Substrate processing method and substrate processing device

Abstract

The substrate processing method includes the following steps: a processing liquid supplying step, supplying a processing liquid containing a solute and a solvent to the surface of a substrate; a processing film forming step, solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate for retaining a removal object existing on the surface of the substrate; and a removal step, supplying the removal liquid in a droplet state to the surface of the substrate so that the physical force of the droplets of the removal liquid acts on the processing film and the removal object, thereby removing the processing film and the removal object from the surface of the substrate.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing device for processing a substrate. The substrate (substrate) as the processing object includes, for example, semiconductor wafers, liquid crystal display device substrates, organic EL (Electroluminescence) display device FPD (Flat Panel Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates and the like. Background Art

[0002] In the manufacturing process of semiconductor devices, a cleaning process is performed to remove various contaminants adhering to the substrate, processing liquid used in the previous process, residues of resist, and various particles (hereinafter collectively referred to as "removal objects").

[0003] In the cleaning process, a cleaning liquid such as deionized water (DIW) is usually supplied to the substrate to remove the removal object by the physical action of the cleaning liquid, or a chemical solution that chemically reacts with the removal object is supplied to the substrate to chemically remove the removal object.

[0004] However, the concavo-convex pattern formed on the substrate has become increasingly fine and complex, and therefore, it has become increasingly difficult to remove the object to be removed using a cleaning solution or a chemical solution while suppressing damage to the concavo-convex pattern.

[0005] Therefore, a method has been proposed in which a processing liquid containing a volatile component is supplied to the upper surface of a substrate, a processing film is formed by volatilization of the volatile component, and then the processing film is removed (see Patent Document 1).

[0006] In this method, the treatment film is formed by solidifying or hardening the treatment liquid, so that the removal object is covered by the treatment film. Next, a stripping treatment liquid is supplied to the upper surface of the substrate. The stripping treatment liquid penetrates the treatment film and enters between the substrate and the treatment film. By allowing the stripping treatment liquid to enter between the substrate and the treatment film, the removal object and the treatment film are stripped from the upper surface of the substrate together.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: U.S. Patent Application Publication No. 2015 / 128994 Summary of the invention

[0010] Problems to be solved by the invention

[0011] For example, when the size of the object to be removed on the substrate is large and the object to be removed cannot be held by the processing film with an appropriate holding force, the object to be removed may remain on the substrate when the processing film is peeled off from the upper surface of the substrate using the method of Patent Document 1. Thus, there is a possibility that the object to be removed cannot be fully removed from the substrate.

[0012] Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of efficiently removing a removal object existing on the surface of a substrate.

[0013] Means for solving problems

[0014] One embodiment of the present invention provides a substrate processing method, which includes the following steps: a processing liquid supplying step, supplying a processing liquid containing a solute and a solvent to the surface of a substrate; a processing film forming step, solidifying or hardening the processing liquid supplied to the surface of the substrate to form a processing film on the surface of the substrate for retaining a removal object present on the surface of the substrate; and a removal step, supplying a removal liquid in a droplet state to the surface of the substrate so that the physical force of the removal liquid in a droplet state acts on the processing film and the removal object, thereby removing the processing film and the removal object from the surface of the substrate.

[0015] According to this method, a treatment film for holding the removal object is formed by solidifying or hardening the treatment liquid supplied to the surface of the substrate. Then, the removal liquid is supplied to the surface of the substrate in the form of droplets. Thus, the physical force of the droplets of the removal liquid acts on the treatment film and the removal object.

[0016] Specifically, the physical force of the droplets of the removing liquid acts on the processing film, so that the processing film with the removal object is split and peeled off from the surface of the substrate to be removed from the surface of the substrate. Furthermore, the physical force of the droplets of the removing liquid acts on the removal object, so that the removal object is removed from the surface of the substrate.

[0017] Therefore, the physical force of the droplets of the removing liquid can be applied to the processing film to remove most of the removal objects from the surface of the substrate together with the processing film. In addition, by applying the physical force of the droplets of the removing liquid to the removal objects, the removal objects that are not removed together with the processing film are removed from the surface of the substrate.

[0018] As a result, the removal object existing on the surface of the substrate can be removed efficiently.

[0019] In one embodiment of the present invention, the processing film forming step includes a step of forming the processing film having a film thickness smaller than a radius of the removal object held by the processing film.

[0020] When the film thickness of the processing film is smaller than the radius of the object to be removed, it is difficult for the processing film to enter between the object to be removed and the substrate. Therefore, in this case, there is a possibility that the processing film cannot hold the object to be removed with sufficient holding force.

[0021] Therefore, if the removal liquid is supplied to the surface of the substrate in the form of droplets, the physical force of the droplets of the removal liquid acts not only on the treatment film but also on the removal object. Thus, even if the thickness of the treatment film is smaller than the radius of the removal object, the removal object can be fully removed from the surface of the substrate.

[0022] In one embodiment of the present invention, the removal liquid is water or an alkaline liquid. When the removal liquid is water or an alkaline liquid, the physical force of the droplets can act not only on the treatment film but also on the removal object. When the removal liquid is an alkaline liquid, the treatment film is easily dissolved compared to when the removal liquid is water. Therefore, the physical force can be applied to the treatment film while the strength of the treatment film is reduced. Conversely, when the removal liquid is water, the treatment film is less likely to be dissolved compared to when the removal liquid is an alkaline liquid. Therefore, the physical force can be applied to the treatment film while the number of removal objects retained on the treatment film is increased as much as possible.

[0023] In one embodiment of the present invention, the substrate processing method further includes a protective liquid film forming process, in which, before the removal process begins, protective liquid is supplied to the surface of the substrate in a continuous flow, thereby forming a liquid film of the protective liquid on the surface of the substrate covering the supply area to which the removal liquid is supplied in a droplet state in the removal process.

[0024] The physical force from the droplets of the removal liquid acting on the surface of the substrate is particularly large in the supply region. Therefore, if the supply region is covered with a liquid film of the protection liquid before the removal process begins, the physical force from the droplets of the removal liquid acting on the supply region can be appropriately reduced, so that the physical force of the droplets of the removal liquid is dispersed over the entire surface of the substrate. In this way, the processing film and the removal object can be removed from the surface of the substrate while protecting the surface of the substrate.

[0025] In particular, when a concavo-convex pattern is formed on the surface of the substrate, the concavo-convex pattern may collapse in the supply region due to the physical force from the droplets of the removal liquid acting on the surface of the substrate. If the supply region is covered with a liquid film of the protection liquid before the removal process begins, the physical force acting on the concavo-convex pattern can be appropriately reduced in the supply region to protect the concavo-convex pattern.

[0026] The physical force acting on the surface of the substrate when a continuous flow of liquid is supplied to the surface of the substrate is much smaller than the physical force acting on the surface of the substrate when droplets are supplied to the surface of the substrate. Therefore, it is possible to suppress or prevent the surface damage of the substrate caused by the supply of the protective liquid. In particular, when a concave-convex pattern is formed on the surface of the substrate, if the protective liquid is supplied to the surface of the substrate in a continuous flow, the collapse of the concave-convex pattern caused by the supply of the protective liquid can be suppressed or prevented.

[0027] In one embodiment of the present invention, the substrate processing method further includes a protection liquid parallel supply step of supplying the protection liquid to the surface of the substrate in a continuous flow while the removal liquid is supplied to the surface of the substrate in a droplet state in the removal step.

[0028] According to this method, during the period when the removal liquid is supplied to the surface of the substrate in the form of droplets in the removal process, the protection liquid is supplied to the surface of the substrate in a continuous flow. Therefore, the surface of the substrate can be kept covered by the protection liquid in the removal process. As a result, the physical force acting on the area of ​​the substrate surface to which the removal liquid is supplied in the form of droplets can be appropriately reduced, and the physical force of the droplets of the removal liquid can be dispersed to the entire surface of the substrate. As a result, the processing film and the removal object can be removed from the surface of the substrate while protecting the surface of the substrate (especially the concave-convex pattern formed on the surface of the substrate).

[0029] In one embodiment of the present invention, the protective liquid has a property of partially dissolving the treatment film.

[0030] According to this method, the processing film is partially dissolved by the protective liquid. Therefore, while the strength of the processing film is reduced by the protective liquid, the physical force of the droplets of the removal liquid can be applied to the processing film. As a result, the processing film can be efficiently split and the processing film can be efficiently peeled off from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

[0031] In one embodiment of the present invention, the protective liquid is water or an alkaline liquid. When the protective liquid is water or an alkaline liquid, the physical force of the droplets of the removal liquid acting on the surface of the substrate can be appropriately reduced, so that the physical force of the droplets of the removal liquid is dispersed to the entire surface of the substrate. When the protective liquid is an alkaline liquid, it is easier to dissolve the treatment film than when the protective liquid is water. Therefore, it is easy to reduce the strength of the treatment film. On the contrary, when the protective liquid is water, it is not easy to dissolve the treatment film compared to when the protective liquid is an alkaline liquid, so it is easy to maintain the treatment film in a state of removing the object.

[0032] In one embodiment of the present invention, the substrate processing method further includes a residue removal process, wherein a dissolving liquid for dissolving the processing film is supplied to the surface of the substrate to remove the residue of the processing film remaining on the surface of the substrate after the removal process.

[0033] After the process film is removed from the surface of the substrate in the removal process, there may be residues of the process film remaining on the surface of the substrate. Therefore, by supplying a dissolving liquid that dissolves the process film to the surface of the substrate, the residues of the process film remaining on the surface of the substrate can be removed. Thus, the surface of the substrate can be well cleaned.

[0034] In one embodiment of the present invention, the removing step includes a step of supplying the removing liquid in a droplet state to the surface of the substrate to partially dissolve the processing film in the removing liquid.

[0035] According to this method, the treatment film is partially dissolved by the removal liquid. Therefore, the physical force of the droplets of the removal liquid can be applied to the treatment film while the strength of the treatment film is reduced. Thus, the treatment film can be efficiently split and the treatment film can be efficiently peeled off from the surface of the substrate. As a result, the treatment film can be efficiently removed from the surface of the substrate.

[0036] In one embodiment of the present invention, the solute includes a high-soluble substance and a low-soluble substance whose solubility in the removal solution is lower than that of the high-soluble substance. The process film forming step includes a step of forming the process film including the high-soluble substance in a solid state and the low-soluble substance in a solid state. Furthermore, the removal step includes a step of promoting the peeling of the process film from the surface of the substrate and the splitting of the process film by selectively dissolving the high-soluble substance in a solid state in the process film in the removal solution.

[0037] According to this method, the solid high-soluble substances in the treated film are selectively dissolved by the removal liquid. The so-called "solid high-soluble substances are selectively dissolved" does not mean that only the solid high-soluble substances are dissolved, but that a small amount of solid low-soluble substances are also dissolved, and most of the solid high-soluble substances are dissolved.

[0038] Therefore, although the strength of the treatment film is reduced, the state in which the object to be removed is held by the treatment film is maintained. Therefore, in the state in which the object to be removed is still held by the treatment film and the strength of the treatment film is reduced, the physical force of the droplets of the removal liquid can be applied to the treatment film in the removal process. Thus, the treatment film can be efficiently split and the treatment film can be efficiently peeled off from the surface of the substrate.

[0039] In one embodiment of the present invention, the solute contains a solubility enhancing substance. Furthermore, the removal step includes a step of enhancing the solubility of the removal solution supplied to the surface of the substrate for dissolving the treatment film by dissolving the solubility enhancing substance from the treatment film into the removal solution supplied to the surface of the substrate, and partially dissolving the treatment film in the removal solution with enhanced solubility.

[0040] According to this method, by making the dissolving power strengthening substance dissolve from the treatment film into the removal liquid, the dissolving power of the removal liquid to dissolve the treatment film is strengthened, and the treatment film is partially dissolved by the removal liquid. Therefore, even when a liquid with low dissolving power is used as the removal liquid, the physical force of the droplets of the removal liquid can be applied to the treatment film while reducing the strength of the treatment film. Thus, the treatment film can be efficiently split and the treatment film can be efficiently peeled off from the surface of the substrate. As a result, the treatment film can be efficiently removed from the surface of the substrate.

[0041] Other embodiments of the present invention provide a substrate processing device, comprising: a processing liquid supply unit, which supplies a processing liquid containing a solute and a solvent to the surface of a substrate; a solid forming unit, which solidifies or hardens the processing liquid; a removing liquid supply unit, which supplies the removing liquid in a droplet state to the surface of the substrate; and a controller, which controls the processing liquid supply unit, the solid forming unit and the removing liquid supply unit.

[0042] Furthermore, the controller is programmed to perform the following processes: a processing liquid supplying process, in which the processing liquid is supplied from the processing liquid supplying unit to the surface of the substrate; a processing film forming process, in which the processing liquid supplied to the surface of the substrate is solidified or hardened by the solid forming unit, thereby forming a processing film on the surface of the substrate for retaining the removal object existing on the surface of the substrate; and a removal process, in which the removal liquid is supplied from the removing liquid supplying unit to the surface of the substrate in a droplet state so that the physical force of the droplets of the removal liquid acts on the processing film and the removal object, thereby removing the processing film and the removal object from the surface of the substrate.

[0043] According to the device, a treatment film for holding the removal object is formed by solidifying or hardening the treatment liquid supplied to the surface of the substrate. Then, the removal liquid is supplied to the surface of the substrate in the form of droplets. Thus, the physical force of the droplets of the removal liquid acts on the treatment film and the removal object.

[0044] Specifically, the controller is programmed to perform the following steps in the removal process: a treatment film removal step, in which the physical force of droplets of the removing liquid is applied to the treatment film, thereby peeling the treatment film, which retains the removal object, from the surface of the substrate and splitting it to remove it from the surface of the substrate; and a removal object removal step, in which the physical force of droplets of the removing liquid is applied to the removal object, thereby removing the removal object from the surface of the substrate.

[0045] Therefore, the physical force of the droplets of the removal liquid can be applied to the treatment film to remove most of the removal objects from the surface of the substrate together with the treatment film. In addition, by applying the physical force of the droplets of the removal liquid to the removal objects, the removal objects that are not removed together with the treatment film can also be removed from the surface of the substrate.

