 40 is equipped with a hydrophilic film-forming liquid valve 50A for opening and closing the flow path within the piping 40, and a hydrophilic film-forming liquid flow rate regulating valve 50B for adjusting the flow rate of the hydrophilic film-forming liquid within that flow path.

[0122] If the hydrophilic film forming liquid valve 50A is opened, the hydrophilic film forming liquid is continuously ejected from the nozzle 10 downwards at a flow rate corresponding to the opening of the hydrophilic film forming liquid flow rate regulating valve 50B. The hydrophilic film forming liquid nozzle 10 is an example of a hydrophilic film forming liquid supply component.

[0123] The flushing fluid nozzle 11 is connected to one end of the flushing fluid pipe 41 that guides the flushing fluid to the nozzle 11. The other end of the flushing fluid pipe 41 is connected to a flushing fluid tank (not shown). The flushing fluid pipe 41 is equipped with a flushing fluid valve 51A that opens and closes the flow path within the pipe, and a flushing fluid flow rate regulating valve 51B that adjusts the flow rate of the flushing fluid within that flow path. When the flushing fluid valve 51A is opened, the flushing fluid is continuously ejected from the nozzle outlet of the flushing fluid nozzle 11 downwards at a flow rate corresponding to the opening of the flushing fluid flow rate regulating valve 51B.

[0124] The hydrophilic membrane removal fluid nozzle 12 is connected to one end of a hydrophilic membrane removal fluid piping 42 that guides the hydrophilic membrane removal fluid to the nozzle 12. The other end of the hydrophilic membrane removal fluid piping 42 is connected to a hydrophilic membrane removal fluid tank (not shown). The hydrophilic membrane removal fluid piping 42 is equipped with a hydrophilic membrane removal fluid valve 52A for opening and closing the flow path within the piping 42, and a hydrophilic membrane removal fluid flow rate regulating valve 52B for adjusting the flow rate of the hydrophilic membrane removal fluid within the flow path. When the hydrophilic membrane removal fluid valve 52A is opened, the hydrophilic membrane removal fluid is continuously sprayed downwards from the nozzle outlet of the hydrophilic membrane removal fluid nozzle 12 at a flow rate corresponding to the opening degree of the hydrophilic membrane removal fluid flow rate regulating valve 52B.

[0125] The processing unit 2 further includes: a processing film forming liquid nozzle 13 for supplying a processing film forming liquid capable of forming a processing film to the upper surface of the substrate W; and a stripping liquid nozzle 14 for supplying a stripping liquid that peels the processing film from the upper surface of the substrate W to the upper surface of the substrate W.

[0126] The treatment film forming solution contains a solvent and a solute. A solid or semi-solid treatment film is formed by the evaporation (evaporation) of at least a portion of the solvent in the treatment film forming solution. The treatment film retains particles or other substances present on the substrate W that are being removed. Similar to the formation of hydrophilic films, the formation of the treatment film can also be confirmed by the disappearance of interference fringes.

[0127] The membrane-forming solution contains a low-soluble component as a solute and a high-soluble component with a higher solubility than the low-soluble component in the stripping solution. The low-soluble and high-soluble components can be substances with different solubility relative to the removal solution described later. The low-soluble component is also a hydrophobic component with lower hydrophilicity than the hydrophilic component contained in the hydrophilic membrane-forming solution.

[0128] Examples of low-soluble components include phenolic varnishes. Low-soluble components are organic compounds having a main chain (backbone) and multiple side chains bonded to the main chain. Low-soluble components are hydrophobic components with lower hydrophilicity than the hydrophilic components contained in hydrophilic film-forming liquids. The multiple side chains include multiple hydrophobic side chains and multiple hydrophilic side chains. Hydrophobic side chains contain hydrophobic groups, and hydrophilic side chains contain hydrophilic groups. The proportion of hydrophilic side chains in the multiple side chains of a low-soluble component is smaller than the proportion of hydrophilic side chains in the multiple side chains of a hydrophilic component.

[0129] Low-soluble components do not necessarily need to be present in the main chain; they can be organic compounds that have both hydrophilic and hydrophobic groups and whose hydrophilicity is lower than that of the hydrophilic component.

[0130] The hydrophobic group (second hydrophobic group) of a low-solubility component is, for example, a hydrocarbon group. Examples of hydrocarbon groups include alkyl, vinyl, and phenyl groups. The hydrophilic group (second hydrophilic group) of a hydrophilic component is, for example, a hydroxyl, amino, thiol, aldehyde, amide (amide bond), or carbonyl group. Multiple hydrophobic groups do not need to be of the same type, and a hydrophilic component may contain multiple types of hydrophobic groups. Similarly, multiple hydrophilic groups do not need to be of the same type, and a hydrophilic component may contain multiple types of hydrophilic groups.

[0131] Highly soluble components include, for example, 2,2-bis(4-hydroxyphenyl)propane. A highly soluble component does not necessarily need to form the main backbone; it is an organic compound containing a hydrocarbon group as a hydrophobic group and at least one of a hydroxyl or carbonyl group as a hydrophilic group. Furthermore, highly soluble components tend to have higher hydrophilicity than less soluble components. Highly soluble components can also be organic compounds having a main chain (main backbone) and multiple side chains bonded to the main chain.

[0132] The treated membrane is mainly composed of a solid component with low solubility (low-soluble solids) and a solid component with high solubility (high-soluble solids). The solvent in the membrane-forming solution only needs to be a liquid that dissolves both the low-soluble and high-soluble components. The membrane-forming solution may also contain corrosion-resistant components. This will be discussed in detail later; an example corrosion-resistant component is BTA (benzotriazole).

[0133] A stripping solution is a liquid that removes the treatment film from the main surface of the substrate W without peeling off the hydrophilic film. The stripping solution is, for example, an alkaline liquid (alkaline aqueous solution) such as ammonia. However, the stripping solution used is not limited to ammonia. It can also be an aqueous solution of TMAH (tetramethylammonium hydroxide), an aqueous solution of choline, or any combination thereof. The stripping solution only needs to remove the treatment film from the main surface of the substrate W without peeling off the hydrophilic film; it does not need to be an aqueous solution.

[0134] Both the processing film forming fluid nozzle 13 and the stripping fluid nozzle 14 are movable nozzles that can move at least in the horizontal direction. The processing film forming fluid nozzle 13 and the stripping fluid nozzle 14 are moved horizontally by a second nozzle moving mechanism 36. The second nozzle moving mechanism 36 includes a second arm 36A that commonly supports the processing film forming fluid nozzle 13 and the stripping fluid nozzle 14, and a second arm moving mechanism 36B that moves the second arm 36A horizontally. The second arm moving mechanism 36B includes actuators such as an electric motor and a cylinder.

[0135] Unlike this embodiment, the processing film forming liquid nozzle 13 and the stripping liquid nozzle 14 can also move in the vertical direction. Unlike this embodiment, the processing film forming liquid nozzle 13 and the stripping liquid nozzle 14 can also be fixed nozzles with their horizontal and vertical positions fixed. Alternatively, the processing film forming liquid nozzle 13 and the stripping liquid nozzle 14 can be individually movable.

[0136] The processing film forming fluid nozzle 13 is connected to one end of a processing film forming fluid pipe 43 that guides the processing film forming fluid to the nozzle 13. The other end of the processing film forming fluid pipe 43 is connected to a processing film forming fluid tank (not shown). The processing film forming fluid pipe 43 is equipped with a processing film forming fluid valve 53A that opens and closes the flow path within the pipe 43, and a processing film forming fluid flow rate regulating valve 53B that adjusts the flow rate of the processing film forming fluid within the flow path. When the processing film forming fluid valve 53A is opened, the processing film forming fluid is continuously ejected from the nozzle 13 downwards at a flow rate corresponding to the opening of the flow rate regulating valve 53B. The processing film forming fluid nozzle 13 is an example of a processing film forming fluid supply component.

[0137] The stripper nozzle 14 is connected to one end of a stripper pipe 44 that guides the stripper fluid to the nozzle. The other end of the stripper pipe 44 is connected to a stripper tank (not shown). The stripper pipe 44 is equipped with a stripper valve 54A that opens and closes the flow path within the pipe, and a stripper flow rate regulating valve 54B that adjusts the flow rate of the stripper fluid within that flow path. When the stripper valve 54A is opened, the stripper fluid is continuously ejected from the nozzle outlet of the stripper nozzle 14 downwards at a flow rate corresponding to the opening of the stripper flow rate regulating valve 54B. The stripper nozzle 14 is an example of a stripper fluid supply component.

[0138] The processing unit 2 also includes a residue removal liquid nozzle 15 that supplies residue removal liquid, which removes processing film residue remaining on the upper surface of the substrate W, to the upper surface of the substrate W.

[0139] The residue removal solution is preferably compatible with rinsing solutions and acidic liquids. The residue removal solution dissolves the residue in the treated membrane. Therefore, the residue removal solution is also called a residue dissolving solution. The residue removal solution can be, for example, an organic solvent, or a liquid containing at least one of IPA, HFE (hydrofluoroether), methanol, EtOH, acetone, PGEE, and trans-1,2-dichloroethylene.

[0140] The residue removal liquid nozzle 15 is a movable nozzle that can move at least in the horizontal direction. The residue removal liquid nozzle 15 moves horizontally via a third nozzle moving mechanism 37. The third nozzle moving mechanism 37 includes a third arm 37A that supports the residue removal liquid nozzle 15, and a third arm moving mechanism 37B that moves the third arm 37A horizontally. The third arm moving mechanism 37B includes actuators such as an electric motor and a cylinder.

[0141] Unlike this embodiment, the residue removal liquid nozzle 15 can also move in the vertical direction. The residue removal liquid nozzle 15, unlike in this embodiment, can also be a fixed nozzle whose horizontal and vertical positions are fixed.

[0142] The residue removal liquid nozzle 15 is connected to one end of the residue removal liquid pipe 45 that guides the residue removal liquid to the nozzle 15. The other end of the residue removal liquid pipe 45 is connected to a residue removal liquid tank (not shown). The residue removal liquid pipe 45 is equipped with a residue removal liquid valve 55A that opens and closes the flow path within the pipe 45, and a residue removal liquid flow rate regulating valve 55B that adjusts the flow rate of the residue removal liquid within the flow path. When the residue removal liquid valve 55A is opened, the residue removal liquid is continuously sprayed downwards from the nozzle outlet of the residue removal liquid nozzle 15 at a flow rate corresponding to the opening degree of the flow rate regulating valve 55B.

[0143] Figure 3 This is a block diagram illustrating an example of the configuration of the control system of the substrate processing apparatus 1. The controller 3 includes a microcomputer and controls the controlled objects included in the substrate processing apparatus 1 according to a predetermined control program.

[0144] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B for storing control programs. The controller 3 is configured to execute various controls for substrate processing by executing the control programs through the processor 3A.

[0145] In particular, the controller 3 is programmed to control the conveying robot IR, CR, rotary drive component 23, first nozzle moving mechanism 35, second nozzle moving mechanism 36, third nozzle moving mechanism 37, energizing component 64, heater lifting drive mechanism 65, imaging component 80, hydrophilic film forming liquid valve 50A, hydrophilic film forming liquid flow rate adjustment valve 50B, rinsing liquid valve 51A, rinsing liquid flow rate adjustment valve 51B, hydrophilic film removal liquid valve 52A, hydrophilic film removal liquid flow rate adjustment valve 52B, treatment film forming liquid valve 53A, treatment film forming liquid flow rate adjustment valve 53B, stripping liquid valve 54A, stripping liquid flow rate adjustment valve 54B, residue removal liquid valve 55A, residue removal liquid flow rate adjustment valve 55B, etc.

[0146] The controller 3 controls whether fluid is ejected from the corresponding nozzle or the flow rate of fluid ejected from the corresponding nozzle by controlling the valve.

[0147] The following steps are executed by controller 3, which controls these components. In other words, controller 3 is programmed to execute the following steps.

[0148] <An example of substrate processing>

[0149] Figure 4 This is a flowchart illustrating an example of substrate processing performed by substrate processing apparatus 1. Figure 4 This mainly refers to the processing achieved by executing a program through controller 3. Figures 5A to 5I This is a schematic diagram illustrating the steps of substrate processing performed by substrate processing apparatus 1.

[0150] The substrate processing performed by the substrate processing apparatus 1, for example, Figure 4 As shown, the following steps are performed sequentially: substrate loading (step S1), hydrophilic film forming solution supply (step S2), hydrophilic film forming (step S3), film thickness reduction (step S4), processing film forming solution supply (step S5), processing film forming (step S6), stripping solution supply (step S7), first rinsing (step S8), residue removal solution supply (step S9), hydrophilic film removal solution supply (step S10), second rinsing (step S11), rotary drying (step S12), and substrate unloading (step S13).

[0151] The following refers primarily to the substrate processing performed by the substrate processing apparatus 1. Figure 2 and Figure 4 Please provide an explanation. (References may vary.) Figures 5A to 5I .

[0152] First, the untreated substrate W is transported by the robotic arms IR and CR (see reference). Figure 1The substrate W is transferred from the conveyor C to the processing unit 2 and then handed over to the rotary chuck 5 (substrate loading step: step S1). The substrate W is then held horizontally by the rotary chuck 5 (substrate holding step). The holding of the substrate W by the rotary chuck 5 continues until the rotary drying step (step S12) ends.

[0153] Next, after the transport robot CR retracts outside the processing unit 2, it performs the hydrophilic film-forming liquid supply step (step S2) to supply hydrophilic film-forming liquid to the upper surface of the substrate W. Specifically, the first nozzle moving mechanism 35 moves the hydrophilic film-forming liquid nozzle 10 to the processing position, and with the hydrophilic film-forming liquid nozzle 10 in the processing position, the hydrophilic film-forming liquid valve 50A is opened. Thus, as... Figure 5A As shown, a hydrophilic film forming liquid is supplied from the hydrophilic film forming liquid nozzle 10 to the upper surface of the substrate W (hydrophilic film forming liquid supply step). The hydrophilic film forming liquid ejected from the hydrophilic film forming liquid nozzle 10 falls onto the upper surface of the substrate W.

[0154] In this substrate processing, the processing position of the hydrophilic film forming liquid nozzle 10 is the central position opposite to the central region of the upper surface of the substrate W. Therefore, the hydrophilic film forming liquid will fall onto the central region of the upper surface of the substrate W.

[0155] During the supply of the hydrophilic film-forming solution to the upper surface of the substrate W, the substrate W can also be rotated at a low speed (e.g., 10 rpm) (first low-speed rotation step). Alternatively, the rotation of the substrate W can be stopped during the supply of the hydrophilic film-forming solution to the upper surface of the substrate W. By setting the rotation speed of the substrate W to a low speed or stopping the rotation of the substrate W, the hydrophilic film-forming solution supplied to the substrate W remains in the central region of the upper surface of the substrate W. This reduces the amount of hydrophilic film-forming solution used.

[0156] The hydrophilic film-forming solution is supplied at a specified flow rate and continuously for a specified supply period. The supply period is, for example, 5 seconds or more but less than 30 seconds. The supply flow rate is, for example, 500 mL / min.

[0157] Next, as Figure 5B and Figure 5C As shown, the process involves rotating a substrate W on which a hydrophilic film-forming liquid has been applied to its upper surface to form a hydrophilic film 100 on the upper surface of the substrate W (see reference). Figure 5C The hydrophilic membrane formation step (step S3).

[0158] Specifically, the hydrophilic film-forming liquid valve 50A is closed, stopping the ejection of the hydrophilic film-forming liquid from the hydrophilic film-forming liquid nozzle 10. After closing the hydrophilic film-forming liquid valve 50A, as... Figure 5BAs shown, the rotation of substrate W is accelerated to a predetermined first spin-off speed (first spin-off acceleration step). The first spin-off speed is, for example, 1500 rpm. The first spin-off step is performed for, for example, 20 seconds.

[0159] The hydrophilic film-forming liquid, initially present in the central region of the upper surface of substrate W, expands towards the periphery of the upper surface of substrate W due to the centrifugal force caused by the rotation of substrate W. Thus, the hydrophilic film-forming liquid spreads to the entire upper surface of substrate W. Figure 5B As shown, a portion of the hydrophilic film-forming liquid on the substrate W is diffused from the periphery of the substrate W to the outside of the substrate W, and the liquid film of the hydrophilic film-forming liquid on the substrate W becomes a thin film (first spin-off step).

[0160] The hydrophilic film-forming liquid on the upper surface of substrate W does not necessarily need to be dispersed outside substrate W. It can be spread to the entire upper surface of substrate W by utilizing the centrifugal force of substrate W's rotation.

[0161] The centrifugal force caused by the rotation of substrate W acts not only on the hydrophilic film-forming liquid on substrate W, but also on the gas in contact with the hydrophilic film-forming liquid on substrate W. Therefore, through the action of centrifugal force, this gas forms an airflow from the center side of the upper surface of substrate W towards the periphery. Through this airflow, the gaseous solvent in contact with the hydrophilic film-forming liquid on substrate W is removed from the environment in contact with substrate W. Therefore, as... Figure 5C As shown, the solvent is promoted to evaporate (evaporate) from the hydrophilic film forming liquid on the substrate W to form a hydrophilic film 100 (hydrophilic film forming step).

[0162] Thus, the hydrophilic film forming liquid nozzle 10 and the rotation drive member 23 function as a hydrophilic film forming unit. The thickness of the hydrophilic film 100 formed by the hydrophilic film forming step is, for example, 20 nm or more and 30 nm or less.

[0163] Next, a film thickness reduction step (step S4) is performed, which reduces the thickness of the hydrophilic membrane 100 by dissolving the hydrophilic membrane 100 in the rinsing solution.

[0164] Specifically, the first nozzle moving mechanism 35 moves the flushing fluid nozzle 11 to the processing position, and while the flushing fluid nozzle 11 is in the processing position, the flushing fluid valve 51A is opened. Thus, as... Figure 5D As shown, rinsing fluid is supplied from rinsing fluid nozzle 11 to the upper surface of substrate W (rinsing fluid supply step). The rinsing fluid sprayed from rinsing fluid nozzle 11 will fall onto the upper surface of substrate W. The rinsing fluid supplied to the upper surface of substrate W is spread to the entire upper surface of substrate W by centrifugal force. In this substrate processing, since the processing position of rinsing fluid nozzle 11 is located in the center, the rinsing fluid will fall in the central area of ​​the upper surface of substrate W.

[0165] The supply of rinsing fluid to the upper surface of substrate W can also begin after a predetermined period has elapsed since the start of the first spin-off step. Alternatively, the timing of the start of the supply of rinsing fluid to the upper surface of substrate W can be determined by monitoring the state of the upper surface of substrate W during substrate processing.