[0046] As a result, the removal object existing on the surface of the substrate can be removed efficiently.

[0047] In another embodiment of the present invention, the controller is programmed to form the processing film having a film thickness smaller than a radius of the removal object held by the processing film in the processing film forming step.

[0048] When the thickness of the treatment film is smaller than the radius of the object to be removed, it is difficult for the treatment film to enter between the object to be removed and the substrate. Therefore, in this case, there is a possibility that the treatment film cannot hold the object to be removed with sufficient holding force. Therefore, in the method of peeling the treatment film holding the object to be removed from the surface of the substrate, the object to be removed is likely to remain on the surface of the substrate because the treatment film cannot take the object to be removed away from the surface of the substrate.

[0049] Therefore, if the removal liquid is supplied to the surface of the substrate in the form of droplets, the physical force of the droplets of the removal liquid acts not only on the treatment film but also on the removal object. Thus, even if the thickness of the treatment film is smaller than the radius of the removal object, the removal object can be fully removed from the surface of the substrate.

[0050] In another embodiment of the present invention, the substrate processing device further comprises a first protection liquid supply unit, which supplies the protection liquid to the surface of the substrate in a continuous flow. In addition, the controller is programmed to perform the following protection liquid film forming process, that is, before the removal process starts, the protection liquid is supplied from the first protection liquid supply unit in a continuous flow to the surface of the substrate, thereby forming a liquid film of the protection liquid on the surface of the substrate covering the supply area to which the removal liquid is supplied in the form of droplets in the removal process.

[0051] The physical force from the droplets of the removal liquid acting on the surface of the substrate is particularly large in the supply region. Therefore, if the supply region is covered with a liquid film of the protection liquid before the removal process begins, the physical force from the droplets of the removal liquid acting on the supply region can be appropriately reduced, and the physical force of the droplets of the removal liquid can be dispersed to the entire surface of the substrate. In this way, the processing film and the removal object can be removed from the surface of the substrate while protecting the surface of the substrate.

[0052] In particular, when a concavo-convex pattern is formed on the surface of the substrate, the concavo-convex pattern may collapse in the supply region due to the physical force acting on the surface of the substrate from the droplets of the removal liquid. If the supply region is covered with a liquid film of the protection liquid before the removal process begins, the physical force acting on the concavo-convex pattern in the supply region can be appropriately reduced to protect the concavo-convex pattern.

[0053] The physical force acting on the surface of the substrate when a continuous flow of liquid is supplied to the surface of the substrate is much smaller than the physical force acting on the surface of the substrate when droplets are supplied to the surface of the substrate. Therefore, it is possible to suppress or prevent the surface damage of the substrate caused by the supply of the protective liquid. In particular, when a concave-convex pattern is formed on the surface of the substrate, if the protective liquid is supplied to the surface of the substrate in a continuous flow, the collapse of the concave-convex pattern caused by the supply of the protective liquid can be suppressed or prevented.

[0054] In another embodiment of the present invention, the substrate processing apparatus further comprises a second protection liquid supply unit, which supplies the protection liquid to the surface of the substrate in a continuous flow. Furthermore, the controller is programmed to perform the following protection liquid parallel supply process, that is, during the period when the removal liquid is supplied to the surface of the substrate in a droplet state in the removal process, the protection liquid is supplied to the surface of the substrate from the second protection liquid supply unit in a continuous flow.

[0055] According to the device, during the period when the removal liquid is supplied to the surface of the substrate in the form of droplets in the removal process, the protection liquid is supplied to the surface of the substrate in a continuous flow. Therefore, it is possible to maintain the state in which the surface of the substrate is covered by the protection liquid in the removal process. As a result, the physical force acting on the area of ​​the surface of the substrate to which the removal liquid is supplied in the form of droplets can be appropriately reduced, and the physical force of the droplets of the removal liquid can be dispersed to the entire surface of the substrate. As a result, the processing film and the removal object can be removed from the surface of the substrate while protecting the surface of the substrate (especially the concave-convex pattern formed on the surface of the substrate).

[0056] In another embodiment of the present invention, the protective liquid has a property of partially dissolving the treatment film.

[0057] According to the device, the processing film is partially dissolved by the protective liquid. Therefore, the physical force of the droplets of the removal liquid can be applied to the processing film while the strength of the processing film is reduced by the protective liquid. Thus, the processing film can be efficiently split and the processing film can be efficiently peeled off from the surface of the substrate. As a result, the processing film can be efficiently removed from the surface of the substrate.

[0058] In another embodiment of the present invention, the substrate processing apparatus further comprises a dissolving liquid supply unit, which supplies a dissolving liquid to the surface of the substrate to dissolve the processing film. Furthermore, the controller is programmed to perform the following residue removal process, that is, the dissolving liquid is supplied from the dissolving liquid supply unit to remove the residue of the processing film remaining on the surface of the substrate after the removal process.

[0059] After the process film is removed from the surface of the substrate in the removal process, residues of the process film may remain on the surface of the substrate. Therefore, by supplying a dissolving liquid that dissolves the process film to the surface of the substrate, the residues of the process film remaining on the surface of the substrate can be removed. Thus, the surface of the substrate can be well cleaned.

[0060] In another embodiment of the present invention, the controller executes, in the removing step, a step of partially dissolving the processing film in the removing liquid by supplying the removing liquid in a droplet state to the surface of the substrate.

[0061] According to the device, the process film is partially dissolved by the removal liquid. Therefore, the physical force of the droplets of the removal liquid can be applied to the process film while the strength of the process film is reduced. Thus, the process film can be efficiently split and the process film can be efficiently peeled off from the surface of the substrate. As a result, the process film can be efficiently removed from the surface of the substrate.

[0062] The above and other objects, features and effects of the present invention will become more apparent from the following description of the embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] Figure 1 It is a schematic plan view showing the layout of the substrate processing apparatus according to the first embodiment of the present invention.

[0064] Figure 2 It is a schematic partial cross-sectional view showing a schematic structure of a processing unit included in the substrate processing apparatus.

[0065] Figure 3A It is a schematic side view of a removing liquid supply unit and a protecting liquid supply unit included in the substrate processing apparatus.

[0066] Figure 3B4 is a schematic plan view of the removing liquid supply unit and the protecting liquid supply unit.

[0067] Figure 4 It is a block diagram showing the electrical structure of the main parts of the substrate processing apparatus.

[0068] Figure 5 This is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus.

[0069] Fig. 6A It is a schematic diagram for explaining the process of supplying the processing liquid (step S5) of the substrate processing.

[0070] Figure 6B It is a schematic diagram for explaining the thinning step (step S6) of the substrate processing.

[0071] Figure 6C It is a schematic diagram for explaining the thinning step (step S6) of the substrate processing.

[0072] Fig.6D It is a schematic diagram for explaining the state of the solid forming step (step S7) of the substrate processing.

[0073] Fig. 6E It is a schematic diagram for explaining the state of the protective liquid film forming step (step S8) of the substrate processing.

[0074] Fig. 6F It is a schematic diagram for explaining the state of the removal process (step S9) of the above-mentioned substrate processing.

[0075] Figure 6G It is a schematic diagram for explaining the state of the second rinsing process (step S10) of the substrate processing.

[0076] Figure 6H It is a schematic diagram for explaining the state of the second organic solvent supplying step (step S11) of the substrate processing.

[0077] Fig.6I It is a schematic diagram for explaining the spin drying process (step S12) of the substrate processing.

[0078] Fig. 7A It is a schematic diagram for explaining the state when the processing film is removed from the substrate in the above-mentioned substrate processing.

[0079] Figure 7B It is a schematic diagram for explaining the state when the processing film is removed from the substrate in the above-mentioned substrate processing.

[0080] Figure 7CIt is a schematic diagram for explaining the state when the processing film is removed from the substrate in the above-mentioned substrate processing.

[0081] Figure 8 This is a schematic diagram for explaining the state of removing the processing film from the substrate when an alkaline aqueous solution is used as the protective liquid.

[0082] Fig. 9A This is a schematic diagram for explaining a state when a processing film is removed from a substrate during substrate processing by the substrate processing apparatus according to the second embodiment of the present invention.

[0083] Fig. 9B This is a schematic diagram for explaining a state when a processing film is removed from a substrate during substrate processing by the substrate processing apparatus according to the second embodiment.

[0084] Fig. 9C This is a schematic diagram for explaining a state when a processing film is removed from a substrate during substrate processing by the substrate processing apparatus according to the second embodiment.

[0085] Fig. 10A This is a schematic diagram for explaining a situation when a processing film is removed from a substrate during substrate processing by the substrate processing apparatus according to the third embodiment of the present invention.

[0086] Fig. 10B This is a schematic diagram for explaining a situation when a processing film is removed from a substrate during substrate processing by the substrate processing apparatus according to the third embodiment.

[0087] Fig. 10C This is a schematic diagram for explaining a state when a processing film is removed from a substrate during substrate processing by the substrate processing apparatus according to the third embodiment.

[0088] Fig.11 It is a schematic diagram for explaining the state of the removal step (step S9) when the protection liquid film forming step is omitted in the substrate processing.

[0089] Fig.12 This is a schematic diagram for explaining the state of the removal step (step S9) in the case where the supply of the protection liquid in the removal step is omitted in the substrate processing.

[0090] Fig.13 It is a schematic diagram for explaining the state of the removal step (step S9) in the case where the supply of the protection liquid in the removal step and the protection liquid film formation step are omitted in the substrate processing.

[0091] Fig.14 The figure is a schematic diagram showing a structure in which the protection liquid supply unit is held on the nozzle holder together with other protection liquid supply units. DETAILED DESCRIPTION

[0092] <First embodiment>

[0093] Figure 1 It is a schematic plan view showing the layout of the substrate processing apparatus 1 according to the first embodiment of the present invention.

[0094] The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates W such as silicon wafers one by one. In the present embodiment, the substrate W is a disk-shaped substrate.

[0095] The substrate processing device 1 includes: multiple processing units 2, which use fluid to process the substrate W; a loading port LP, on which a carrier C is loaded, wherein the carrier C accommodates multiple substrates W processed by the processing unit 2; transfer robots IR and CR, which transfer the substrate W between the loading port LP and the processing unit 2; and a controller 3, which controls the substrate processing device 1.

[0096] The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing unit 2. The plurality of processing units 2 have, for example, the same structure. As will be described in detail later, the processing fluid supplied to the substrate W in the processing unit 2 includes a chemical solution, a rinsing solution, a processing solution, a removal solution, a protective solution, a heat medium, a dissolving solution, an inactive gas, and the like.

[0097] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and processes the substrate W in the processing cup 7. The chamber 4 is formed with an entrance (not shown) through which the substrate W is carried in or carried out by the transfer robot CR. The chamber 4 includes a shutter unit (not shown) for opening and closing the entrance.

[0098] Figure 2 1 is a schematic diagram for explaining a configuration example of the processing unit 2. The processing unit 2 includes a spin chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 8, a second moving nozzle 9, a third moving nozzle 10, a fourth moving nozzle 11, a central nozzle 14, and a lower surface nozzle 15.

[0099] The spin chuck 5 rotates the substrate W around a vertical rotation axis A1 (vertical axis) passing through the center of the substrate W while holding the substrate W horizontally. The spin chuck 5 includes a plurality of chuck pins 20 , a rotating base 21 , a rotating shaft 22 , and a rotating motor 23 .

[0100] The rotating base 21 has a disk shape along the horizontal direction. On the upper surface of the rotating base 21, a plurality of chuck pins 20 for holding the periphery of the substrate W are arranged at intervals along the circumferential direction of the rotating base 21. The rotating base 21 and the plurality of chuck pins 20 constitute a substrate holding unit for holding the substrate W horizontally. The substrate holding unit is also called a substrate holder.

[0101] The rotating shaft 22 extends in the vertical direction along the rotating axis A1. The upper end of the rotating shaft 22 is connected to the center of the lower surface of the rotating base 21. The rotating motor 23 applies a rotating force to the rotating shaft 22. By rotating the rotating shaft 22 by the rotating motor 23, the rotating base 21 rotates. As a result, the substrate W rotates around the rotating axis A1. The rotating motor 23 is an example of a substrate rotating unit that rotates the substrate W around the rotating axis A1.

[0102] The opposing member 6 is opposed to the substrate W held by the spin chuck 5 from above. The opposing member 6 is formed in a disk shape having a diameter greater than or equal to the diameter of the substrate W. The opposing member 6 has an opposing surface 6a opposed to the upper surface (upper surface) of the substrate W. The opposing surface 6a is arranged above the spin chuck 5 along a substantially horizontal plane.

[0103] A hollow shaft 60 is fixed to the opposing member 6 on the side opposite to the opposing surface 6a. A communicating hole 6b is formed in the opposing member 6 at a portion that coincides with the rotation axis A1 in a plan view. The communicating hole 6b vertically penetrates the opposing member 6 and communicates with the internal space 60A of the hollow shaft 60.

[0104] The opposing member 6 blocks the atmosphere in the space between the opposing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the opposing member 6 is also called a blocking plate.

[0105] The processing unit 2 further includes an opposing member lifting unit 61 for driving the opposing member 6 to move upward and downward. The opposing member lifting unit 61 can position the opposing member 6 at any position (height) from a lower position to an upper position. The lower position is a position where the opposing surface 6a is closest to the substrate W within the movable range of the opposing member 6. The upper position is a position where the opposing surface 6a is farthest away from the substrate W within the movable range of the opposing member 6.

[0106] The opposing member lifting unit 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) supporting the hollow shaft 60, and an electric motor (not shown) for imparting a driving force to the ball screw mechanism. The opposing member lifting unit 61 is also referred to as an opposing member lifter (partition plate lifter).

[0107] The processing cup 7 includes: a plurality of protective covers 71 that receive liquid flying outward from the substrate W held on the spin chuck 5; a plurality of cups 72 that receive liquid guided downward by the plurality of protective covers 71; and a cylindrical outer wall member 73 that surrounds the plurality of protective covers 71 and the plurality of cups 72.