[0166] As described above, the formation of the hydrophilic film 100 can be confirmed by the disappearance of interference fringes. Therefore, the start time of the film thickness reduction liquid supply step (the time of opening the rinsing liquid valve 51A) is simultaneously with the disappearance of interference fringes, or after a predetermined period (e.g., 5 seconds) has elapsed since the disappearance of interference fringes. For example, the controller 3 can determine whether the formation of the hydrophilic film 100 is complete (hydrophilic film formation determination step) based on image data acquired by the imaging member 80 at predetermined intervals (e.g., 1-second intervals), and start the film thickness reduction liquid supply step at the appropriate time. Specifically, the controller 3 monitors the upper surface of the substrate W during the period until the formation of the hydrophilic film 100, and opens the rinsing liquid valve 51A when it determines that the formation of the hydrophilic film 100 is complete.

[0167] A portion of the hydrophilic film 100 is dissolved using a rinsing liquid adhering to the upper surface of the substrate W (strictly speaking, the surface of the hydrophilic film 100). This reduces the thickness of the hydrophilic film 100 on the upper surface of the substrate W (film thickness reduction step). The thickness of the hydrophilic film 100 after the film thickness reduction step is, for example, 1 Å or more and 10 Å or less. Thus, the rinsing liquid functions as a film thickness reduction liquid to reduce the thickness of the hydrophilic film 100. Therefore, the rinsing liquid supply step is an example of a film thickness reduction liquid supply step that supplies film thickness reduction liquid to the upper surface of the substrate W. Similarly, the rinsing liquid nozzle 11 is an example of a film thickness reduction liquid supply member.

[0168] The rinsing solution, used as the film thickness reduction solution, is supplied at a specified flow rate and continues for a specified film thickness reduction period. The film thickness reduction period is, for example, 5 seconds or more and 30 seconds or less. The supply flow rate of the rinsing solution is, for example, 2000 mL / min. The rotation speed of the substrate W during the film thickness reduction step is, for example, 1500 rpm.

[0169] Next, after the film thickness reduction step, a processing film forming liquid supply step (step S5) is performed to supply processing film forming liquid to the upper surface of the substrate W. Specifically, the second nozzle moving mechanism 36 moves the processing film forming liquid nozzle 13 to the processing position. With the processing film forming liquid nozzle 13 in the processing position, the processing film forming liquid valve 53A is opened. Thus, as Figure 5EAs shown, a processing film forming liquid is supplied to the upper surface of the substrate W from the processing film forming liquid nozzle 13 (processing film forming liquid supply step). The processing film forming liquid ejected from the processing film forming liquid nozzle 13 will fall onto the upper surface of the substrate W. In this substrate processing, since the processing position of the processing film forming liquid nozzle 13 is located in the center, the processing film forming liquid will fall into the central area of ​​the upper surface of the substrate W.

[0170] The rinsing fluid valve 51A is closed before the processing film forming fluid valve 53A is opened. After the rinsing fluid valve 51A is closed, the rinsing fluid nozzle 11 is moved to a retracted position by the first nozzle moving mechanism 35. The retracted position is a position that is not opposite to the upper surface of the substrate W and is located outside the processing cup 7 when viewed from above.

[0171] During the supply of the processing film forming solution to the upper surface of the substrate W, the substrate W can also be rotated at a low speed (e.g., 10 rpm) (second low-speed rotation step). Alternatively, the rotation of the substrate W can be stopped during the supply of the processing film forming solution to the upper surface of the substrate W. By setting the rotation speed of the substrate W to a low speed, or stopping the rotation of the substrate W, the processing film forming solution supplied to the substrate W remains in the central region of the upper surface of the substrate W. As a result, the amount of processing film forming solution used can be reduced.

[0172] The treatment membrane forming solution is supplied continuously at a specified flow rate for a specified treatment membrane forming solution supply period. The treatment membrane forming solution supply period is, for example, more than 2 seconds and less than 4 seconds. The treatment membrane forming solution supply flow rate is, for example, 1.0 mL / min.

[0173] Next, as Figure 5F and Figure 5G As shown, the process involves rotating a substrate W, whose upper surface is coated with a processing film forming liquid, to form a processing film 101 on the upper surface of the substrate W (see reference). Figure 5G The membrane formation step (step S5) is performed.

[0174] Specifically, the process membrane forming liquid valve 53A is closed to stop the ejection of the hydrophilic membrane forming liquid from the process membrane forming liquid nozzle 13. After closing the process membrane forming liquid valve 53A, as... Figure 5F As shown, the substrate W is rotated and accelerated to a predetermined second rotation speed (second rotation acceleration step). The second rotation speed is, for example, 1500 rpm. The second rotation step is performed for, for example, 30 seconds.

[0175] The processing film forming liquid, which remains in the central region of the upper surface of substrate W, expands towards the periphery of the upper surface of substrate W due to the centrifugal force caused by the rotation of substrate W. Thus, the processing film forming liquid expands to cover the entire upper surface of substrate W. Figure 5FAs shown, a portion of the processing film forming liquid on the substrate W is dispersed from the periphery of the substrate W to the outside of the substrate W, and the liquid film of the processing film forming liquid on the substrate W becomes a thin film (second spin-off step).

[0176] The liquid used to form the treatment film on the upper surface of the substrate W does not necessarily need to be dispersed outside the substrate W. It can be spread to the entire upper surface of the substrate W by utilizing the centrifugal force of the rotating substrate W.

[0177] Similar to the hydrophilic film formation step, utilizing the centrifugal force caused by the rotation of the substrate W, the gas in liquid phase contact with the processed film on the substrate W can also form an airflow from the center side of the upper surface of the substrate W towards the periphery. Through this airflow, such as Figure 5G As shown, the solvent is promoted to evaporate (evaporate) from the processing film forming liquid on the substrate W to form a processing film 101 (processing film forming step). In this way, the processing film forming liquid nozzle 13 and the rotation drive member 23 function as a processing film forming unit. The thickness of the processing film 101 formed by the processing film forming step is, for example, 100 nm or more and 200 nm or less.

[0178] Next, after the film formation step, a stripping liquid supply step (step S7) is performed to supply stripping liquid to the upper surface of the substrate W. Specifically, the second nozzle moving mechanism 36 moves the stripping liquid nozzle 14 to the processing position, and while the stripping liquid nozzle 14 is in the processing position, the stripping liquid valve 54A is opened. By opening the stripping liquid valve 54A, as... Figure 5H As shown, stripping fluid is supplied from the stripping fluid nozzle 14 to the upper surface of the rotating substrate W (stripping fluid supply step). The stripping fluid ejected from the stripping fluid nozzle 14 will fall onto the upper surface of the substrate W. The stripping fluid supplied to the upper surface of the substrate W is spread to the entire substrate W by centrifugal force. In this substrate processing, since the processing position of the stripping fluid nozzle 14 is in the center position, the stripping fluid will fall into the central area of ​​the upper surface of the substrate W.

[0179] The stripping liquid supplied to the upper surface of the substrate W dissolves a portion (highly soluble component) of the treatment film 101, reaches the interface between the upper surface of the substrate W and the treatment film 101, and enters the space between the treatment film 101 and the upper surface of the substrate W. By continuously supplying the stripping liquid, the treatment film 101 is peeled off and removed from the surface of the hydrophilic film 100 (treatment film removal step). On the other hand, the hydrophilic film 100 remains on the upper surface of the substrate W.

[0180] The stripping fluid supply step can also begin after a predetermined period from the start of the second spin-off step. Alternatively, as explained in the film thickness reduction step (step S4), the timing of the start of the stripping fluid supply step can also be determined by monitoring the state of the upper surface of the substrate W during substrate processing.

[0181] After the stripping fluid supply step, the first rinsing step (step S8) of rinsing the upper surface of the substrate W and the residue removal fluid supply step (step S9) of supplying residue removal fluid to the upper surface of the substrate W are performed in sequence.

[0182] Specifically, the first nozzle moving mechanism 35 moves the rinsing fluid nozzle 11 to the processing position, and while the rinsing fluid nozzle 11 is in the processing position, the rinsing fluid valve 51A is opened. This supplies rinsing fluid to the upper surface of the substrate W from the rinsing fluid nozzle 11 (rinsing fluid supply step). The rinsing fluid supplied to the upper surface of the substrate W is spread to the entire substrate W using centrifugal force. This washes away the stripping fluid adhering to the upper surface of the substrate W, and the stripping fluid is discharged from the upper surface of the substrate W (first rinsing step). Since a hydrophilic film 100 has been formed on the upper surface of the substrate W, strictly speaking, the stripping fluid is discharged from the surface of the hydrophilic film 100.

[0183] Before the flushing fluid valve 51A is opened, the stripping fluid valve 54A is closed. After the stripping fluid valve 54A is closed, the second nozzle moving mechanism 36 moves the stripping fluid nozzle 14 to the retracted position.

[0184] During a specified time period, after rinsing liquid is supplied to the upper surface of the substrate W, the third nozzle moving mechanism 37 moves the residue removal liquid nozzle 15 to the processing position. With the residue removal liquid nozzle 15 in the processing position, the residue removal liquid valve 55A is opened. As a result, residue removal liquid is supplied to the upper surface of the substrate W from the residue removal liquid nozzle 15 (residue removal liquid supply step). The residue removal liquid supplied to the upper surface of the substrate W is spread to the entire substrate W by centrifugal force. As a result, the residue of the processing film 101 adhering to the upper surface of the substrate W (strictly speaking, the surface of the hydrophilic film 100) is dissolved by the residue removal liquid and removed from the upper surface of the substrate W along with the residue removal liquid (residue removal step). In this substrate processing, since the processing position of the residue removal liquid nozzle 15 is the central position, the rinsing liquid will fall on the central area of ​​the upper surface of the substrate W.

[0185] After the residue removal liquid supply step (step S9), a hydrophilic membrane removal liquid supply step (step S10) is performed to supply hydrophilic membrane removal liquid to the upper surface of the substrate W. Specifically, the first nozzle moving mechanism 35 moves the hydrophilic membrane removal liquid nozzle 12 to the processing position, and with the hydrophilic membrane removal liquid nozzle 12 in the central position, the hydrophilic membrane removal liquid valve 52A is opened. Thus, as... Figure 5IAs shown, a hydrophilic film removal solution is supplied from the hydrophilic film removal solution nozzle 12 to the upper surface of the substrate W (hydrophilic film removal solution supply step). The hydrophilic film removal solution sprayed from the hydrophilic film removal solution nozzle 12 will fall onto the upper surface of the substrate W. The hydrophilic film removal solution supplied to the upper surface of the substrate W will spread to the entire substrate W by centrifugal force. In this substrate processing, since the processing position of the hydrophilic film removal solution nozzle 12 is the central position, the hydrophilic film removal solution will fall on the central area of ​​the upper surface of the substrate W.

[0186] By supplying a hydrophilic film removal solution to the upper surface of the substrate W, the hydrophilic film 100 held on the upper surface of the substrate W is dissolved by the hydrophilic film removal solution and removed from the upper surface of the substrate W together with the hydrophilic film removal solution (hydrophilic film removal step).

[0187] Before opening the hydrophilic membrane removal liquid valve 52A, close the residue removal liquid valve 55A. After closing the residue removal liquid valve 55A, the residue removal liquid nozzle 15 is moved to the retracted position by the third nozzle moving mechanism 37.

[0188] Following the hydrophilic film removal solution supply step, a second rinsing step (step S11) is performed to rinse the upper surface of the substrate W. Specifically, the first nozzle moving mechanism 35 moves the rinsing solution nozzle 11 to the processing position, and while the rinsing solution nozzle 11 is in the processing position, the rinsing solution valve 51A is opened. As a result, rinsing solution is supplied to the upper surface of the substrate W from the rinsing solution nozzle 11 (rinsing solution supply step). The rinsing solution supplied to the upper surface of the substrate W is spread to the entire substrate W by centrifugal force. As a result, the hydrophilic film removal solution adhering to the upper surface of the substrate W is washed away by the rinsing solution, and the hydrophilic film removal solution is discharged from the upper surface of the substrate W (second rinsing step).

[0189] The hydrophilic membrane removal liquid valve 52A is closed before the flushing liquid valve 51A is opened. After the hydrophilic membrane removal liquid valve 52A is closed, the hydrophilic membrane removal liquid nozzle 12 is moved to the retracted position by the first nozzle moving mechanism 35.

[0190] Next, a rotary drying step (step S12) is performed, in which the substrate W is rotated at high speed to dry the upper surface of the substrate W. Specifically, the rinsing liquid valve 51A is closed. This stops the supply of rinsing liquid to the upper surface of the substrate W.

[0191] Then, the rotation drive member 23 accelerates the rotation of the substrate W, causing it to rotate at high speed. The substrate W rotates at a drying speed, for example, 1500 rpm. As a result, a large centrifugal force acts on the rinsing liquid on the substrate W, and the rinsing liquid on the substrate W is thrown off to the surrounding area of ​​the substrate W. Subsequently, the rotation of the substrate W is stopped by the rotation drive member 23.

[0192] After the substrate W stops rotating, the transport robot CR enters the processing unit 2, where the rotary chuck 5 picks up the processed substrate W and moves it out of the processing unit 2 (substrate removal step: step S13). The substrate W is then handed over by the transport robot CR to the transport robot IR, which stores it in the conveyor C.

[0193] <Top surface condition of the substrate during substrate processing>

[0194] Next, use Figures 6A-6H This section provides a detailed description of the condition of the upper surface of substrate W during substrate processing. Figures 6A-6H This is a schematic diagram illustrating the situation near the upper surface of substrate W during substrate processing.

[0195] Figure 6A This describes the condition of the upper surface of the substrate W before substrate processing. Before substrate processing, a removal target 103, such as particles, is attached to the upper surface of the substrate W. The particle size R of the removal target 103 is, for example, 15 nm.

[0196] The hydrophilic membrane 100 formed in the hydrophilic membrane formation step (step S3) is as follows: Figure 6B As shown, it is attached to the upper surface of the substrate W. The thickness T1 of the hydrophilic film 100 is, for example, 20 nm or more and 30 nm or less, and is generally larger than the particle size R of the object to be removed 103.

[0197] The thickness T1 of the hydrophilic film 100 is the width of the hydrophilic film 100 in a direction orthogonal to the upper surface of the substrate W. When the upper surface of the substrate W is flat, the direction orthogonal to the upper surface of the substrate W is consistent with the thickness direction of the substrate W. When a circuit pattern has been formed, the thickness T1 of the hydrophilic film 100 on the side of the structure constituting the circuit pattern is the width of the hydrophilic film 100 in a direction intersecting the thickness direction of the substrate W. The thicknesses T2 and T3 described below are the same.

[0198] The thickness T2 of the hydrophilic membrane 100 after performing the membrane thickness reduction step (step S4) is as follows: Figure 6C As shown, the particle size R is smaller than that of the object to be removed 103, for example, it is 1 Å or more and 10 Å or less. The object to be removed 103 is exposed from the surface of the hydrophilic membrane 100. By setting the thickness of the hydrophilic membrane 100 to a thickness T2 that is smaller than the particle size of the object to be removed 103, most of the surface of the object to be removed 103 can be exposed from the surface of the hydrophilic membrane 100.

[0199] The thickness T3 of the treatment film 101 formed in the treatment film formation step (step S3) is greater than the particle size R of the object to be removed 103, for example, 100 nm or more and 200 nm or less.

[0200] Treatment membrane 101 Figure 6DAs shown, the object to be removed 103 is retained. The term "retaining the object to be removed 103" means retaining the object to be removed 103 by either physical retention (taking the object to be removed 103 into the interior of the treatment membrane 101) or chemical retention (adsorbing the object to be removed 103 onto the treatment membrane 101 through chemical interactions (e.g., intermolecular forces or ionic bonds).

[0201] The treatment film 101 is not in direct contact with the upper surface of the substrate W, but is formed on the surface of the hydrophilic film 100 formed on the upper surface of the substrate W. The treatment film 101 contains a highly soluble component in a solid state (highly soluble solid 110) and a less soluble component in a solid state (less soluble solid 111). The highly soluble solid 110 and the less soluble solid 111 are formed by the evaporation of at least a portion of the solvent contained in the treatment film forming solution.

[0202] In the treatment membrane 101, the highly soluble solids 110 and the low-soluble solids 111 are not uniformly dispersed. The treatment membrane 101 is composed of a portion containing more (partially) low-soluble solids 111 and a portion containing more (partially) high-soluble solids 110.

[0203] Reference Figure 6E The highly soluble solid 110 is selectively dissolved using the stripping liquid supplied to the upper surface of the substrate W in the stripping liquid supply step (step S7). That is, the treated film 101 is partially dissolved (dissolution step, partial dissolution step).

[0204] The term "selective dissolution of highly soluble solids 110" does not mean that only highly soluble solids 110 in solid state are dissolved, but rather that less soluble solids 111 are also slightly dissolved, while most of the highly soluble solids 110 are dissolved. Taking advantage of the selective dissolution of highly soluble solids 110, through-holes 102 are formed in the portion of the treated membrane 101 where highly soluble solids 110 remain, serving as a path for the stripping liquid (through-hole formation step).

[0205] The through-hole 102 is, for example, a size of several nm in diameter. The through-hole 102 does not need to be specifically designed to be observable. That is, it is sufficient that a stripping liquid path is formed on the processing film 101 to allow the stripping liquid to move from the surface of the processing film 101 to the upper surface of the substrate W, as long as this stripping liquid path runs through the entire processing film 101.

[0206] Here, when a moderate amount of solvent remains in the treated membrane 101, i.e., when the treated membrane 101 is in a semi-solid state, the stripping liquid dissolves into the solvent remaining in the treated membrane 101 while partially dissolving the treated membrane 101. More specifically, the stripping liquid dissolves into the solvent remaining in the treated membrane 101 while dissolving the highly soluble solids 110 in the treated membrane 101 to form through-holes 102. Therefore, the stripping liquid can easily enter into the treated membrane 101 (dissolution entry step). The stripping liquid reaches the interface between the hydrophilic membrane 100 and the treated membrane 101 (the interface with the less soluble solids 111) through the through-holes 102.

[0207] The stripping solution that reaches the surface of the hydrophilic membrane 100 acts on the contact interface between the treatment membrane 101 and the hydrophilic membrane 100, peeling the treatment membrane 101 off from the hydrophilic membrane 100, and removing the peeled treatment membrane 101 from the hydrophilic membrane 100 (stripping and removal step).

[0208] In detail, the low-soluble solids 111 have low solubility relative to the stripping fluid, and most of the low-soluble solids 111 remain in a solid state. Therefore, the stripping fluid reaching the vicinity of the hydrophilic membrane 100 through the through-holes 102 causes a slight dissolution of the portion of the low-soluble solids 111 near the hydrophilic membrane 100. Thus, as... Figure 6E As shown in the enlarged view, the stripping liquid gradually dissolves the poorly soluble solids 111 near the hydrophilic membrane 100 while entering the gap G between the treatment membrane 101 and the hydrophilic membrane 100 (stripping liquid entry step).

[0209] like Figure 6D As shown in the enlarged view, near the interface between the hydrophilic membrane 100 and the treatment membrane 101, due to the interaction between the hydrophilic components of the hydrophilic membrane 100 and the highly soluble components of the treatment membrane 101 (details will be described later), both low-soluble solids 111 and highly soluble solids 110 are present. Therefore, during the stripping liquid entry step, the stripping liquid dissolves both low-soluble solids 111 and highly soluble solids 110. Consequently, compared to the case where only low-soluble solids 111 are present near the interface between the hydrophilic membrane 100 and the treatment membrane 101, the stripping liquid can more easily enter the interface between the treatment membrane 101 and the hydrophilic membrane 100.