[0108] In the present embodiment, an example is shown in which two protection covers 71 (a first protection cover 71A and a second protection cover 71B) and two cups 72 (a first cup 72A and a second cup 72B) are provided.

[0109] Each of the first cup 72A and the second cup 72B has a shape of an annular groove that is open upward.

[0110] The first protection cover 71A is disposed so as to surround the spin base 21. The second protection cover 71B is disposed so as to surround the spin base 21 outward in the radial direction of rotation of the substrate W than the first protection cover 71A.

[0111] The first protection cover 71A and the second protection cover 71B each have a substantially cylindrical shape. The upper end of each protection cover 71 is inclined inwardly toward the rotating base 21 .

[0112] The first cup 72A receives the liquid guided downward by the first protective cover 71A. The second cup 72B is formed integrally with the first protective cover 71A, and receives the liquid guided downward by the second protective cover 71B.

[0113] The processing unit 2 includes a shield lifting unit 74 that independently lifts the first shield 71A and the second shield 71B. The shield lifting unit 74 lifts the first shield 71A between a lower position and an upper position. The shield lifting unit 74 lifts the second shield 71B between a lower position and an upper position.

[0114] When the first protection cover 71A and the second protection cover 71B are both in the upper position, the first protection cover 71A receives the liquid scattered from the substrate W. When the first protection cover 71A is in the lower position and the second protection cover 71B is in the upper position, the liquid scattered from the substrate W is received by the second protection cover 71B.

[0115] The shield lifting unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first shield 71A, a first motor (not shown) for imparting a driving force to the first ball screw mechanism, a second ball screw mechanism (not shown) coupled to the second shield 71B, and a second motor (not shown) for imparting a driving force to the second ball screw mechanism. The shield lifting unit 74 is also referred to as a shield lifter.

[0116] The first movable nozzle 8 is an example of a chemical liquid nozzle (chemical liquid supplying means) that discharges (discharges) a chemical liquid toward the upper surface of the substrate W held by the spin chuck 5 .

[0117] The first movable nozzle 8 is moved in the horizontal direction and the vertical direction by the first nozzle moving unit 36. The first movable nozzle 8 is movable between a center position and a home position (retracted position) along the horizontal direction.

[0118] When the first movable nozzle 8 is located at the center position, it is opposed to the rotation center of the upper surface of the substrate W. The rotation center of the upper surface of the substrate W is the intersection position with the rotation axis A1 on the upper surface of the substrate W. When the first movable nozzle 8 is located at the home position, it is not opposed to the upper surface of the substrate W and is located outside the processing cup 7 in a plan view.

[0119] The first movable nozzle 8 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0120] The first nozzle moving unit 36 ​​includes, for example, a rotation shaft (not shown) extending in the vertical direction, an arm (not shown) connected to the rotation shaft and extending horizontally, and a rotation shaft driving unit (not shown) for lifting or rotating the rotation shaft.

[0121] The rotation axis driving unit swings the arm by rotating the rotation axis around a vertical rotation axis. In addition, the rotation axis driving unit moves the arm up and down by raising and lowering the rotation axis in the vertical direction. The first movable nozzle 8 is fixed to the arm. The first movable nozzle 8 moves in the horizontal direction and the vertical direction in accordance with the swinging and raising and lowering of the arm.

[0122] The first moving nozzle 8 is connected to a chemical liquid pipe 40 for guiding the chemical liquid. When a chemical liquid valve 50 provided on the chemical liquid pipe 40 is opened, the chemical liquid is continuously ejected downward from the first moving nozzle 8.

[0123] The liquid medicine sprayed from the first moving nozzle 8 is a solution containing at least one of sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, hydrogen peroxide, organic acid (e.g., citric acid, oxalic acid, etc.), organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and preservative. Examples of liquid medicine obtained by mixing the above components include SPM liquid (sulfuric acid / hydrogen peroxide mixture) and SC1 liquid (ammonia-hydrogenperoxide mixture).

[0124] The second movable nozzle 9 is an example of a processing liquid nozzle (processing liquid supplying unit) that supplies (discharges) the processing liquid onto the upper surface of the substrate W held by the spin chuck 5 .

[0125] The second movable nozzle 9 is moved in the horizontal direction and the vertical direction by the second nozzle moving unit 37. The second movable nozzle 9 can move between the center position and the home position (retreat position) along the horizontal direction. When the second movable nozzle 9 is located at the center position, it is opposite to the rotation center of the upper surface of the substrate W. When the second movable nozzle 9 is located at the home position, it is not opposite to the upper surface of the substrate W, and is located outside the processing cup 7 when viewed from above. The second movable nozzle 9 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving along the vertical direction.

[0126] The second nozzle moving unit 37 has the same structure as the first nozzle moving unit 36. That is, the second nozzle moving unit 37 includes, for example, a rotation axis (not shown) along the vertical direction, an arm (not shown) connected to the rotation axis and the second moving nozzle 9 and extending horizontally, and a rotation axis driving unit (not shown) for lifting or rotating the rotation axis.

[0127] The second moving nozzle 9 is connected to a process liquid pipe 41 for guiding the process liquid. When a process liquid valve 51 attached to the process liquid pipe 41 is opened, the process liquid is continuously ejected downward from the second moving nozzle 9.

[0128] The processing liquid ejected from the second movable nozzle 9 contains a solute and a solvent. The processing liquid solidifies or hardens by at least a portion of the solvent volatilizing (evaporating). The processing liquid solidifies or hardens on the substrate W, thereby forming a processing film that holds the removal object such as particles existing on the substrate W. The removal object is, for example, foreign matter attached to the surface of the substrate W after dry etching or ashing.

[0129] The solute contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, novolac. The solvent contained in the treatment liquid ejected from the second moving nozzle 9 may be a liquid that dissolves the solute, for example, an alcohol such as IPA. The solvent contained in the treatment liquid is preferably a liquid that is compatible (miscible) with the removal liquid.

[0130] As the solvent contained in the treatment liquid used in the first embodiment, the substances listed as the solvent contained in the treatment liquid used in the second embodiment described later can be used. As the solute contained in the treatment liquid used in the first embodiment, the substances listed as the low-soluble substances contained in the treatment liquid used in the second embodiment described later can be used.

[0131] Here, "solidification" means that the solute becomes solid due to the forces between molecules and atoms, for example, accompanying the volatilization of the solvent. "Hardening" means that the solute becomes solid due to chemical changes such as polymerization and cross-linking. Therefore, "solidification or hardening" means that the solute "hardens" due to various factors.

[0132] The third movable nozzle 10 is a spray nozzle that sprays a large amount of droplets of a removal liquid. It is an example of a removal liquid nozzle (removal liquid supply unit) that supplies (sprays) a removal liquid such as pure water to the upper surface of the substrate W held on the spin chuck 5 in a droplet state. The removal liquid is a liquid for removing a processing film formed on the upper surface of the substrate W and a removal object existing on the upper surface of the substrate W from the upper surface of the substrate W.

[0133] The third movable nozzle 10 is moved in the horizontal direction and the vertical direction by the third nozzle moving unit 38. The third movable nozzle 10 is movable between a center position and a home position (retracted position) along the horizontal direction.

[0134] When the third movable nozzle 10 is located at the center position, it is opposed to the rotation center of the upper surface of the substrate W. When the third movable nozzle 10 is located at the home position, it is not opposed to the upper surface of the substrate W and is located outside the processing cup 7 in a plan view. The third movable nozzle 10 can approach the upper surface of the substrate W or retreat upward from the upper surface of the substrate W by moving in the vertical direction.

[0135] The third nozzle moving unit 38 includes, for example, a rotation shaft 38C extending in the vertical direction, a nozzle arm 38A connected to the rotation shaft and the third moving nozzle 10 and extending horizontally, and a rotation shaft driving unit 38D for lifting or rotating the rotation shaft.

[0136] The rotation axis driving unit 38D causes the nozzle arm 38A to swing by rotating the rotation axis 38C around the vertical rotation axis A2. In addition, the rotation axis driving unit 38D causes the nozzle arm 38A to move up and down by raising and lowering the rotation axis 38C in the vertical direction. The third movable nozzle 10 is fixed to the front end of the nozzle arm 38A. The third movable nozzle 10 moves in the horizontal direction and the vertical direction in accordance with the swinging and raising and lowering of the nozzle arm 38A.

[0137] The third moving nozzle 10 is connected to the removing liquid supply source via the removing liquid pipe 42. The third moving nozzle 10 is also connected to the discharge pipe 43 provided with a discharge valve 53. The removing liquid valve 52 and the pump 90 are disposed between the removing liquid supply source and the removing liquid pipe 42.

[0138] The removing liquid is fed from the removing liquid supply source to the removing liquid pipe 42 by a pump 90. The removing liquid is always supplied at a predetermined pressure (for example, 10 MPa or less) to the third moving nozzle 10. The pump 90 can change the pressure of the removing liquid supplied to the third moving nozzle 10 to any pressure.

[0139] A piezo element 91 is built into the third movable nozzle 10. The piezo element 91 is connected to a voltage applying unit 93 via a wiring 92. The voltage applying unit 93 includes, for example, an inverter. The voltage applying unit 93 applies an AC voltage to the piezo element 91. When the AC voltage is applied to the piezo element 91, the piezo element 91 vibrates at a frequency corresponding to the frequency of the applied AC voltage. The voltage applying unit 93 can change the frequency of the AC voltage applied to the piezo element 91 to an arbitrary frequency (for example, hundreds of kHz to several MHz).

[0140] The removal liquid ejected from the third moving nozzle 10 is, for example, pure water (preferably DIW). The removal liquid is not limited to pure water, and may be an alkaline aqueous solution (alkaline liquid), or any one of a neutral and an acidic aqueous solution (non-alkaline aqueous solution). Specific examples of alkaline aqueous solutions include ammonia water, SC1 solution, TMAH aqueous solution, choline aqueous solution, and a combination of any of the above.

[0141] The fourth movable nozzle 11 is an example of a protection liquid nozzle (protection liquid supply unit) that supplies the protection liquid in a continuous flow to the upper surface of the substrate W. The protection liquid is a liquid for protecting the concavo-convex pattern formed on the surface of the substrate W from the removal liquid in a droplet state.

[0142] The fourth movable nozzle 11 is held by a nozzle holder 38B attached to the nozzle arm 38A. Therefore, the fourth movable nozzle 11 is moved integrally with the third movable nozzle 10 by the third nozzle moving unit 38 .

[0143] The fourth moving nozzle 11 is connected to the protection liquid pipe 47. The protection liquid pipe 47 is provided with a protection liquid valve 57A and a protection liquid flow rate regulating valve 57B.

[0144] The protective liquid sprayed from the fourth moving nozzle 11 is, for example, pure water (preferably DIW). The protective liquid is not limited to pure water, and may be an alkaline aqueous solution (alkaline liquid), or any one of a neutral and an acidic aqueous solution (non-alkaline aqueous solution). Specific examples of alkaline aqueous solutions include ammonia water, SC1 solution, TMAH aqueous solution, choline aqueous solution, and a combination of any of the above.

[0145] The central nozzle 14 is accommodated in the internal space 60a of the hollow shaft 60 of the opposing member 6. The ejection port 14a provided at the front end of the central nozzle 14 is opposed from above to the central area of ​​the upper surface of the substrate W. The central area of ​​the upper surface of the substrate W is an area on the upper surface of the substrate W including the rotation center of the substrate W and its surroundings.

[0146] The central nozzle 14 includes a plurality of tubes (a first tube 31, a second tube 32, and a third tube 33) for ejecting fluid downward, and a cylindrical housing 30 surrounding the plurality of tubes. The plurality of tubes and the housing 30 extend in the vertical direction along the rotation axis A1. The ejection port 14a of the central nozzle 14 is also the ejection port of the first tube 31, the ejection port of the second tube 32, and the ejection port of the third tube 33.

[0147] The first tube 31 (central nozzle 14) is an example of a rinse liquid supply unit that supplies the rinse liquid in a continuous flow toward the upper surface of the substrate W. The second tube 32 (central nozzle 14) is an example of a gas supply unit that supplies gas between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6. The third tube 33 (central nozzle 14) is an example of an organic solvent supply unit that supplies an organic solvent such as IPA in a continuous flow toward the upper surface of the substrate W.

[0148] The first tube 31 is connected to an upper rinse liquid pipe 44 that guides the rinse liquid to the first tube 31. When an upper rinse liquid valve 54 installed on the upper rinse liquid pipe 44 is opened, the rinse liquid is ejected from the first tube 31 (central nozzle 14) toward the central area of ​​the upper surface of the substrate W in a continuous flow.

[0149] Examples of the rinse liquid include DIW, carbonated water, electrolyzed ionized water, diluted hydrochloric acid water (eg, about 1 ppm to 100 ppm), diluted ammonia water (eg, about 1 ppm to 100 ppm), reduced water (hydrogen water), and the like.

[0150] The second tube 32 is connected to a gas pipe 45 that guides gas to the second tube 32. When a gas valve 55 attached to the gas pipe 45 is opened, gas is continuously ejected downward from the second tube 32 (central nozzle 14).

[0151] The gas ejected from the second pipe 32 is, for example, an inert gas such as nitrogen (N2). The gas ejected from the second pipe 32 may also be air. The inert gas is not limited to nitrogen, but is a gas that is inert to the upper surface of the substrate W or the pattern formed on the upper surface of the substrate W. As an example of the inert gas, in addition to nitrogen, rare gases such as argon can be cited.

[0152] The third pipe 33 is connected to an organic solvent pipe 46 that guides the organic solvent to the third pipe 33. When an organic solvent valve 56 installed in the organic solvent pipe 46 is opened, the organic solvent is ejected from the third pipe 33 (central nozzle 14) toward the central area of ​​the upper surface of the substrate W in a continuous flow.

[0153] The organic solvent ejected from the third pipe 33 is a residue removing liquid for removing residues remaining on the upper surface of the substrate W after the processing film is removed by the removing liquid. The organic solvent ejected from the third pipe 33 is preferably compatible with the processing liquid and the rinsing liquid.

[0154] Examples of the organic solvent ejected from the third pipe 33 include a solution containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

[0155] The organic solvent ejected from the third pipe 33 does not necessarily have to include a single component, but may be a liquid mixed with other components, such as a mixed liquid of IPA and DIW, or a mixed liquid of IPA and HFE.

[0156] The lower surface nozzle 15 is inserted into a through hole 21a opened in the center of the upper surface of the rotating base 21. The ejection port 15a of the lower surface nozzle 15 is exposed from the upper surface of the rotating base 21. The ejection port 15a of the lower surface nozzle 15 is opposed to the central area of ​​the lower surface (the lower surface) of the substrate W from below. The central area of ​​the lower surface of the substrate W refers to the area of ​​the lower surface of the substrate W including the rotation center of the substrate W.

[0157] One end of a common pipe 80 is connected to the lower surface nozzle 15, which guides the rinsing liquid, the removing liquid, and the heat medium to the lower surface nozzle 15 in common. A lower rinsing liquid pipe 81, which guides the rinsing liquid to the common pipe 80, a lower removing liquid pipe 82, which guides the removing liquid to the common pipe 80, and a heat medium pipe 83, which guides the heat medium to the common pipe 80, are connected to the other end of the common pipe 80.

[0158] When the lower rinsing liquid valve 86 installed on the lower rinsing liquid pipe 81 is opened, the rinsing liquid is ejected from the lower surface nozzle 15 in a continuous flow toward the central area of ​​the lower surface of the substrate W. When the lower removing liquid valve 87 installed on the lower removing liquid pipe 82 is opened, the removing liquid is ejected from the lower surface nozzle 15 in a continuous flow toward the central area of ​​the lower surface of the substrate W. When the heat medium valve 88 installed on the heat medium pipe 83 is opened, the heat medium is ejected from the lower surface nozzle 15 in a continuous flow toward the central area of ​​the lower surface of the substrate W.

[0159] The lower surface nozzle 15 is an example of a lower side rinsing liquid supply unit that supplies a rinsing liquid to the lower surface of the substrate W in a continuous flow. In addition, the lower surface nozzle 15 is an example of a lower side removing liquid supply unit that supplies a removing liquid to the lower surface of the substrate W in a continuous flow. In addition, the lower surface nozzle 15 is an example of a heat medium supply unit that supplies a heat medium for heating the substrate W to the substrate W in a continuous flow. The lower surface nozzle 15 is also a substrate heating unit that heats the substrate W.

[0160] The heat medium ejected from the lower surface nozzle 15 is, for example, high-temperature DIW having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid. When the solvent contained in the processing liquid is IPA, DIW at 60°C to 80°C is used as the heat medium. The heat medium ejected from the lower surface nozzle 15 is not limited to high-temperature DIW, but may also be a high-temperature inert gas, high-temperature air, or other high-temperature gas having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid.

[0161] Figure 3A It is a schematic side view of the third moving nozzle 10 and the fourth moving nozzle 11 . Figure 3B It is a schematic plan view of the third moving nozzle 10 and the fourth moving nozzle 11 .

[0162] like Figure 3A As shown, the third moving nozzle 10 includes a main body 94 for ejecting droplets of the removing liquid, a cover 95 covering the main body 94 , a piezoelectric element 91 covered by the cover 95 , and a sealing portion 96 interposed between the main body 94 and the cover 95 .

[0163] The main body 94 and the cover 95 are both made of a chemical-resistant material. The main body 94 is made of, for example, quartz, and the cover 95 is made of, for example, a fluorine-based resin.

[0164] The sealing portion 96 is formed of an elastic material such as EPDM (ethylene-propylene-diene rubber). The main body 94 has pressure resistance. A part of the main body 94 and the piezoelectric element 91 are accommodated in the inside of the cover 95. One end of the wiring 92 is connected to the voltage applying unit 93. The other end of the wiring 92 is connected to the piezoelectric element 91 in the inside of the cover 95 by soldering, for example. The inside of the cover 95 is sealed by the sealing portion 96.

[0165] The main body 94 includes a supply port 94a for supplying a removing liquid, a discharge port 94b for discharging the removing liquid supplied to the supply port 94a, a removing liquid flow path 94c connecting the supply port 94a and the discharge port 94b, and a plurality of ejection ports 94d (ejection ports) connected to the removing liquid flow path 94c.

[0166] The removal liquid flow passage 94c is provided inside the main body 94. The supply port 94a, the discharge port 94b, and the injection port 94d are opened on the surface of the main body 94. The supply port 94a and the discharge port 94b are located above the injection port 94d. The lower surface of the main body 94 is, for example, a horizontal flat surface, and the injection port 94d is opened on the lower surface of the main body 94. The injection port 94d is a fine hole having a diameter of, for example, several μm to several tens of μm. The removal liquid piping 42 and the discharge piping 43 are connected to the supply port 94a and the discharge port 94b, respectively.

[0167] like Figure 3BAs shown, a plurality of injection ports 94d constitute a plurality of (for example, 4) columns L. Each column L is composed of a large number (for example, more than 10) injection ports 94d arranged at equal intervals. Each column L extends in a straight line along the horizontal longitudinal direction D1. Each column L is not limited to a straight line, but may also be a curved line. The four columns L are parallel. Two of the four columns L are adjacent in a horizontal direction orthogonal to the longitudinal direction D1. Similarly, the remaining two columns L are also adjacent in a horizontal direction orthogonal to the longitudinal direction D1.

[0168] Two adjacent columns L form a pair. In the two columns L that form a pair, the plurality of injection ports 94d constituting one column L and the plurality of injection ports 94d constituting the other column L are offset in the length direction D1. When viewed from the vertical direction, the third movable nozzle 10 is held by the nozzle arm 38A in a manner such that, for example, four columns L intersect the moving trajectory of the third movable nozzle 10.

[0169] The removal liquid is always supplied to the third movable nozzle 10 at high pressure. The removal liquid supplied to the supply port 94a is supplied to the removal liquid flow passage 94c. When the discharge valve 53 is closed, the pressure (hydraulic pressure) of the removal liquid in the removal liquid flow passage 94c is high. Therefore, when the discharge valve 53 is closed, the removal liquid is sprayed from each injection port 94d by hydraulic pressure. In addition, when the discharge valve 53 is closed, if an AC voltage is applied to the piezoelectric element 91, the vibration of the piezoelectric element 91 is imparted to the removal liquid flowing in the removal liquid flow passage 94c, and the removal liquid sprayed from each injection port 94d is separated by the vibration. Therefore, when the discharge valve 53 is closed, if an AC voltage is applied to the piezoelectric element 91, the removal liquid in the droplet state is sprayed from each injection port 94d. Thus, a large amount of droplets of the removal liquid with uniform particle size are sprayed simultaneously at a uniform speed.

[0170] On the other hand, when the discharge valve 53 is open, the removal liquid supplied to the removal liquid flow passage 94c is discharged from the discharge port 94b to the discharge pipe 43. That is, when the discharge valve 53 is open, the hydraulic pressure in the removal liquid flow passage 94c does not rise sufficiently, so the removal liquid supplied to the removal liquid flow passage 94c is not ejected from the ejection port 94d as a fine hole, but is discharged from the ejection port 94b to the discharge pipe 43. Therefore, the ejection of the removal liquid from the ejection port 94d is controlled by the opening and closing of the discharge valve 53.

[0171] The region on the upper surface of the substrate W to which the removal liquid in a droplet state is supplied (the region to which the droplets of the removal liquid are blown) is referred to as a supply region S. The fourth movable nozzle 11 sprays the protection liquid toward a target position P1 on the substrate W. The target position P1 is a position on the upstream side of the supply region S in the rotation direction Dr of the substrate W.

[0172] Figure 41 is a block diagram showing the electrical configuration of a main part of the substrate processing apparatus 1. The controller 3 includes a microcomputer and controls a control target included in the substrate processing apparatus 1 according to a predetermined control program.

[0173] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B storing a control program. The controller 3 is configured to execute various controls for performing substrate processing by executing the control program by the processor 3A.

[0174] In particular, the controller 3 is programmed to control the transport robot arms IR, CR, the rotary motor 23, the first nozzle moving unit 36, the second nozzle moving unit 37, the third nozzle moving unit 38, the opposing member lifting unit 61, the protective cover lifting unit 74, the pump 90, the voltage applying unit 93, the chemical liquid valve 50, the treatment liquid valve 51, the removal liquid valve 52, the discharge valve 53, the upper rinse liquid valve 54, the gas valve 55, the organic solvent valve 56, the protection liquid valve 57A, the protection liquid flow rate regulating valve 57B, the lower rinse liquid valve 86, the lower removal liquid valve 87, and the heat medium valve 88. By controlling the valves by the controller 3, whether the treatment fluid is ejected from the corresponding nozzle and the ejection flow rate of the treatment fluid from the corresponding nozzle are controlled.

[0175] Figure 5 1 is a flowchart for explaining an example of substrate processing performed by the substrate processing apparatus 1 . Figure 5 Mainly, the processing realized by the controller 3 executing the program is shown. FIG. 6A to FIG. 6I It is a schematic diagram for explaining the situation of each process of the said substrate processing.

[0176] In the substrate processing performed by the substrate processing apparatus 1, for example, Figure 5 As shown, the substrate carrying-in process (step S1), the chemical solution supplying process (step S2), the first rinsing process (step S3), the first organic solvent supplying process (step S4), the processing liquid supplying process (step S5), the thin film process (step S6), the solid forming process (step S7), the protective liquid film forming process (step S8), the removal process (step S9), the second rinsing process (step S10), the second organic solvent supplying process (step S11), the spin drying process (step S12) and the substrate carrying-out process (step S13) are performed in sequence.

[0177] First, an unprocessed substrate W is transported by the transfer robots IR and CR (see Figure 1 ) is carried from the carrier C to the processing unit 2 and handed over to the spin chuck 5 (step S1). Thus, the substrate W is held horizontally by the spin chuck 5 (substrate holding step). The spin chuck 5 holds the substrate W until the spin drying step (step S12) is completed. When the substrate W is carried in, the opposing member 6 retreats to the upper position.

[0178] Next, after the transport robot CR retreats outside the processing unit 2, the chemical solution supply process (step S2) starts. Specifically, the rotary motor 23 rotates the rotary base 21. As a result, the substrate W held horizontally rotates (substrate rotating process). The protective cover lifting unit 74 moves the first protective cover 71A and the second protective cover 71B to the upper position.

[0179] The first nozzle moving unit 36 ​​moves the first movable nozzle 8 to the processing position. The processing position of the first movable nozzle 8 is, for example, the central position. Then, the liquid medicine valve 50 is opened. Thus, the liquid medicine is supplied (discharged) from the first movable nozzle 8 toward the central area of ​​the upper surface of the substrate W in a rotating state. The liquid medicine supplied to the upper surface of the substrate W is radially diffused by the centrifugal force, covering the entire upper surface of the substrate W. Thus, the upper surface of the substrate W is processed with the liquid medicine. The discharge of the liquid medicine from the first movable nozzle 8 continues for a predetermined time, for example, 30 seconds. In the liquid medicine supply process, the substrate W is rotated at a predetermined liquid medicine rotation speed, for example, 800 rpm.

[0180] Next, the first rinsing process (step S3) starts. In the first rinsing process, the chemical solution on the substrate W is rinsed with the rinsing liquid.

[0181] Specifically, the chemical liquid valve 50 is closed. Thus, the supply of chemical liquid to the substrate W is stopped. Then, the first nozzle moving unit 36 ​​moves the first movable nozzle 8 to the home position. Then, the opposing member lifting unit 61 moves the opposing member 6 to the processing position between the upper position and the lower position. When the opposing member 6 is located at the processing position, the distance between the upper surface of the substrate W and the opposing surface 6a is, for example, 30 mm. In the first rinsing step, the first protective cover 71A and the second protective cover 71B are maintained in the upper position.

[0182] When the opposing member 6 is located at the processing position, the upper rinsing liquid valve 54 is opened. As a result, the rinsing liquid is supplied (discharged) from the central nozzle 14 to the central area of ​​the upper surface of the rotating substrate W. The rinsing liquid supplied from the central nozzle 14 to the upper surface of the substrate W is radially diffused by the centrifugal force and spreads over the entire upper surface of the substrate W. As a result, the chemical solution on the upper surface of the substrate W is washed out of the substrate W. In the first rinsing step, the substrate W is rotated at a predetermined first rinsing rotation speed, for example, 800 rpm.

[0183] At substantially the same time as the upper rinsing liquid valve 54 is opened, the lower rinsing liquid valve 86 is opened. As a result, the rinsing liquid is supplied (discharged) from the lower surface nozzle 15 to the central area of ​​the lower surface of the rotating substrate W. The rinsing liquid supplied from the lower surface nozzle 15 to the lower surface of the substrate W is radially diffused by centrifugal force and spreads over the entire lower surface of the substrate W. Even in the case where the chemical liquid scattered from the substrate W in the chemical liquid supplying step adheres to the lower surface, the chemical liquid adhered to the lower surface is washed away by the rinsing liquid supplied from the lower surface nozzle 15.

[0184] The spraying of the rinse liquid from the central nozzle 14 and the lower surface nozzle 15 is continued for a predetermined time, for example, 30 seconds.

[0185] Next, the first organic solvent supplying process (step S4) starts. In the first organic solvent supplying process, the rinsing liquid on the substrate W is replaced with the organic solvent.

[0186] Specifically, the upper rinsing liquid valve 54 and the lower rinsing liquid valve 86 are closed. As a result, the supply of the rinsing liquid to the upper and lower surfaces of the substrate W is stopped. Furthermore, the protective cover lifting unit 74 moves the first protective cover 71A to the lower position while maintaining the second protective cover 71B in the upper position. The opposing member 6 is maintained in the processing position.

[0187] The organic solvent valve 56 is opened while the opposing member 6 is maintained at the processing position. As a result, the organic solvent is supplied (discharged) from the central nozzle 14 to the central region of the upper surface of the rotating substrate W.