[0210] Starting from the periphery of the through-hole 102, cracks form in the treated membrane 101. Therefore, the highly soluble solid 110 is also referred to as the crack-inducing component. The treated membrane 101 splits through the formation of cracks, becoming a membrane sheet 104. For example... Figure 6F As shown, the membrane 104 of the processing membrane 101 is peeled off from the substrate W while maintaining the object to be removed 103 (processing membrane splitting step, processing membrane removal step).

[0211] Then, by continuously supplying the stripping liquid, the treatment film 101, which becomes the film 104, is rinsed off by the stripping liquid while maintaining the object to be removed 103. In other words, the film 104 holding the object to be removed 103 is pushed out of the substrate W and removed from the upper surface of the substrate W (treatment film removal step, object to be removed step). As a result, the upper surface of the substrate W can be cleaned well.

[0212] As described above, by supplying a stripping solution to the upper surface of the substrate W, the highly soluble solid 110 is dissolved, causing the treated film 101 to peel off from the hydrophilic film 100.

[0213] The object to be removed 103 is removed together with the treatment film 101 using a stripping solution, while the hydrophilic film 100 remains on the upper surface of the substrate W. For example... Figure 6G As shown, the hydrophilic film removal solution supplied to the upper surface of the substrate W in the hydrophilic film removal solution supply step (step S10) dissolves the hydrophilic film 100 on the upper surface of the substrate W (hydrophilic film dissolution step). By continuously supplying the hydrophilic film removal solution, such as Figure 6H As shown, the hydrophilic film 100 can be removed from the upper surface of the substrate W.

[0214] According to this embodiment, by forming a hydrophilic film 100 on the upper surface of the substrate W, the upper surface of the substrate W can be pseudo-hydrophilicized. Strictly speaking, the properties of the upper surface of the substrate W itself are not changed. When the hydrophilicity of the portion forming the contact interface with the processing film 101 is increased by forming an aqueous film 100 between the processing film 101 and the upper surface of the substrate W, it is manifested as "pseudo-hydrophilicizing the upper surface of the substrate W".

[0215] By forming a hydrophilic film 100, the upper surface of the substrate W is pseudo-hydrophilized, making it easier for the stripping liquid to enter the interface between the upper surface of the substrate W and the treatment film 101, specifically the interface between the treatment film 101 and the hydrophilic film 100. Therefore, the treatment film 101, which maintains the state of having the object to be removed 103 present on the upper surface of the substrate W, can be effectively peeled off from the upper surface of the substrate W.

[0216] Furthermore, in this embodiment, before peeling the treatment film 101 from the hydrophilic film 100, the thickness of the hydrophilic film 100 is reduced using a film thickness reduction liquid (rinsing liquid). Therefore, the object to be removed 103 present on the upper surface of the substrate W can be well exposed from the hydrophilic film 100. Thus, if the treatment film 101 is formed on the surface of the hydrophilic film 100 with reduced thickness, the object to be removed 103 can be firmly held in the treatment film 101. Therefore, by subsequently supplying a stripping liquid, the object to be removed 103 and the treatment film 101 can be effectively removed together.

[0217] As described above, even when the upper surface of the substrate W is a hydrophobic surface, that is, regardless of the state of the upper surface of the substrate W, the object to be removed 103 can be effectively removed from the upper surface of the substrate W.

[0218] Furthermore, in this embodiment, the hydrophilic membrane 100 is dissolved by a membrane thickness reduction liquid, so that the thickness T2 of the hydrophilic membrane 100 becomes smaller than the particle size R of the object to be removed 103. Therefore, the object to be removed 103 can be more effectively exposed from the surface of the hydrophilic membrane 100. Consequently, the object to be removed 103 can be more firmly retained on the treatment membrane 101. Thus, with the subsequent supply of a stripping liquid, the object to be removed 103 can be effectively removed together with the treatment membrane 101.

[0219] Unlike this embodiment, when the chemical properties of the substrate's upper surface are altered, it can be difficult to restore the substrate's upper surface to its state before substrate processing. However, in this embodiment, a hydrophilic film removal solution is supplied to the upper surface of the substrate W after the stripping solution supply step. Therefore, since forming the hydrophilic film 100 on the upper surface of the substrate W does not change the chemical properties of the substrate's upper surface itself, removing the hydrophilic film 100 can restore the upper surface of the substrate W to its state before substrate processing. Thus, after the object to be removed 103 is removed, the upper surface of the substrate W can be restored to its state before the formation of the hydrophilic film 100, i.e., a hydrophobic surface. As a result, the procedure of restoring the properties of the upper surface of the substrate to their original state after substrate processing is saved.

[0220] Furthermore, according to this embodiment, the processing film forming liquid contains a highly soluble component and a less soluble component that is not easily soluble in the stripping liquid. Therefore, by supplying the stripping liquid to the upper surface of the substrate W, the highly soluble solids 110 in the processing film 101 can be selectively dissolved in the stripping liquid. Thus, the stripping liquid moves towards the contact interface between the processing film 101 and the hydrophilic film 100 while selectively dissolving the highly soluble solids 110. As a result, the stripping liquid can form a stripping liquid path (through hole 102) in the processing film 101. After the stripping liquid path is formed by the dissolution of the highly soluble component, the stripping liquid efficiently reaches the contact interface between the processing film 101 and the hydrophilic film 100 via the stripping liquid path. Thus, the stripping liquid can effectively act on the contact interface between the processing film 101 and the hydrophilic film 100.

[0221] On the other hand, since most of the low-soluble solids 111 in the treatment film 101 are not dissolved by the stripping liquid, the object to be removed 103 can be retained in the low-soluble solids 111. As a result, the treatment film 101 can be quickly peeled off from the upper surface of the substrate W, and the object to be removed 103 and the treatment film 101 can be efficiently pushed to the outside of the upper surface of the substrate W by the flow of the stripping liquid.

[0222] <The hydrophilic film in substrate processing and the composition of the processed film>

[0223] Figure 7A This is a schematic diagram illustrating the composition (hydrophilic component, low-soluble component, and high-soluble component) near the upper surface of the substrate W, in which the hydrophilic film 100 and the treatment film 101 have been formed during the above-described substrate processing. Figure 7A In this paper, taking the case where hydrophilic components, low-soluble components, and high-soluble components have main chains and side chains as examples, the components near the upper surface of the substrate W are explained.

[0224] The hydrophilic membrane 100 contains at least a hydrophilic component 200. The hydrophilic component 200 has a main chain 201 and multiple side chains bonded to the main chain 201. The multiple side chains include multiple hydrophobic side chains 202 and multiple hydrophilic side chains 203. The number of hydrophilic side chains 203 is greater than the number of hydrophobic side chains 202.

[0225] The treated membrane 101 contains at least a low-soluble component 211 and a high-soluble component 210. The low-soluble component 211 has a main chain 220 and multiple side chains bonded to the main chain 220. The multiple side chains include multiple hydrophobic side chains 221 and multiple hydrophilic side chains 222. When the low-soluble component 211 is a phenolic varnish, the main chain 220 has a phenyl group, the hydrophobic side chain 221 has a methyl group, and the hydrophilic side chain 222 has a hydroxyl group.

[0226] The highly soluble component 210 has a main chain 230 and multiple side chains linked to the main chain 230. The multiple side chains include multiple hydrophobic side chains 231 and multiple hydrophilic side chains 232. When the highly soluble component 210 is 2,2-bis(4-hydroxyphenyl)propane, the main chain 230 has a phenyl group, the hydrophobic side chain 231 has a methyl group, and the hydrophilic side chain 232 has a hydroxyl group.

[0227] The hydrophilic component 200 has both hydrophobic groups (hydrophobic side chains 202) and hydrophilic groups (hydrophilic side chains 203). Because it has more hydrophilic side chains 203 than hydrophobic side chains 202, it can fully expose a highly hydrophilic surface (the surface of the hydrophilic membrane 100). Therefore, the hydrophilic side chains 203 of the hydrophilic membrane 100 interact with the hydrophilic side chains 222 of the low-soluble component 211 and the hydrophilic side chains 232 of the high-soluble component 210 in the treatment membrane 101. Consequently, a large number of hydrophilic groups exist at the interface between the hydrophilic membrane 100 and the treatment membrane 101. Near the interface between the hydrophilic membrane 100 and the treatment membrane 101, both the low-soluble component 211 and the high-soluble component 210 are present.

[0228] By forming a hydrophilic film 100, the upper surface of the substrate W is made hydrophilic, allowing the stripping liquid to easily penetrate into the interface between the upper surface of the substrate W and the treatment film 101, specifically the interface between the treatment film 101 and the hydrophilic film 100. Therefore, the treatment film 101, which retains the object to be removed 103 on the upper surface of the substrate W, can be effectively peeled off from the upper surface of the substrate W.

[0229] Furthermore, since the hydrophilic component 200 has hydrophobic side chains 202, an interaction can occur between the hydrophobic side chains 202 and the hydrophobic surface. A large number of hydrophobic groups exist at the contact interface between the hydrophilic film 100 and the substrate W, making it difficult for the stripping liquid to penetrate.

[0230] The hydrophilicity of the less soluble component 211 is lower than that of the hydrophilic component 200. Therefore, as... Figure 7B As in the substrate processing of the reference example shown, when a treatment film 101 is formed on the hydrophobic surface of the substrate W without forming a hydrophilic film 100, the low-solubility component 211 in the treatment film 101 interacts with the upper surface of the substrate W hydrophobically. The treatment film 101 is retained on the upper surface of the substrate W through the hydrophobic interaction and is not easily peeled off by a stripping liquid.