[0188] The organic solvent supplied from the central nozzle 14 to the upper surface of the substrate W is radially diffused by centrifugal force and spreads over the entire upper surface of the substrate W. Thus, the rinse liquid on the substrate W is replaced with the organic solvent. The ejection of the organic solvent from the central nozzle 14 is continued for a predetermined time, for example, 10 seconds.

[0189] In the first organic solvent supplying step, the substrate W is rotated at a predetermined first organic solvent rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not need to be rotated at a constant rotation speed in the first organic solvent supplying step. For example, the rotation motor 23 may rotate the substrate W at 300 rpm at the start of the supply of the organic solvent, and accelerate the rotation of the substrate W to 1500 rpm while supplying the organic solvent to the substrate W.

[0190] Next, a process liquid supplying process (step S5) starts. In the process liquid supplying process, the organic solvent on the substrate W is replaced with the process liquid.

[0191] Specifically, the organic solvent valve 56 is closed. Thus, the supply of the organic solvent to the substrate W is stopped. Then, the opposing member lifting unit 61 moves the opposing member 6 to the upper position. Then, the protective cover lifting unit 74 moves the first protective cover 71A to the upper position. In the process liquid supply step, the substrate W is rotated at a predetermined process liquid rotation speed, for example, 1500 rpm.

[0192] When the opposing member 6 is retracted to the upper position, Fig. 6A As shown in FIG. 1 , the second nozzle moving unit 37 moves the second moving nozzle 9 to the processing position. The processing position of the second moving nozzle 9 is, for example, the center position.

[0193] When the second movable nozzle 9 is located at the processing position, the processing liquid valve 51 is opened. Thus, the processing liquid is supplied (discharged) from the second movable nozzle 9 to the central area of ​​the upper surface of the rotating substrate W (processing liquid supplying step, processing liquid discharging step). Thus, the organic solvent on the substrate W is replaced by the processing liquid, and a liquid film 101 of the processing liquid is formed in the central area of ​​the upper surface of the substrate W (processing liquid film forming step, processing liquid core forming step). The liquid film 101 of the processing liquid formed in the central area of ​​the upper surface of the substrate W is called a processing liquid core 102. The supply of the processing liquid from the second movable nozzle 9 continues for a predetermined time, for example, 2 seconds to 4 seconds.

[0194] Alternatively, the processing liquid valve 51 may be opened after most of the organic solvent on the substrate W is removed by centrifugal force. In this case, compared with a state where a liquid film of the organic solvent remains on the substrate W, the processing liquid supplied to the central region of the upper surface of the substrate W is less likely to spread on the upper surface of the substrate W, and thus a processing liquid core 102 is more likely to be formed in the central region of the upper surface of the substrate W.

[0195] Next, a treatment film forming step is performed (step S6 and step S7). In the treatment film forming step, the treatment liquid on the substrate W solidifies or hardens to form a treatment film 100 (see FIG. 100 ) on the upper surface of the substrate W that retains the removal object on the substrate W. Fig.6D ).

[0196] In the process film forming step, a thinning step is first performed (step S6 ) In the thinning step, the process liquid on the substrate W is removed by centrifugal force, so that the process liquid film 101 formed on the upper surface of the substrate W becomes thinner.

[0197] Specifically, in the thin film forming step, the processing liquid valve 51 is first closed. Thus, the supply of the processing liquid to the substrate W is stopped. Then, the second movable nozzle 9 is moved to the home position by the second nozzle moving unit 37. In the thin film forming step, the opposing member 6, the first protective cover 71A, and the second protective cover 71B are maintained in the upper position.

[0198] like Figure 6B As shown in FIG. 1 , in the thin filming process, the substrate W is rotated at a predetermined increasing speed. The increasing speed is, for example, 1500 rpm, which is a high speed similar to the processing liquid rotation speed. Therefore, the liquid film 101 (processing liquid core 102) quickly spreads to the periphery of the substrate W and becomes thinner (expanding the thin filming process). When the liquid film 101 spreads to the periphery of the substrate W, as shown in FIG. Figure 6C As shown, the processing liquid begins to be discharged from the upper surface of the substrate W to the outside of the substrate W.

[0199] By increasing the rotation speed (increasing speed) of the substrate W in the thinning step (e.g., to 1500 rpm), the processing liquid can easily and evenly spread on the upper surface of the substrate W. This can suppress the occurrence of a phenomenon (spike phenomenon) in which the upper surface of the substrate W is partially exposed in the processing film 100.

[0200] When the processing liquid starts to be discharged from the upper surface of the substrate W to the outside of the substrate W, the rotary motor 23 changes the rotation speed of the substrate W to a predetermined film thickness adjustment speed. As a result, the liquid film 101 of the processing liquid is adjusted to a desired thickness (film thickness adjustment step). The film thickness adjustment speed is, for example, 300 rpm or 1500 rpm.

[0201] The amount of the liquid film 101 remaining on the upper surface of the substrate W after the thin-filming step is completed (the thickness of the liquid film 101) is determined according to the value of the film thickness adjustment speed, and the thickness of the process film 100 after the process film forming step is determined (the film thickness). The higher the film thickness adjustment speed, the thinner the film thickness of the process film 100. Therefore, when the film thickness adjustment speed is 1500 rpm, the film thickness of the process film 100 formed by the process film forming step becomes smaller than when the film thickness adjustment speed is 300 rpm.

[0202] In this way, the substrate rotation speed is changed by the rotation motor 23, so that the liquid film 101 of the processing liquid is thinned and the film thickness of the processing film 100 is adjusted. That is, the rotation motor 23 functions as a thinning unit for thinning the liquid film 101 of the processing liquid and functions as a processing film thickness adjusting unit for adjusting the film thickness of the processing film 100.

[0203] In the process film forming step, after the thin film forming step (step S6), a solid forming step (step S7) is performed to solidify or harden the liquid film 101 of the process liquid. In the solid forming step, the liquid film 101 on the substrate W is heated to volatilize (evaporate) a part of the solvent of the process liquid on the substrate W.

[0204] Specifically, in the solid formation process, such as Fig.6DAs shown, the opposing member lifting unit 61 moves the opposing member 6 to a close position between the upper position and the lower position. The close position may also be the lower position. The close position is a position where the distance from the upper surface of the substrate W to the opposing surface 6a is, for example, 1 mm. During the heating process, the first protective cover 71A and the second protective cover 71B are maintained in the upper position.

[0205] Then, the gas valve 55 is opened, thereby supplying gas to the space between the upper surface of the substrate W (the upper surface of the liquid film 101 ) and the facing surface 6 a of the facing member 6 (gas supplying step).

[0206] By blowing gas toward the liquid film 101 on the substrate W, the evaporation (volatization) of the solvent in the liquid film 101 is promoted (solvent evaporation step, solvent evaporation promotion step). Therefore, the time required for forming the process film 100 can be shortened. The central nozzle 14 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the process liquid.

[0207] In addition, the heat medium valve 88 is opened. Thus, the heat medium is supplied (ejected) from the lower surface nozzle 15 (heat medium supply process, heat medium ejection process). The heat medium supplied from the lower surface nozzle 15 to the lower surface of the substrate W is radially diffused by the centrifugal force and spreads over the entire lower surface of the substrate W. The supply of the heat medium to the substrate W continues for a predetermined time, for example, 60 seconds. In the solid formation process, the substrate W is rotated at a predetermined solid formation rotation speed, for example, 1000 rpm.

[0208] By supplying a heat medium to the lower surface of the substrate W, the liquid film 101 on the substrate W is heated via the substrate W (heating process). As a result, the evaporation (volatization) of the solvent in the liquid film 101 is promoted (solvent evaporation process, solvent evaporation promotion process). Therefore, the time required for forming the processing film 100 can be shortened. The lower surface nozzle 15 functions as an evaporation unit (evaporation promotion unit) that evaporates the solvent in the processing liquid.

[0209] By performing the film forming process and the solid forming process, the processing liquid is solidified or hardened. Fig.6D As shown, the process film 100 is formed on the substrate W. As described above, the substrate rotating unit (rotation motor 23), the central nozzle 14 and the lower surface nozzle 15 constitute a solid forming unit that solidifies or hardens the process liquid to form a solid (process film 100).

[0210] In the solid formation step, the substrate W is preferably heated so that the temperature of the processing liquid on the substrate W is lower than the boiling point of the solvent. By heating the processing liquid to a temperature lower than the boiling point of the solvent, the solvent can be appropriately left in the processing film 100. As a result, in the subsequent removal step, the solvent remaining in the processing film 100 interacts with the removing liquid, so that the removing liquid easily penetrates into the processing film 100, compared with a case where no solvent remains in the processing film 100. Therefore, the processing film 100 can be easily removed using the removing liquid.

[0211] The heat medium scattered outside the substrate W due to the centrifugal force is received by the first protective cover 71A. The heat medium received by the first protective cover 71A may bounce back from the first protective cover 71A. However, since the opposing member 6 is close to the upper surface of the substrate W, the upper surface of the substrate W can be protected from the heat medium rebounded from the first protective cover 71A. Therefore, the heat medium can be prevented from adhering to the upper surface of the processing film 100, and the generation of particles caused by the heat medium rebounding from the first protective cover 71A can be prevented.

[0212] In addition, if Fig.6D As shown in FIG. 1 , by supplying gas from the central nozzle 14, a gas flow F is formed in the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W, which moves from the central region of the upper surface of the substrate W toward the peripheral edge of the upper surface of the substrate W. By forming the gas flow F that moves from the central region of the upper surface of the substrate W toward the peripheral edge of the upper surface of the substrate W, the heat medium rebounded from the first protective cover 71A can be pushed back to the first protective cover 71A. Therefore, it is possible to further suppress the heat medium from adhering to the upper surface of the processing film 100.

[0213] In this substrate processing, Fig. 6A In the process liquid supplying step (step S5) shown in FIG. 1 , the process liquid supplied to the upper surface of the substrate W may spread along the periphery of the substrate W to the lower surface of the substrate W. In addition, the process liquid scattered from the substrate W may bounce off the first protective cover 71A and adhere to the lower surface of the substrate W. Even in this case, Fig.6D As shown, since the heat medium is supplied to the lower surface of the substrate W in the solid forming step (step S7), the processing liquid can also be removed from the lower surface of the substrate W by the flow of the heat medium.

[0214] Next, a protective liquid film forming step is performed (step S8 ). In the protective liquid film forming step, a protective liquid film (protective liquid film 105 ) is formed on the upper surface of the substrate W.

[0215] Specifically, the heat medium valve 88 is closed, thereby stopping the supply of the heat medium to the lower surface of the substrate W. In addition, the gas valve 55 is closed, thereby stopping the supply of the gas from the central nozzle 14 to the space between the facing surface 6a of the facing member 6 and the upper surface of the substrate W.

[0216] In a state where the supply of gas from the central nozzle 14 is stopped, the opposing member lifting unit 61 moves the opposing member 6 to the upper position. Fig. 6E As shown, the third nozzle moving unit 38 moves the third moving nozzle 10 to the processing position.

[0217] The processing position of the third moving nozzle 10 is, for example, the central position. In this case, the fourth moving nozzle 11 is arranged on the side of the central position. Figure 3B In order to set the target position P1 on the substrate W where the fourth movable nozzle 11 sprays the protective liquid to a position upstream of the supply area S in the rotation direction Dr of the substrate W, the third movable nozzle 10 can also be arranged at a position slightly offset toward the peripheral side of the substrate W compared to the central position.

[0218] Then, the protection liquid valve 57A is opened. Fig. 6E As shown in FIG. 1 , the protective liquid is supplied (discharged) from the fourth movable nozzle 11 in a continuous flow toward the central area of ​​the upper surface of the rotating substrate W. The protective liquid supplied to the upper surface of the substrate W is radially diffused by the centrifugal force and spreads over the entire upper surface of the substrate W. Thus, a protective liquid film 105 is formed on the upper surface of the substrate W. In this way, the fourth movable nozzle 11 functions as a first protective liquid supply unit.

[0219] The protection liquid is discharged from the fourth moving nozzle 11 for a predetermined time, for example, 30 seconds. In the protection liquid supplying step, the substrate W is rotated at a predetermined protection liquid rotation speed, for example, 800 rpm.

[0220] Next, a removal process is performed (step S9 ). In the removal process, the processing film 100 is removed from the upper surface of the substrate W.

[0221] Specifically, the removal valve 52 is opened and the discharge valve 53 is closed. The voltage applying unit 93 applies an AC voltage to the piezoelectric element 91. Fig. 6F As shown, the removing liquid is supplied (discharged) from the third movable nozzle 10 in the form of droplets to the central area of ​​the upper surface of the rotating substrate W (upper removing liquid supplying step, upper removing liquid discharging step, droplet supplying step).

[0222] The supply of the removal liquid to the upper surface of the substrate W is continued for a predetermined time, for example, 60 seconds. In the removal step, the substrate W is rotated at a predetermined removal rotation speed, for example, 800 rpm.

[0223] During the period when the removal liquid is supplied to the upper surface of the substrate W in the form of droplets, Fig. 6FAs shown, the supply of the protection liquid from the fourth movable nozzle 11 is continued (protection liquid parallel supply process). In this way, the fourth movable nozzle 11 functions as a second protection liquid supply unit. The supply of the protection liquid from the fourth movable nozzle 11 to the upper surface of the substrate W is continued from the protection liquid film forming process.

[0224] In addition, the lower side removal liquid valve 87 is opened. As a result, the removal liquid is supplied (discharged) from the lower surface nozzle 15 in a continuous flow toward the central area of ​​the lower surface of the rotating substrate W (lower side removal liquid supplying step, lower side removal liquid discharging step). The removal liquid supplied to the lower surface of the substrate W is spread over the entire lower surface of the substrate W due to the centrifugal force.

[0225] When the removing liquid is supplied to the upper surface of the substrate W in a droplet state, a physical force of the droplet 106 acts on the processing film 100. The physical force of the removing liquid droplet 106 is the impact (kinetic energy) when the removing liquid droplet 106 collides with the protective liquid film 105.

[0226] The physical force of the droplets 106 can be adjusted by changing the frequency of the AC voltage applied to the piezoelectric element 91. Specifically, the larger the frequency of the AC voltage applied to the piezoelectric element 91, the smaller the size of the droplets 106, and the number of droplets 106 ejected per unit time by the third movable nozzle 10 increases. Therefore, the physical force of the droplets 106 acting on the upper surface of the substrate W increases.

[0227] The physical force of the droplets 106 can also be adjusted by changing the pressure of the pump 90. Specifically, the higher the pressure of the pump 90, the greater the flow rate of the removal liquid ejected from the ejection port 94d of the third moving nozzle 10 and the greater the amount of the droplets 106. Therefore, the physical force of the droplets 106 acting on the upper surface of the substrate W increases.

[0228] The physical force of the droplet 106 is transmitted to the processing film 100 and the removal object via the protective liquid film 105. As a result, the processing film 100 and the removal object are peeled off from the upper surface of the substrate W (peeling step, processing film peeling step, removal object peeling step). In addition, the processing film 100 is split into film pieces when being peeled off from the upper surface of the substrate W (splitting step).

[0229] When supplying the droplets 106 of the removal solution to the upper surface of the substrate W, the third nozzle moving unit 38 may reciprocate the third movable nozzle 10 between the center position and the peripheral position opposite to the peripheral region of the upper surface of the substrate W. Thus, the droplets 106 can be made to collide with the entire upper surface of the substrate W without omission, so that the portion where the physical force of the droplets 106 acts can be dispersed to the entire processing film 100.

[0230] When the supply area S is the central area of ​​the upper surface of the substrate W, the physical force of the droplet 106 always acts on the same position on the upper surface of the substrate W regardless of the rotation angle of the substrate W. On the other hand, when the supply area S is an area other than the central area (e.g., the peripheral area) on the upper surface of the substrate W, the position on the upper surface of the substrate W that receives the physical force of the droplet 106 changes along with the rotation of the substrate W. Therefore, when the supply area S is fixed to the central area of ​​the upper surface of the substrate W, the concave-convex pattern on the upper surface of the substrate W is easily damaged. Therefore, by reciprocating the third movable nozzle 10 between the central position and the peripheral position, it is possible to avoid the physical force from being concentrated on the central area of ​​the upper surface of the substrate W.

[0231] After the process film 100 is peeled off and split, the removal liquid is continuously supplied to the upper surface of the substrate W, so that the film pieces of the process film 100 formed by the splitting are discharged to the outside of the substrate W together with the removal liquid. Thus, the removal object and the film pieces of the process film 100 are removed from the upper surface of the substrate W (removal step).

[0232] After the removal process (step S9), the second rinsing process (step S10) is performed. Specifically, the protection liquid valve 57A and the lower side removal liquid valve 87 are closed, and the discharge valve 53 is opened. As a result, the supply of the protection liquid to the upper surface of the substrate W and the supply of the removal liquid to the upper surface and the lower surface of the substrate W are stopped. The removal liquid valve 52 may also be always open. Then, the voltage applying unit 93 stops the application of the AC voltage to the piezoelectric element 91. Then, the third nozzle moving unit 38 moves the third movable nozzle 10 and the fourth movable nozzle 11 to the home position.

[0233] When the third movable nozzle 10 and the fourth movable nozzle 11 are moved to their original positions, Figure 6G As shown, the opposing member lifting unit 61 moves the opposing member 6 to the processing position. In the second rinsing step, the substrate W is rotated at a predetermined second rinsing rotation speed, for example, 800 rpm. The first protection cover 71A and the second protection cover 71B are maintained in the upper position.

[0234] Then, the upper rinse liquid valve 54 is opened. Thus, the rinse liquid is supplied (discharged) from the central nozzle 14 to the central area of ​​the upper surface of the rotating substrate W (second upper rinse liquid supplying step, second upper rinse liquid discharging step). The rinse liquid supplied to the upper surface of the substrate W is spread over the entire upper surface of the substrate W due to the centrifugal force. Thus, the removal liquid attached to the upper surface of the substrate W is washed away by the rinse liquid.

[0235] In addition, the lower side rinsing liquid valve 86 is opened. As a result, the rinsing liquid is supplied (discharged) from the lower surface nozzle 15 to the central area of ​​the lower surface of the rotating substrate W (second lower side rinsing liquid supplying step, second lower side rinsing liquid discharging step). As a result, the removal liquid attached to the lower surface of the substrate W is flushed by the rinsing liquid. The supply of the rinsing liquid to the upper surface and the lower surface of the substrate W is continued for a predetermined time, for example, 35 seconds.

[0236] Next, a second organic solvent supplying process is performed (step S11 ). In the second organic solvent supplying process, an organic solvent is supplied to the upper surface of the substrate W, so that the residue of the processing film 100 remaining on the upper surface of the substrate W is dissolved in the organic solvent and removed.

[0237] Specifically, the upper rinsing liquid valve 54 and the lower rinsing liquid valve 86 are closed. As a result, the supply of the rinsing liquid to the upper surface and the lower surface of the substrate W is stopped. Figure 6H As shown, the shield lifting unit 74 moves the first shield 71A to the lower position. Also, the opposing member 6 is maintained at the processing position. In the second organic solvent supplying step, the substrate W is rotated at a predetermined second organic solvent rotation speed, for example, 300 rpm.

[0238] While the opposing member 6 is maintained at the processing position, the organic solvent valve 56 is opened. As a result, the organic solvent is supplied (ejected) from the central nozzle 14 to the central area of ​​the upper surface of the rotating substrate W (second organic solvent supplying step, second organic solvent ejecting step, residue removing liquid supplying step). The supply of the organic solvent to the upper surface of the substrate W is continued for a predetermined time, for example, 30 seconds.

[0239] The organic solvent supplied to the upper surface of the substrate W is diffused radially by the centrifugal force and diffuses to the entire upper surface of the substrate W. Thus, the rinsing liquid on the upper surface of the substrate W is replaced by the organic solvent. The organic solvent supplied to the upper surface of the substrate W dissolves the residue of the process film 100 remaining on the upper surface of the substrate W and is then discharged from the periphery of the upper surface of the substrate W (residue removal step). Thus, the residue of the process film 100 is removed from the upper surface of the substrate W, and the upper surface of the substrate W can be cleaned well.

[0240] Thus, in the second organic solvent supplying step, the organic solvent functions as a dissolving liquid for dissolving the residue of the processing film 100 on the upper surface of the substrate W. In addition, the central nozzle 14 functions as a dissolving liquid supplying unit for dissolving the dissolving liquid onto the upper surface of the substrate W.

[0241] Next, a spin drying process is performed (step S12 ). By performing the spin drying process, the upper surface and the lower surface of the substrate W are dried.

[0242] Specifically, the organic solvent valve 56 is closed. Thus, the supply of the organic solvent to the upper surface of the substrate W is stopped. Fig.6I As shown in FIG. 1 , the opposing member lifting unit 61 moves the opposing member 6 to a drying position below the processing position. When the opposing member 6 is located at the drying position, the distance between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 55 is opened. Thus, gas is supplied to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6.

[0243] Then, the rotation motor 23 accelerates the rotation of the substrate W and rotates the substrate W at a high speed. The substrate W in the spin drying process rotates at a drying speed, for example, 1500 rpm. The spin drying process is continuously performed for a predetermined time, for example, 30 seconds. As a result, a large centrifugal force acts on the organic solvent on the substrate W, and the organic solvent on the substrate W is thrown out to the periphery of the substrate W. In the spin drying process, gas is supplied to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6, thereby promoting the evaporation of the organic solvent.

[0244] Then, the rotation motor 23 stops the rotation of the substrate W. The shield lift unit 74 moves the first shield 71A and the second shield 71B to the lower position. The gas valve 55 is closed. Then, the opposing member lift unit 61 moves the opposing member 6 to the upper position.

[0245] The transfer robot CR enters the processing unit 2, lifts the processed substrate W from the chuck pins 20 of the spin chuck 5, and carries it out of the processing unit 2 (step S13). The substrate W is transferred from the transfer robot CR to the transfer robot IR, and is stored in the carrier C by the transfer robot IR.

[0246] Next, refer to Figure 7A to Figure 7C , describing changes in the situation near the upper surface of the substrate W when the processing film 100 is removed from the substrate W when both the protective liquid and the removing liquid are pure water.

[0247] Fig. 7A The state near the upper surface of the substrate W is shown immediately after the solid forming step (step S7) is completed. Figure 7B The state of the upper surface of the substrate W immediately after the protective liquid film forming step (step S8) is shown. Figure 7C The state near the upper surface of the substrate W during the removal step (step S9) is shown.

[0248] In the solid forming step (step S7) performed in the process film forming step, as described above, the liquid film 101 on the upper surface of the substrate W is heated by the heat medium via the substrate W. At least a part of the solvent evaporates, so that Fig. 7AAs shown, a processing film 100 holding removal objects 103 such as particles is formed.

[0249] The film thickness T of the processing film 100 is about several tens of nm (for example, 30 nm). The film thickness T of the processing film 100 is the thickness of the processing film 100 at a location where the removal object 103 does not exist. The removal objects 103 of various sizes are attached to the upper surface of the substrate W. Fig. 7A The removal objects 103 of three sizes are shown.

[0250] On the substrate W, there may be a first removal object 103A having a radius R larger than the film thickness T of the process film 100 and a second removal object 103B having a radius smaller than the film thickness T of the process film 100 .

[0251] In the aforementioned processing liquid supplying step, the processing liquid enters between the second removal object 103B and the upper surface of the substrate W. Therefore, the solid of the solute enters between the second removal object 103B and the upper surface of the substrate W. The second removal object 103B is firmly held by the processing film 100 .

[0252] On the other hand, in the aforementioned processing liquid supplying step, the processing liquid may not smoothly enter the space between the first removal object 103A and the upper surface of the substrate W below the height position of the center of the first removal object 103A.

[0253] The height of the center of the first removal object 103A corresponds to the radius of the first removal object 103A. The space below the height position of the center of the first removal object 103A is also the space below the horizontal section passing through the center of the first removal object 103A.

[0254] In this case, there is a case where a cavity 104 is formed between the first removal object 103A and the upper surface of the substrate W. Alternatively, even if the processing liquid enters a space below the height position of the center of the first removal object 103A between the first removal object 103A and the upper surface of the substrate W, the processing liquid may form the cavity 104 when solidified. In any of the above cases, the holding force of the processing film 100 holding the first removal object 103A is smaller than the holding force of the processing film 100 holding the second removal object 103B.

[0255] Furthermore, by supplying the protective liquid to the upper surface of the substrate W in the protective liquid film forming step, Figure 7B As shown, a protective liquid film 105 covering the processing film 100 is formed on the upper surface of the substrate W.

[0256] Then, in a state where the protective liquid film 105 is formed on the upper surface of the substrate W, Figure 7CAs shown, by supplying droplets 106 of the removal solution in the removal step, the physical force of the droplets 106 acts on the process film 100 and the removal object 103. By the physical force of the droplets 106 acting on the process film 100, the process film 100 is split and becomes a film sheet 107, and the film sheet 107 is peeled off from the upper surface of the substrate W (process film splitting step, process film peeling step).

[0257] The second removal object 103B is firmly held by the film sheet 107 of the process film 100. Therefore, the second removal object 103B is pulled by the film sheet 107 of the process film 100 and is peeled off from the substrate W when the process film 100 is peeled off.

[0258] Since the first removal object 103A is not held by the processing film 100 with sufficient holding force, there is a case where the adhesive force to the substrate W is greater than the holding force of the processing film 100. In this case, the processing film 100 cannot remove the first removal object 103A from the upper surface of the substrate W. However, the physical force of the droplets 106 of the removal liquid directly acts on the removal object 103. Therefore, the first removal object 103A can be peeled off from the upper surface of the substrate W (removal object peeling step).

[0259] When the process film 100 is split, a plurality of cracks are formed in the process film 100. The so-called crack is a long and narrow groove, and the crack becomes the base point of the splitting of the process film 100. Depending on the formation position of the crack, the second removal object 103B having a radius smaller than the film thickness T of the process film 100 may be separated from the process film 100. In such a case, the second removal object 103B is also peeled off from the upper surface of the substrate W due to the physical force of the droplet 106 of the removal solution acting on the second removal object 103B.

[0260] In this manner, the removal object 103 can be peeled off from the upper surface of the substrate W regardless of the holding force of the processing film 100 on the removal object 103 .

[0261] Then, by continuously supplying the removal liquid, the process film 100 converted into the film piece 107 is washed away (pushed outward from the substrate W) while holding the second removal object 103B, and is removed from the upper surface of the substrate W (removal step).

[0262] The first removal object 103A not sufficiently held by the processing film 100 and the second removal object 103B separated from the processing film 100 are also washed away (pushed out of the substrate W) by the continuous supply of the removal liquid and removed from the upper surface of the substrate W (removal step).

[0263] According to the first embodiment, the processing liquid supplied to the upper surface of the substrate W is solidified or hardened, thereby forming the processing film 100 holding the removal object 103 on the upper surface of the substrate (processing film forming step). Thereafter, the removal liquid is supplied in the form of droplets to the upper surface of the substrate W. Thus, the physical force of the droplets 106 of the removal liquid acts on the processing film 100 and the removal object 103.

[0264] Specifically, the physical force of the droplets 106 of the removal solution is applied to the process film 100, so that the process film 100 with the removal object 103 still thereon is split and peeled off from the upper surface of the substrate W, and is removed from the upper surface of the substrate W (process film removal step). Furthermore, the physical force of the droplets 106 of the removal solution is applied to the removal object 103, so that the removal object 103 is removed from the upper surface of the substrate W (removal object removal step).

[0265] Therefore, the physical force of the removal liquid droplets 106 can be applied to the process film 100 , so that most of the removal objects 103 (second removal objects 103B) can be removed from the upper surface of the substrate W together with the process film 100 .

[0266] Furthermore, by causing the physical force of the removal liquid droplet 106 to act on the removal object, the first removal object 103A that is not held by a sufficient holding force on the processing film 100 and the second removal object 103B that is separated from the processing film 100 can also be removed from the upper surface of the substrate W. That is, even when the film thickness T of the processing film 100 is smaller than the radius R of the first removal object 103A, the first removal object 103A can be sufficiently removed from the upper surface of the substrate W.