[0231] In detail, a large number of hydrophobic groups exist at the contact interface between the treatment film 101 and the substrate W, and hydrophobic interactions occur between the hydrophobic side chains 221 of the low-soluble component 211 in the treatment film 101 and the upper surface of the substrate W. Therefore, the stripping liquid has difficulty penetrating to the contact interface between the treatment film 101 and the substrate W.

[0232] On the other hand, in this embodiment, the processing film 101 is formed on the surface of the hydrophilic film 100. That is, it is formed on the surface of the hydrophilic film 100 between the processing film 101 and the upper surface of the substrate W. Therefore, the hydrophobic interaction between the processing film 101 and the upper surface of the substrate W can be suppressed. As a result, since the stripping liquid can act well on the interface between the processing film 101 and the hydrophilic film 100, the processing film 101 can be peeled off well. Thus, by forming the hydrophilic film 100, the processing film 101 can still be peeled off well even if the upper surface of the substrate W is a hydrophobic surface.

[0233] Thus, the affinity of the stripping solution for the interface between the hydrophilic film 100 and the treatment film 101 is higher than that of the stripping solution for the interface between the substrate W and the hydrophilic film 100. Therefore, by using the stripping solution, the peeling of the hydrophilic film 100 from the upper surface of the substrate W can be suppressed and the hydrophilic film 100 can be maintained on the upper surface of the substrate W, while the treatment film 101 can be peeled off from the hydrophilic film 100.

[0234] <Details on the treatment of the film-forming solution>

[0235] The components of the treatment film forming solution used in the above embodiments will be described below.

[0236] The following "C" x~y “C” x ~C y "and "C x The term "..." refers to the number of carbons in a molecule or substituent. For example, C... 1~6 Alkyl refers to an alkyl chain having one to six carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0237] When a polymer has multiple repeating monomers, these repeating monomers copolymerize. Unless otherwise specified or stated, these copolymerizations can be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, the n or m, etc., in parentheses indicate the number of repeating monomers.

[0238] <Low-soluble components>

[0239] (A) The low-soluble component comprises at least one copolymer of phenolic varnish, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and combinations thereof. Preferably, (A) the low-soluble component comprises at least one copolymer of phenolic varnish, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and combinations thereof. More preferably, (A) the low-soluble component comprises at least one copolymer of phenolic varnish, polyhydroxystyrene, polycarbonate, and combinations thereof. The phenolic varnish may also be a phenolic varnish.

[0240] The treatment film-forming solution may also contain one or more of the preferred examples described above as (A) a low-soluble component. For example, (A) a low-soluble component may also contain both phenolic varnish and polyhydroxystyrene.

[0241] One preferred method for removing (A) low-soluble components is by drying and forming a film, in which the film is removed while still retaining the object to be removed, without being largely dissolved by the stripping liquid. Alternatively, a method is permitted where a very small portion of the (A) low-soluble components can be dissolved using a stripping liquid.

[0242] Preferably, (A) the low-soluble component does not contain fluorine and / or silicon, and more preferably, it does not contain either of these.

[0243] The preferred copolymers are random copolymers and block copolymers.

[0244] The following is not intended to limit the scope of the patent. As specific examples of (A) low-soluble components, examples include the compounds shown in Chemical Formulas 4 to 10 below.

[0245] [Chemistry 4]

[0246] [Chemistry 5]

[0247] [Chemistry 6]

[0248] (asterisk) This represents the bond that forms a unit with its adjacent components.

[0249] [Chemistry 7]

[0250] (R represents C) 1~4 Alkyl and other substituents. (Astro) This represents the bond that forms a unit with its adjacent components.

[0251] [Chemistry 8]

[0252] [Chemistry 9]

[0253] [Chemistry 10]

[0254] (Me stands for methyl. Asterisk) This represents the bond that forms a unit with its adjacent components.

[0255] (A) The weight average molecular weight (Mw) of the low-soluble component is preferably 150 to 500,000, more preferably 300 to 300,000, even more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

[0256] (A) The low-soluble component can be obtained through synthesis. Alternatively, it can be purchased. For example, the following suppliers can be cited as suppliers. These suppliers can also synthesize (A) polymers.

[0257] Phenolic varnishes: Showa Kasei Corporation, Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0258] Polyhydroxystyrene: Nippon Soda (Co., Ltd.), Maruzen Petrochemical (Co., Ltd.), Toho Chemical Industry (Co., Ltd.)

[0259] Polyacrylic acid derivatives: (Nippon Shokubai Co., Ltd.)

[0260] Polycarbonate: Sigma Aldrich

[0261] Polymethacrylic acid derivatives: Sigma Aldrich

[0262] Compared to the total mass of the membrane forming solution, (A) the low-soluble component is 0.1~50% by mass, more preferably 0.5~30% by mass, even more preferably 1~20% by mass, and still more preferably 1~10% by mass. That is, with the total mass of the membrane forming solution set at 100% by mass, (A) the low-soluble component is 0.1~50% by mass. In other words, "compared to" can be replaced with "based on". Unless otherwise specified, the same applies below.

[0263] Solubility can be evaluated using known methods. For example, under conditions of 20°C to 35°C (preferably 25±2°C), add 100 ppm of (A) above or (B) below to 5.0% by mass ammonia water in a flask, cap and shake for 3 hours. The solubility can be determined by whether (A) or (B) dissolves. Shaking can also be done by stirring. Solubility can be judged visually. If it does not dissolve, its solubility is less than 100 ppm; if it dissolves, its solubility is set to 100 ppm or more. Solubility less than 100 ppm is considered insoluble or sparingly soluble, and solubility 100 ppm or more is considered soluble. Broadly speaking, soluble includes slightly soluble. Solubility decreases in the order of insoluble, sparingly soluble, and soluble. Narrowly speaking, slightly soluble has lower solubility than soluble, and slightly soluble has higher solubility than sparingly soluble.

[0264] <Highly soluble ingredients>

[0265] (B) The highly soluble component is (B') crack-promoting component. (B') crack-promoting component contains a hydrocarbon, and further contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). When (B') crack-promoting component is a polymer, each constituent unit contains a hydrocarbon, and thus has a hydroxyl group and / or a carbonyl group. Examples of carbonyl groups include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, with carboxylic acids being preferred.

[0266] The following is not intended to limit the scope of the patent, nor is it a theoretical constraint; it can be considered that the treatment film forming liquid is dried to form a treatment film on the substrate, and when the treatment film is peeled off by the stripping liquid, the highly soluble component (B) is generated as a trigger point for the peeling of the treatment film. Therefore, the highly soluble component (B) has better solubility in the stripping liquid than the less soluble component (A). As a crack-promoting component (B'), it may contain a ketone as a carbonyl group, for example, a cyclic hydrocarbon. As specific examples, 1,2-cyclohexanedione or 1,3-cyclohexanedione.

[0267] More specifically, (B) the highly soluble component is represented by at least one of (B-1), (B-2), and (B-3) described below. (B-1) is a compound containing 1 to 6 (preferably 1 to 4) of the following chemical formula 11 as constituent units, each constituent unit being linked by a linker (L1). Here, the linker L1 can be a single bond or a C bond. 1~6 Lynyl group. The above C 1~6 The alkyl group, acting as a linking group, will form a unit link and is not limited to a divalent group. A divalent to tetravalent group is preferred. The above C 1~6 The alkyl group can be either straight-chain or branched.

[0268] [Chemistry 11]

[0269] C y1 C 5~30 The hydrocarbon ring is preferably phenyl, cyclohexane, or naphthyl, more preferably phenyl. As a preferred embodiment, the linker L1 connects multiple C... y1 link.

[0270] R1 is independently C 1~5 Alkyl groups, preferably methyl, ethyl, propyl, or butyl. The above C 1~5 Alkyl groups can be either straight-chain or branched.

[0271] n b1 The value can be 1, 2, or 3, preferably 1 or 2, and even better, 1. b1’ The value can be 0, 1, 2, 3 or 4, with 0, 1 or 2 being preferred.

[0272] The following chemical formula 12 is a chemical formula in which the constituent units described in chemical formula 11 are represented by the linker group L9. The linker group L9 is preferably a single bond, methylene, ethyl, or propyl.

[0273] [Chemistry 12]

[0274] The following is not intended to limit the scope of the patent. As preferred examples of (B-1), examples include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane. These can also be obtained by polymerization or condensation.

[0275] The following description uses 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, as shown in chemical formula 13, as an example. In (B-1), this compound has three constituent units of chemical formula 11, which are linked by a linker group L1 (methylene). b1 =n b1’ =1, R1 is methyl.

[0276] [Chemistry 13]

[0277] (B-2) is represented by the following chemical formula 14.

[0278] [Chemistry 14]

[0279] R 21 R 22 R 23 and R 24 Each can be independently hydrogen or C 1-5 The alkyl group is preferably hydrogen, methyl, ethyl, tert-butyl or isopropyl, more preferably hydrogen, methyl or ethyl, and even more preferably methyl or ethyl.

[0280] Linkage base L 21 and connecting base L 22 Each is independently C 1~20 alkyl groups, C 1~20 cycloalkyl, C 2~4 enylene, C 2~4 The acetylenic group, or C 6~20 The extended aryl groups. These groups can also be derived from C. 1~5 Alkyl or hydroxyl substitution. Here, alkenyl refers to a divalent hydrocarbon group having one or more double bonds, and alkyne refers to a divalent hydrocarbon group having one or more triple bonds. Linking group L 21 and connecting base L 22 C is preferred 2~4 The alkyl, ethynyl (C2 ethynyl) or phenyl group, preferably C2 2~4 The alkyl or ethynyl group, preferably ethynyl.

[0281] n b2 It can be 0, 1, or 2, preferably 0 or 1, and even better is 0.

[0282] The following is not intended to limit the scope of the patent. Preferred examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyn-2,5-diol. Alternatively, preferred examples of (B-2) include 3-hexyn-2,5-diol, 1,4-butynediol, 2,4-hexadiyn-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzyldiethanol.

[0283] (B-3) is a polymer containing the constituent units shown in chemical formula 15 below, with a weight average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, more preferably 700 to 3,000.

[0284] [Chemistry 15]

[0285] Here, R 25 The constituent units are -H, -CH3, or -COOH, preferably -H or -COOH. It is also permissible for a (B-3) polymer to contain more than two constituent units represented by chemical formula 15.

[0286] The following is not intended to limit the scope of the patent. Preferred examples of polymers (B-3) include polymers of acrylic acid, maleic acid, or combinations thereof. More preferred examples are polyacrylic acid and maleic acid-acrylic acid copolymers.

[0287] In copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is even more preferred.

[0288] The example is a maleic acid-acrylic acid copolymer of the following chemical formula 16. This copolymer contains (B-3) and has two constituent units as shown in chemical formula 15, with R in one constituent unit. 25 For -H, R is another constituent unit. 25 It is -COOH.

[0289] [Chemistry 16]

[0290] It goes without saying that the treatment membrane forming solution may also contain one or more of the above-mentioned preferred examples as (B) highly soluble components. For example, (B) highly soluble components may also contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0291] (B) The molecular weight of the highly soluble component can be 80 to 10,000. Preferably, the molecular weight of the highly soluble component is 90 to 5,000, more preferably 100 to 3,000. When the highly soluble component in (B) is a resin, polymer, or a polymer compound, the molecular weight is expressed as the weight average molecular weight (Mw).

[0292] (B) Highly soluble components can be obtained through synthesis or purchase. Examples of suppliers include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

[0293] In the treatment membrane forming solution, the mass percentage of the highly soluble component (B) relative to the low-soluble component (A) is preferably 1 to 100% by mass, more preferably 1 to 50% by mass. In the treatment membrane forming solution, the mass percentage of the highly soluble component (B) relative to the low-soluble component (A) is preferably 1 to 30% by mass.

[0294] <solvent>

[0295] (C) The solvent preferably contains an organic solvent. (C) The solvent may also be volatile. Volatility means that it is more volatile than water. For example, the boiling point of the solvent at 1 atmosphere is preferably 50~250℃. The boiling point of the solvent at 1 atmosphere is more preferably 50~200℃, and even more preferably 60~170℃. The boiling point of the solvent at 1 atmosphere is even more preferably 70~150℃.

[0296] (C) The solvent may also contain a small amount of pure water. The amount of pure water contained in the solvent (C) is preferably 30% by mass or less compared to the total amount of solvent (C). The amount of pure water contained in the solvent is preferably 20% by mass or less, more preferably 10% by mass or less. The amount of pure water contained in the solvent is even more preferably 5% by mass or less. A solvent containing no pure water (0% by mass) is also a preferred method. Pure water is preferably DIW (diluted water).

[0297] Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactates such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These organic solvents can be used alone or in mixtures of two or more.

[0298] As one of the preferred methods, (C) the organic solvent contained in the solvent is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When there is a combination of two organic solvents, the volume ratio is preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

[0299] The content of solvent (C) is 0.1 to 99.9% by mass relative to the total mass of the membrane forming solution. The content of solvent (C) is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass, relative to the total mass of the membrane forming solution. The content of solvent (C) is even more preferably 80 to 99% by mass, and still more preferably 85 to 99% by mass, relative to the total mass of the membrane forming solution.

[0300] <Anti-corrosion ingredients>

[0301] Besides BTA, other anti-corrosion components that can be identified as (D) include uric acid, caffeine, butenyne, adenine, glyoxylic acid, glucose, fructose, and mannose.

[0302] <Other Additives>

[0303] The membrane-forming solution of the present invention may further contain (E) other additives. As one aspect of the present invention, (E) other additives include surfactants, acids, bases, antibacterial agents, bactericides, preservatives, or antifungal agents (preferably surfactants), or any combination thereof.

[0304] As one aspect of the present invention, compared to the mass of (A) the low-soluble component in the membrane forming solution, (E) other additives (or the sum of multiple additives) are 0 to 100% by mass (preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, and still more preferably 0 to 1% by mass). The presence of no (E) other additives (0% by mass) in the membrane forming solution is also one aspect of the present invention.

[0305] <Membrane peeling experiment>

[0306] Next, the results of the treatment film peeling experiment, in which the treatment film was peeled off from the main surface of the substrate from which the hydrophilic film had been formed, will be explained. Figure 8This table presents the results of the treated film peeling experiment. In this experiment, peeling performance was compared using various substrates and hydrophilic films. Specifically, as substrate types, hydrophilic Si substrates, hydrophobic Si substrates, aC substrates, and SiCN substrates were used. Five hydrophilic films (samples UL1, UL2, UL3, UL4, and UL5) were used. These samples have different backbone lengths. Sample UL1 has the longest backbone, followed by sample UL2. Sample UL3 has a shorter backbone than sample UL2, and sample UL4 has an even shorter backbone. Sample UL5 has the shortest backbone.

[0307] The membrane peeling test was performed in the following order.

[0308] (1) First, prepare a small sheet substrate (small sheet substrate). The small sheet substrate is a four-cornered shape with one side 3cm when viewed from the normal direction of the main surface. As a small sheet substrate, a small sheet substrate (Si substrate) with Si exposed on the surface, a small sheet substrate (aC substrate) with aC (amorphous carbon) exposed on the surface, and a small sheet substrate (SiCN substrate) with SiCN exposed are used.

[0309] (2) Place the small substrate on a rotatable stage, and while rotating the stage, supply a hydrophilic film forming liquid to the surface of the small substrate to form a hydrophilic film.

[0310] (3) The thickness of the hydrophilic film is adjusted by supplying DIW to the surface of the small substrate.

[0311] (4) A treatment film forming solution is supplied to the surface of a small substrate with a hydrophilic film that has been formed and the film thickness has been adjusted, and a treatment film is formed on the hydrophilic film.

[0312] (5) Apply diluted ammonia (dNH4OH 1:68) to the surface of the small substrate to peel off the treatment film.

[0313] (6) Subsequently, visually confirm the peeling of the treatment membrane and use a scanning electron microscope (SEM) to confirm the particle removal rate.

[0314] Next, the results of the treatment film peeling experiment are explained. Regardless of which sample was used as the hydrophilic film, the treatment film could be peeled off from the hydrophilic Si substrate using ammonia. When any of samples UL1, UL2, and UL3 were used as the hydrophilic film, the treatment film could be peeled off from the hydrophobic Si substrate using ammonia. Experiments on peeling the treatment film from the hydrophobic Si substrate using samples UL4 and UL5 as hydrophilic films were not conducted.

[0315] When using sample UL4 as the hydrophilic film to peel the treatment film from the aC substrate with ammonia, the peeling was insufficient (NG), but when using samples UL1, UL2, UL3, and UL5 as hydrophilic films to peel the treatment film from the aC substrate with ammonia, the peeling was sufficient (OK). Similarly, when using sample UL5 as the hydrophilic film to peel the treatment film from the SiCN substrate with ammonia, the peeling was insufficient, but when using samples UL1, UL2, UL3, and UL4 as hydrophilic films to peel the treatment film from the SiCN substrate with ammonia, the peeling was sufficient.

[0316] <Particle Removal Experiment>

[0317] Next, the results of the particle removal experiment, which measures the particle removal efficiency when the treatment film is peeled off from the main surface of the substrate, will be explained. Figure 9 A table showing the results of particle removal experiments.

[0318] In the particle removal experiments, various hydrophilic membranes were used to compare particle removal performance. Specifically, five hydrophilic membranes (samples UL1, UL2, UL3, UL4, and UL5) were used. Samples without a hydrophilic membrane formed on the substrate surface were also used in the particle removal experiments. Figure 9 (The "hydrophobic membrane").

[0319] The particle removal experiments were conducted in the following order.

[0320] (1) First, prepare a small substrate of aC substrate with SiO2 particles attached to the main surface.

[0321] (2) Place the small substrate on a rotatable stage, and while rotating the stage, supply a hydrophilic film forming liquid to the surface of the small substrate to form a hydrophilic film.

[0322] (3) The thickness of the hydrophilic film is adjusted by supplying DIW to the surface of the small substrate.

[0323] (4) A treatment film forming solution is supplied to the surface of a small substrate with a hydrophilic film that has been formed and the film thickness has been adjusted, and a treatment film is formed on the hydrophilic film.

[0324] (5) Apply diluted ammonia (dNH4OH 1:68) to the surface of the small substrate to peel off the treatment film.

[0325] (6) Subsequently, the surface of the small substrate is rinsed with DIW, and then IPA is supplied to the surface of the small substrate to remove the residue of the polymer film.

[0326] (7) After removing the residue from the polymer film, the small substrate is rotated at high speed for rotary drying.

[0327] (8) Subsequently, the peeling of the treatment membrane was visually confirmed, and the particle removal rate was confirmed using a scanning electron microscope (SEM).

[0328] According to particle removal experiments, regardless of which of the samples UL1, UL2, UL3, UL4, and UL5 was used as the hydrophilic film, the particle removal rate exceeded 80%. On the other hand, when a treatment film was formed on the aC substrate without forming a hydrophilic film, and the treatment film was then peeled off, the particle removal rate was 0%. Thus, by forming a hydrophilic film on the surface of the small substrate, particles can be sufficiently removed from the main surface of the small substrate.