[0267] As a result, the object 103 can be removed from the upper surface of the substrate W efficiently.

[0268] The physical force from the droplets 106 of the removing solution acting on the upper surface of the substrate W is particularly large in the supply region S. Therefore, due to the physical force from the droplets 106 of the removing solution acting on the upper surface of the substrate W, the concavo-convex pattern formed in the supply region S may collapse.

[0269] In the first embodiment, the supply region S is covered with the protective liquid film 105 before the removal process starts. By appropriately reducing the physical force acting on the supply region S from the droplets 106 of the removal liquid, the physical force of the droplets 106 of the removal liquid can be dispersed over the entire upper surface of the substrate W. Thus, the processing film 100 and the removal object 103 can be removed from the upper surface of the substrate W while protecting the concavo-convex pattern formed on the upper surface of the substrate W.

[0270] The physical force acting on the upper surface of the substrate W when a continuous flow of liquid is supplied to the upper surface of the substrate W is much smaller than the physical force acting on the upper surface of the substrate W when droplets are supplied to the upper surface of the substrate W. Therefore, if the protective liquid is supplied to the upper surface of the substrate W in a continuous flow, the collapse of the concave-convex pattern formed on the upper surface of the substrate W caused by the supply of the protective liquid can be suppressed or prevented.

[0271] In the first embodiment, during the period in which the removal liquid is supplied to the upper surface of the substrate W in the form of droplets in the removal process, the protection liquid is supplied to the upper surface of the substrate W in a continuous flow (protection liquid parallel supply process). Therefore, the protection liquid film 105 can be maintained even during the execution of the removal process. As a result, the physical force acting on the supply region S from the droplets 106 of the removal liquid is appropriately reduced, and the physical force of the droplets 106 of the removal liquid can be dispersed to the entire upper surface of the substrate W. As a result, the processing film 100 and the removal object 103 can be removed from the upper surface of the substrate W while protecting the concavo-convex pattern formed on the upper surface of the substrate W.

[0272] In addition, pure water has a higher surface tension than an alkaline aqueous solution such as SC1. Therefore, when pure water is used as the removal liquid, a greater physical force can be applied to the treatment film 100 than when an alkaline aqueous solution such as SC1 is used as the removal liquid.

[0273] When the removal liquid is water, the process film 100 is less likely to be dissolved than when the removal liquid is an alkaline liquid. Therefore, physical force can be applied to the process film 100 while the number of removal objects 103 held on the process film 100 is as large as possible. When the protection liquid is water, the process film 100 is less likely to be dissolved than when the protection liquid is an alkaline liquid, so it is easy to maintain the process film 100 with the removal objects 103 held.

[0274] When both the protective liquid and the removal liquid are pure water (see Figure 7A to Figure 7C ), when pure water is used as the removing liquid and an alkaline aqueous solution such as SC1 liquid is used as the protecting liquid, in the protecting liquid film forming step (step S8), the protecting liquid supplied to the upper surface of the substrate W partially dissolves the processing film 100 to reduce the strength of the processing film 100. The partial dissolution of the processing film 100 means that the processing film 100 is dissolved to the extent that cracks are formed in the processing film 100.

[0275] Specifically, if Figure 8As shown, by using the protective liquid supplied to the upper surface of the substrate W in the protective liquid film forming step to partially dissolve the processing film 100, a crack 108 is formed in the processing film 100. As a result, the processing film 100 becomes easy to split. By forming the crack 108, the protective liquid easily reaches the vicinity of the upper surface of the substrate W. Therefore, the protective liquid enters the gap G1 between the processing film 100 and the substrate W, dissolving the surface of the processing film 100. As a result, the processing film 100 becomes easy to peel off from the upper surface of the substrate W.

[0276] Therefore, in the removal step, while the strength of the process film is reduced by the protective liquid, the physical force of the droplets 106 of the removal liquid can be applied to the process film 100. Thus, the process film 100 can be efficiently split and the process film 100 can be efficiently peeled off from the upper surface of the substrate W. As a result, the process film 100 can be efficiently removed from the upper surface of the substrate W.

[0277] exist Figure 8 In the embodiment, the crack 108 penetrates the processed film 100 , but there are also cases where the crack 108 does not penetrate the processed film 100 and causes the processed film 100 to be partially thinned.

[0278] When both the protective liquid and the removal liquid are pure water (see Figure 7A to Figure 7C ), when an alkaline aqueous solution such as SC1 solution is used as the removing solution and pure water is used as the protective solution, the removing solution supplied to the upper surface of the substrate W in a droplet state causes the processed film 100 to be partially dissolved, thereby reducing the strength of the processed film 100.

[0279] Therefore, in the removal step, the strength of the processing film 100 can be reduced by the removal liquid, and at the same time, the physical force of the droplets 106 of the removal liquid can be applied to the processing film 100. Thus, the processing film 100 can be efficiently split and the processing film 100 can be efficiently peeled off from the upper surface of the substrate W. As a result, the processing film 100 can be efficiently removed from the upper surface of the substrate W. In addition, the physical force of the droplets 106 of the removal liquid can be mitigated by the protective liquid.

[0280] When both the protective liquid and the removal liquid are pure water (see Figure 7A to Figure 7C ), when both the removing solution and the protective solution are alkaline aqueous solutions such as SC1 solution, the processed film 100 is partially dissolved and the strength of the processed film 100 is reduced in the protective solution film forming step and the removing step.

[0281] Therefore, in the removal process, while the strength of the processing film 100 is reduced by the protective liquid and the removing liquid, the physical force of the liquid droplets 106 of the removing liquid can be applied to the processing film 100. Thus, the processing film 100 can be efficiently split and the processing film 100 can be efficiently peeled off from the upper surface of the substrate W. As a result, the processing film 100 can be efficiently removed from the upper surface of the substrate W. In addition, the physical force of the liquid droplets 106 of the removing liquid can be mitigated by the protective liquid.

[0282] <Second embodiment>

[0283] In the second embodiment, a substrate processing apparatus having the same structure as the substrate processing apparatus 1 of the first embodiment can be used, and the same substrate processing as that described in the first embodiment can be performed. The main difference between the second embodiment and the first embodiment is that the solute in the processing liquid ejected from the second movable nozzle 9 contains a low-soluble substance and a high-soluble substance.

[0284] The low-soluble substance and the high-soluble substance may have different solubilities with respect to the removing liquid and the protecting liquid.

[0285] The low-soluble substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, novolac. The high-soluble substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane.

[0286] The solvent contained in the processing liquid ejected from the second moving nozzle 9 may be a liquid that dissolves the low-soluble substance and the high-soluble substance. The solvent contained in the processing liquid is preferably a liquid that is compatible with the removing liquid.

[0287] The details of the solvent, the low-soluble substance, and the high-soluble substance contained in the processing liquid ejected from the second moving nozzle 9 will be described later.

[0288] The substrate processing of the second embodiment is different from that of the first embodiment in the vicinity of the upper surface of the substrate W. Figures 9A to 9C , the situation when the processing film is removed from the substrate W in the substrate processing of the second embodiment is described. Figures 9A to 9C In the description, the case where both the removal liquid and the protection liquid are alkaline aqueous solutions is taken as an example.

[0289] Fig. 9A The state near the upper surface of the substrate W is shown immediately after the solid forming step (step S7) is completed. Fig. 9B The state of the upper surface of the substrate W when the processing film 200 is partially dissolved in the protective liquid film forming step (step S8) and the removing step (step S9) is shown. Fig. 9CThe state of the vicinity of the upper surface of the substrate W when a physical force acts on the processing film 200 in the removal step (step S9 ) is shown.

[0290] In the solid forming step, as described above, the liquid film 101 of the processing liquid on the substrate W is heated by the heat medium via the substrate W. Fig. 9A As shown, a processing film 200 holding the removal objects 103 such as particles is formed.

[0291] Specifically, at least a portion of the solvent evaporates, so that the high-soluble substance contained in the solute of the treatment liquid forms a high-soluble solid 210 (a high-soluble substance in a solid state). In addition, at least a portion of the solvent evaporates, so that the low-soluble substance contained in the solute of the treatment liquid forms a low-soluble solid 211 (a low-soluble substance in a solid state). The low-soluble substance and the high-soluble substance are film-formed together.

[0292] "Membraning together" does not mean that the low-soluble substance and the high-soluble substance form independent layers. One form of "membraning" is "solidification" or "hardening".

[0293] The process film 200 contains a mixture of high-soluble solids 210 and low-soluble solids 211. The high-soluble solids 210 and low-soluble solids 211 are not uniformly distributed throughout the process film 200, but there are portions where the high-soluble solids 210 are concentrated and portions where the low-soluble solids 211 are concentrated. In the process film 200, there is also a case where a cavity 104 is formed between the first removal object 103A and the upper surface of the substrate W.

[0294] By using the protective liquid supplied to the upper surface of the substrate W in the protective liquid film forming step (step S8) and the removing liquid supplied to the upper surface of the substrate W in the removing step (step S9), as shown in FIG. Fig. 9B As shown, the highly soluble solid 210 is selectively dissolved. That is, the process film 200 is partially dissolved. As the highly soluble solid 210 is dissolved, a through hole 202 is formed in the process film 200 at a portion where the highly soluble solid 210 is localized (through hole forming step). The through hole 202 is particularly likely to be formed in a portion where the highly soluble solid 210 extends in the thickness direction D of the substrate W (also the thickness direction of the process film 200). The through hole 202 has a diameter of, for example, several nanometers when viewed from above.

[0295] The protective liquid and the removal liquid reach the vicinity of the upper surface of the substrate W through the through hole 202. The low-soluble solid 211 is slightly dissolved in the alkaline aqueous solution. Therefore, a small amount of the low-soluble solid 211 is dissolved near the upper surface of the substrate W. Fig. 9BAs shown in the enlarged view, the protective liquid and the removing liquid enter the gap G2 between the processing film 200 and the upper surface of the substrate W while gradually dissolving the low-soluble solid 211 near the upper surface of the substrate W (removing liquid entering process, protective liquid entering process).

[0296] Finally, the treated film 200 is split into film pieces 207 starting from the periphery of the through hole 202 due to the physical force of the liquid droplet 106 of the removal liquid. Fig. 9C As shown, the film sheet 207 of the processing film 200 is peeled off from the substrate W while retaining the removal object 103 (splitting step, processing film peeling step). At the same time, the removal object 103 is peeled off from the upper surface of the substrate W by the physical force of the droplet 106 of the removal liquid (removal object peeling step). Therefore, even if the first removal object 103A having a radius R larger than the film thickness T of the processing film 200 exists on the upper surface of the substrate W, the first removal object 103A is peeled off from the upper surface of the substrate W.

[0297] When the processing film 200 is partially dissolved, the second removal object 103B held by the portion where the highly soluble solid 210 is localized in the processing film 200 may be separated from the processing film 200. Even in such a case, the second removal object 103B is peeled off from the upper surface of the substrate W due to the physical force of the droplets 106 of the removal solution acting on the second removal object 103B.

[0298] Then, by continuously supplying the removal liquid, the processing film 200 converted into the membrane 207 is washed away (pushed to the outside of the substrate W) while retaining the second removal object 103B, and is removed from the upper surface of the substrate W (removal step).

[0299] The first removal objects 103A not sufficiently held by the processing film 200 and the second removal objects 103B separated from the processing film 200 are also washed away (pushed out of the substrate W) by the continuous supply of the removal liquid and removed from the upper surface of the substrate W (removal step).

[0300] When one of the protective liquid and the removing liquid is pure water, the removal of the processing film 200 from the substrate W is different from the case where both the protective liquid and the removing liquid are alkaline aqueous solutions (see Figures 9A to 9C ) are slightly different.

[0301] Specifically, when the protective liquid is an alkaline aqueous solution and the removing liquid is pure water, the highly soluble solid 210 is dissolved in the protective liquid, while the treatment film 200 is hardly dissolved in the removing liquid. When the protective liquid is pure water and the removing liquid is an alkaline aqueous solution, the highly soluble solid 210 is dissolved in the removing liquid, while the treatment film 200 is hardly dissolved in the protective liquid.

[0302] The second embodiment has the same effects as those of the first embodiment.

[0303] Furthermore, according to the second embodiment, the high-solubility solid 210 in the solid state in the processing film 200 is selectively dissolved by at least one of the protective liquid and the removal liquid. Therefore, the strength of the processing film 200 is reduced. On the other hand, the low-solubility solid 211 in the processing film 200 is maintained in a solid state with the removal object 103. Therefore, the physical force of the droplet 106 of the removal liquid can be applied to the processing film 200 in the removal process while the removal object 103 is still retained in the processing film 200 and the strength of the processing film 200 is reduced. As a result, the processing film 200 is efficiently split and the processing film 200 is efficiently peeled off from the surface of the substrate.

[0304] However, in this case, since the processing film 200 is hardly dissolved in the protective liquid and the removing liquid, it is broken apart and peeled off from the upper surface of the substrate W basically only by the physical force of the droplets 106 of the removing liquid.

[0305] <Details of the treatment liquid used in the second embodiment>

[0306] Hereinafter, each component in the processing liquid used in the second embodiment will be described.

[0307] Below, "C x～y ”, “C x ~C y ” and “C x " indicates the number of carbon atoms in a molecule or substituent. For example, C 1～6 The alkyl group represents an alkyl chain having 1 or more and 6 or less carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0308] In the case where the polymer has multiple repeating units, these repeating units are copolymerized. Unless otherwise specified, the above copolymerization can be any one of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization or the presence of these at the same time. When the polymer or resin is represented by a structural formula, n, m, etc. marked together with the brackets represent the number of repetitions.

[0309] The same also applies to the description of each component in the processing liquid, the removing liquid, and the protecting liquid in the third embodiment described later.