[0329] <Other Implementation Methods>

[0330] This invention is not limited to the embodiments described above, and can be implemented in other ways.

[0331] For example, in the above substrate processing, the first rinsing step (step S8) and the residue removal liquid supply step (step S9) can be omitted.

[0332] Furthermore, in the above substrate processing, the rinsing solution used in the first rinsing step (step S8) and the second rinsing step (step S11), as well as the rinsing solution used in the film thickness reduction step (step S4), are supplied by the same rinsing solution nozzle 11. However, the rinsing solution used in the film thickness reduction step (step S4) may also be sprayed from a different nozzle than the rinsing solution used in the first rinsing step (step S8) and the second rinsing step (step S11). The rinsing solutions used in the first rinsing step (step S8) and the second rinsing step (step S11) may also be of different types.

[0333] If a sufficiently thin hydrophilic film 100 can be formed in the hydrophilic film formation step, the film thickness reduction step can be omitted.

[0334] In the above substrate processing, the processing position of each nozzle is at the center. However, the processing position is not necessarily at the center, and it can also be at a position deviating from the center. For example, when switching the nozzle that sprays liquid to another nozzle supported by the same arm, the position of the arm can be kept unchanged while switching the nozzle that sprays liquid. More specifically, after the hydrophilic film forming liquid is supplied from the hydrophilic film forming liquid nozzle 10 in the hydrophilic film forming liquid supply step (step S1), the first arm 35A can be maintained in the same position until the supply of rinsing liquid from the rinsing liquid nozzle 11 ends in the film thickness reduction step (step S4). In addition, it is not necessary for the nozzle to remain in a fixed position during liquid spraying, and liquid can be sprayed while moving along the upper surface of the substrate W.

[0335] When the hydrophilic film 100 is formed, the substrate W can also be heated by the heating member 6. Heating the hydrophilic film forming liquid via the substrate W can further promote the evaporation of the solvent from the hydrophilic film forming liquid. The heating method of the substrate W is not limited to heating by a heater; the substrate W can also be heated by supplying a heating fluid such as warm water to the lower surface of the substrate W. In addition, the heating of the hydrophilic film forming liquid does not necessarily need to be through the substrate W; the hydrophilic film forming liquid can also be directly heated by a lamp or the like located above the substrate W. Similarly, the substrate W can also be heated when forming the treatment film 101.

[0336] The above-described substrate processing is performed on a substrate W whose main surface is a hydrophobic surface. However, the above-described substrate processing can also be performed on a substrate W whose main surface is not a hydrophobic surface. In addition, in the above-described substrate processing, the formation and removal of the hydrophilic film 100 and the formation and peeling of the treatment film 101 are performed on the upper surface of the substrate W, but of course, these processes can also be performed on the lower surface (the lower main surface) of the substrate W.

[0337] Furthermore, in the above embodiment, multiple processing units 2 are equipped together with the transfer robots IR and CR and the controller 3 in the substrate processing apparatus 1. However, the substrate processing apparatus may also be composed of only a single processing unit 2. In other words, the processing unit 2 may also be an example of a substrate processing apparatus.

[0338] Alternatively, unlike the above-described embodiments, a rinsing liquid such as DIW can be supplied to the upper surface of the substrate W before the hydrophilic film-forming liquid supply step (step S2) to form a rinsing liquid film in an immersed state (DIW immersion step, rinsing liquid immersion step). If a liquid identical to the solvent of the hydrophilic film-forming liquid (e.g., DIW) is used as the rinsing liquid, the hydrophilic film-forming liquid can rapidly spread to the entire upper surface of the substrate W because it mixes with the rinsing liquid on the upper surface of the substrate W while spreading on the upper surface of the substrate W.

[0339] Furthermore, while the above embodiments use terms such as "along," "horizontal," and "vertical," these terms are not necessarily strictly "along," "horizontal," or "vertical." That is, these various expressions allow for deviations in manufacturing precision, setting precision, etc.

[0340] In this manual, when using "~" or "-" to represent a numerical range, unless otherwise specified, they include both endpoints and are common units.

[0341] The embodiments of the present invention have been described in detail above, but they are limited to specific examples used to illustrate the technical content of the present invention and are not intended to limit the invention to these specific examples. The scope of the present invention is defined only by the scope of the patent.

[0342] This application corresponds to Japan Patent Application No. 2021-039289 filed with the Japan Patent Office on March 11, 2021, all disclosures of which are incorporated herein by reference.

[0343] [Explanation of the labeling in the attached diagram]

[0344] 1: Substrate processing device

[0345] 2: Processing Unit (Substrate Processing Device)

[0346] 10: Hydrophilic film-forming fluid nozzle (hydrophilic film-forming fluid supply component)

[0347] 11: Fluid nozzle (film thickness reduction fluid supply component)

[0348] 13: Treatment film forming fluid nozzle (treatment film forming fluid supply component)

[0349] 14: Stripping fluid nozzle (stripping fluid supply component)

[0350] 100: Hydrophilic membrane

[0351] 101: Membrane Treatment

[0352] 103: Remove object

[0353] 110: Highly soluble solids (highly soluble components)

[0354] 111: Low-soluble solids (low-soluble components, hydrophobic components)

[0355] 200: Hydrophilic component

[0356] 202: Hydrophobic side chain (hydrophobic group)

[0357] 203: Hydrophilic side chain (hydrophilic group)

[0358] 210: Highly soluble components

[0359] 211: Low-soluble components (hydrophobic components)

[0360] T1: Thickness

[0361] T2: Thickness

[0362] W: substrate

Claims

1. A substrate processing method, comprising: In the hydrophilic film forming liquid supply step, a hydrophilic film forming liquid that forms a hydrophilic film on the main surface of a substrate having a target object to be removed is supplied to the main surface of the substrate, thereby forming the hydrophilic film on the main surface of the substrate having a first thickness larger than the particle size of the target object to be removed. In the film thickness reduction liquid supply step, a film thickness reduction liquid that reduces the thickness of the hydrophilic film by dissolving the hydrophilic film is supplied to the main surface of the substrate, so that the thickness of the hydrophilic film is reduced to a second thickness smaller than the particle size of the object to be removed. In the film-forming liquid supply step, after the thickness of the hydrophilic film is reduced to the second thickness through the aforementioned film thickness reduction liquid supply step, the film-forming liquid is supplied to the main surface of the substrate. This film-forming liquid forms a treatment film on the surface of the hydrophilic film to retain the object to be removed on the main surface of the substrate; and In the stripping fluid supply step, the stripping fluid used to peel the treated membrane from the hydrophilic membrane is supplied to the main surface of the substrate.

2. The substrate processing method as described in claim 1, wherein, It also includes a hydrophilic film removal liquid supply step, wherein after the above stripping liquid supply step, the hydrophilic film removal liquid that removes the hydrophilic film from the main surface of the substrate is supplied to the main surface of the substrate.

3. The substrate processing method as described in claim 2, wherein, The above-mentioned hydrophilic membrane removal solution is an acidic liquid.

4. The substrate processing method according to any one of claims 1 to 3, wherein, The aforementioned hydrophilic film-forming liquid contains a hydrophilic component, which has both hydrophobic and hydrophilic groups, with the hydrophilic group being more numerous than the hydrophobic group.

5. The substrate processing method according to any one of claims 1 to 3, wherein, The above-mentioned treatment film forming solution contains highly soluble components and low-soluble components, and the low-soluble components are more difficult to dissolve in the above-mentioned stripping solution than the highly soluble components.

6. The substrate processing method according to any one of claims 1 to 3, wherein, The stripping solution mentioned above is an alkaline liquid.

7. The substrate processing method according to any one of claims 1 to 3, wherein, The main surface of the aforementioned substrate is a hydrophobic surface.

8. The substrate processing method as described in claim 7, wherein, The aforementioned hydrophobic surface is a surface that exposes one or more of amorphous carbon, silicon carbide, and ruthenium.

9. The substrate processing method according to any one of claims 1 to 3, wherein, The liquid used to reduce the film thickness is water.

10. A substrate processing apparatus, comprising: The hydrophilic film forming liquid supply component supplies the hydrophilic film forming liquid, which forms the hydrophilic film, toward the main surface of the substrate; The film thickness reduction liquid supply component supplies film thickness reduction liquid, which dissolves the hydrophilic film and reduces its thickness, to the main surface of the substrate. The processing film forming liquid supply member supplies the processing film forming liquid for forming the processing film to the main surface of the substrate. The stripping fluid supply member supplies stripping fluid, which is used to peel the treated film from the hydrophilic film, toward the main surface of the substrate; and Controller The above controller executes: In the hydrophilic film forming liquid supply step, the hydrophilic film forming liquid is supplied from the hydrophilic film forming liquid supply member to the main surface of the substrate having the object to be removed, and a hydrophilic film having a first thickness larger than the particle size of the object to be removed is formed on the main surface of the substrate. In the film thickness reduction liquid supply step, the film thickness reduction liquid is supplied from the film thickness reduction liquid supply member toward the main surface of the substrate, so that the thickness of the hydrophilic film is reduced to a second thickness smaller than the particle size of the object to be removed. The film-forming liquid supply step involves supplying the film-forming liquid from the film-forming liquid supply member toward the main surface of the substrate after the thickness of the hydrophilic film has been reduced to the second thickness through the aforementioned film thickness reduction liquid supply step; and... In the stripping fluid supply step, the stripping fluid is supplied from the stripping fluid supply member toward the main surface of the substrate.

Images