[0310] <Low soluble substances>

[0311] (A) The low-solubility substance contains at least one of phenolic varnish, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonates, polyvinyl alcohol derivatives, polymethacrylic acid derivatives and copolymers thereof. Preferably, (A) the low-solubility substance may also contain at least one of phenolic varnish, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonates, polymethacrylic acid derivatives and copolymers thereof. More preferably, (A) the low-solubility substance may also contain at least one of phenolic varnish, polyhydroxystyrene, polycarbonates and copolymers thereof. The phenolic varnish may also be a phenolic novolac.

[0312] The treatment liquid may contain one or a combination of two or more of the above-mentioned preferred examples as the (A) low-soluble substance. For example, the (A) low-soluble substance may contain both novolac and polyhydroxystyrene.

[0313] A preferred embodiment is that the (A) low-solubility substance is formed into a film by drying, and the film is mostly not dissolved by the removal liquid, but is peeled off with the object to be removed being retained. It should be noted that a very small part of the (A) low-solubility substance is allowed to be dissolved by the removal liquid.

[0314] The (A) low-soluble substance preferably contains no fluorine and / or silicon, and more preferably contains no fluorine and / or silicon.

[0315] The copolymerization is preferably random copolymerization or block copolymerization.

[0316] Although not intending to limit the scope of the claims, specific examples of the (A) low-solubility substance include compounds represented by the following Chemical Formulas 1 to 7.

[0317] [Chemical formula 1]

[0318]

[0319] [Chemical formula 2]

[0320]

[0321] [Chemical formula 3]

[0322]

[0323] (The asterisk * indicates a bond to an adjacent structural unit.)

[0324] [Chemical formula 4]

[0325]

[0326] (R means C 1～4alkyl and other substituents. The asterisk * indicates a bond to an adjacent structural unit.)

[0327] [Chemical formula 5]

[0328]

[0329] [Chemical formula 6]

[0330]

[0331] [Chemical formula 7]

[0332]

[0333] (Me represents methyl.)

[0334] The weight average molecular weight (Mw) of the (A) low-soluble substance is preferably 150 to 500,000, more preferably 300 to 300,000, further preferably 500 to 100,000, and further preferably 1,000 to 50,000.

[0335] (A) The low-soluble substance can be obtained by synthesis. Alternatively, it can be purchased. In the case of purchase, for example, the supplier is as follows. The (A) polymer can also be synthesized by the supplier.

[0336] Novolac: Showa Chemical Industry Co., Ltd., Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0337] Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd.

[0338] Polyacrylic acid derivatives: Nippon Shokubai Co., Ltd.

[0339] Polycarbonate: Sigma-Aldrich

[0340] Polymethacrylic acid derivatives: Sigma-Aldrich

[0341] A) The low-soluble substance is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 1 to 10% by mass compared to the total mass of the treatment liquid. That is, the total mass of the treatment liquid is set to 100 mass%, and based on this, (A) The low-soluble substance is 0.1 to 50% by mass. That is, "compared to..." can be replaced by "based on...". Unless otherwise specified, the following is the same.

[0342] Solubility can be evaluated by a known method. For example, under the conditions of 20°C to 35°C (more preferably 25±2°C), 100 ppm of the aforementioned (A) or the following (B) is added to 5.0% by mass ammonia water in a flask, the lid is covered, and the mixture is vibrated with a vibrator for 3 hours to determine whether (A) or (B) has dissolved. Vibration may also be stirring. Dissolution can also be visually determined. If it is not dissolved, the solubility is less than 100 ppm, and if it is dissolved, the solubility is greater than 100 ppm. A solubility of less than 100 ppm is defined as insoluble or poorly soluble, and a solubility of more than 100 ppm is defined as soluble. In a broad sense, soluble includes slightly soluble. Solubility decreases in the order of insoluble, poorly soluble, and soluble. In a narrow sense, the solubility of slightly soluble is lower than that of soluble and higher than that of poorly soluble.

[0343] <Highly soluble substances>

[0344] (B) The highly soluble substance is (B') a crack promoting component. (B') The crack promoting component contains hydrocarbons, and further contains hydroxyl groups (-OH) and / or carbonyl groups (-C(=O)-). When (B') The crack promoting component is a polymer, one of the structural units contains hydrocarbons per unit, and further has hydroxyl groups and / or carbonyl groups. Examples of the carbonyl group include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, and carboxylic acids are preferred.

[0345] It is not intended to limit the scope of the rights. In theory, when the treatment liquid is dried and a treatment film is formed on the substrate, and the removal liquid peels off the treatment film, the (B) highly soluble substance forms a portion that becomes the starting point of the treatment film peeling. Therefore, it is preferred that the (B) highly soluble substance has a higher solubility in the removal liquid than the (A) low soluble substance. As the (B') crack promoting component, a cyclic hydrocarbon can be cited as a method of containing a ketone as a carbonyl group. As specific examples, 1,2-cyclohexanedione and 1,3-cyclohexanedione can be cited.

[0346] As a more specific embodiment, (B) the highly soluble substance is represented by at least one of the following (B-1), (B-2) and (B-3).

[0347] (B-1) is a compound comprising 1 to 6 (preferably 1 to 4) of the following chemical formula 8 as structural units, wherein each structural unit is bonded via a linking group (linker L1). 1～6 At least one of the alkylene groups. 1～6 The alkylene group serves as a linker to connect the structural units and is not limited to a divalent group. It is preferably a divalent to tetravalent group. 1～6 The alkylene group may be either a linear chain or a branched chain.

[0348] [Chemical formula 8]

[0349]

[0350] Cy1 is C 5～30 The hydrocarbon ring is preferably phenyl, cyclohexane or naphthyl, and more preferably phenyl. As a preferred embodiment, the linker L1 connects a plurality of Cy1.

[0351] R1 is each independently C 1～5 The alkyl group is preferably a methyl group, an ethyl group, a propyl group or a butyl group. 1～5 The alkyl group may be either a linear chain or a branched chain.

[0352] n b1 is 1, 2 or 3, preferably 1 or 2, and more preferably 1. b1’ It is 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0353] The following Chemical Formula 9 is a chemical formula obtained by using a linker L9 to represent the structural unit represented by Chemical Formula 8. The linker L9 is preferably a single bond, a methylene group, an ethylene group, or a propylene group.

[0354] [Chemical formula 9]

[0355]

[0356] Although not intended to limit the scope of the invention, preferred examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalene diol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These substances can also be obtained by polymerization or condensation.

[0357] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol represented by the following chemical formula 10 is used for illustration. This compound has three structural units of the chemical formula 8 in (B-1), and the structural units are bonded by L1 (methylene). b1 =n b1’ =1, R1 is methyl.

[0358] [Chemical formula 10]

[0359]

[0360] (B-2) is represented by the following chemical formula 11.

[0361] [Chemical formula 11]

[0362]

[0363] R 21 , R 22 , R 23 and R 24 are independently hydrogen or C 1～5 The alkyl group is preferably hydrogen, methyl, ethyl, tert-butyl or isopropyl, more preferably hydrogen, methyl or ethyl, further preferably methyl or ethyl.

[0364] L 21 and L 22 Each independently is C 1～20 Alkylene, C 1～20 Cycloalkylene, C 2～4 Alkenylene, C 2～4 Alkyne or C 6～20 These groups can also be represented by C 1～5 Here, alkenylene represents one or more divalent hydrocarbons having double bonds, and alkynylene represents one or more divalent hydrocarbons having triple bonds. 21 and L 22 C 2～4 alkylene, ethynylene (C2 alkynylene) or phenylene, more preferably C 2～4 An alkylene group or an ethynylene group, and an ethynylene group is more preferable.

[0365] n b2 It is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

[0366] Although not intended to limit the scope of the claims, preferred examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, 3-hexyne-2,5-diol, 1,4-butyne diol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol can also be mentioned as preferred examples of (B-2).

[0367] (B-3) is a polymer containing a structural unit represented by the following Chemical Formula 12 and having a weight average molecular weight (Mw) of 500 to 10000. Preferably, Mw is 600 to 5000, and more preferably 700 to 3000.

[0368] [Chemical formula 12]

[0369]

[0370] Here, R 25It is -H, -CH3 or -COOH, preferably -H or -COOH. It is also acceptable for one (B-3) polymer to contain two or more structural units respectively represented by Chemical Formula 12.

[0371] Although not intended to limit the scope of the claims, preferred examples of the polymer (B-3) include acrylic acid, maleic acid, polymers of acrylic acid or a combination thereof, and polyacrylic acid and maleic acid acrylic acid copolymers are further preferred examples.

[0372] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0373] As an example, a maleic acid acrylic acid copolymer represented by the following chemical formula 13 is used for illustration. The copolymer is contained in (B-3) and has two structural units represented by chemical formula 12. In one structural unit, R 25 is -H, in another structural unit, R 25 It is -COOH.

[0374] [Chemical formula 13]

[0375]

[0376] It goes without saying that the treatment liquid may contain one or a combination of two or more of the above-mentioned preferred examples as the highly soluble substance (B). For example, the highly soluble substance (B) may contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0377] The molecular weight of the highly soluble substance (B) may be 80 to 10000. The molecular weight of the highly soluble substance is preferably 90 to 5000, and more preferably 100 to 3000. When the highly soluble substance (B) is a resin, a polymer (Japanese: polymer) or a polymer (Japanese: polymer), the molecular weight is expressed as a weight average molecular weight (Mw).

[0378] (B) Highly soluble substances can be synthesized or purchased. Examples of suppliers include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

[0379] In the treatment liquid, the amount of the highly soluble substance (B) is preferably 1 to 100% by mass, more preferably 1 to 50% by mass, compared to the amount of the low soluble substance (A). In the treatment liquid, the amount of the highly soluble substance (B) is more preferably 1 to 30% by mass, compared to the amount of the low soluble substance (A).

[0380] <Solvent>

[0381] Preferably, the (C) solvent contains an organic solvent. The (C) solvent may also be volatile. Volatile means that it is more volatile than water. For example, the boiling point of the (C) solvent at 1 atmosphere is preferably 50 to 250°C. More preferably, the boiling point of the solvent at 1 atmosphere is 50 to 200°C, and more preferably 60 to 170°C. Still more preferably, the boiling point of the solvent at 1 atmosphere is 70 to 150°C. The (C) solvent is also allowed to contain a small amount of pure water. Preferably, the pure water contained in the (C) solvent is 30% by mass or less compared to the (C) solvent as a whole. More preferably, the pure water contained in the solvent is 20% by mass or less, and still more preferably 10% by mass or less. Still more preferably, the pure water contained in the solvent is 5% by mass or less. It is also a preferred embodiment that the solvent does not contain pure water (0% by mass). Preferably, the pure water is DIW.

[0382] As the organic solvent, alcohols such as isopropyl alcohol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid methyl, lactic acid ethyl (EL) and other lactic acid esters, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, lactones such as γ-butyrolactone, etc. These organic solvents can be used alone or in combination of two or more.

[0383] As a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When the organic solvent is a combination of two, the volume ratio is preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

[0384] The total mass of the solvent (C) and the treatment liquid is 0.1 to 99.9 mass %. The total mass of the solvent (C) and the treatment liquid is preferably 50 to 99.9 mass %, more preferably 75 to 99.5 mass %. The total mass of the solvent (C) and the treatment liquid is further preferably 80 to 99 mass %, further preferably 85 to 99 mass %.

[0385] <Other additives>

[0386] The treatment liquid of the present invention may further include (D) other additives. As one embodiment of the present invention, (D) other additives include surfactants, acids, bases, antimicrobial agents, bactericides, preservatives or antifungal agents (preferably surfactants), and may also include any combination of the above substances.

[0387] As one embodiment of the present invention, in the treatment liquid, the mass ratio of (D) other additives (the total in the case of multiple types) to the mass ratio of (A) low-soluble substance is 0 to 100 mass% (preferably 0 to 10 mass%, more preferably 0 to 5 mass%, further preferably 0 to 3 mass%, further preferably 0 to 1 mass%). It is also one embodiment of the present invention that the treatment liquid (D) does not contain other additives (0 mass%).

[0388] <Third embodiment>

[0389] In the third embodiment, a substrate processing apparatus having the same structure as the substrate processing apparatus 1 of the first embodiment can be used, and the same substrate processing as that described in the first embodiment can be performed. The main difference between the third embodiment and the first embodiment is that the solute in the processing liquid ejected from the second movable nozzle 9 includes a low-soluble substance, a high-soluble substance, and a solubility enhancing substance.

[0390] Although described in detail later, in the third embodiment, the removal liquid and the protection liquid are, for example, pure water.

[0391] The solubility enhancing substance is a substance that improves the solubility of the removal solution to dissolve the treated film by dissolving in the removal solution. By dissolving the solubility enhancing substance in the protective solution, the solubility of the protective solution to dissolve the treated film is also improved. The solubility enhancing substance is, for example, a salt (alkali component) that dissolves in the removal solution to show alkalinity.

[0392] As will be described later in detail, the solubility enhancing substance is, for example, a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium salt. When the removal liquid is pure water, the solubility enhancing substance is dissolved from the treatment film into the removal liquid, so that the removal liquid becomes an aqueous solution of the primary amine, the secondary amine, the tertiary amine, and the quaternary ammonium salt, i.e., an alkaline aqueous solution (alkaline liquid). When the removal liquid is an alkaline aqueous solution, the solubility enhancing substance is dissolved from the treatment film into the removal liquid, so that the alkalinity of the removal liquid is enhanced.

[0393] The low-soluble substance and the high-soluble substance can use substances with different solubility in the removal liquid. The low-soluble substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, novolac, and the high-soluble substance contained in the treatment liquid ejected from the second moving nozzle 9 is, for example, 2,2-bis(4-hydroxyphenyl)propane.

[0394] The solvent contained in the treatment liquid ejected from the second moving nozzle 9 may be a liquid that dissolves the low-soluble substance, the high-soluble substance, and the solubility enhancing substance. The solvent contained in the treatment liquid is preferably a liquid that is compatible with the removal liquid.

[0395] The details of the solvent, the low-soluble substance, the high-soluble substance, and the solvency enhancing substance contained in the processing liquid ejected from the second moving nozzle 9 will be described later together with the details of the removing liquid ejected from the third moving nozzle 10 .

[0396] The substrate processing of the third embodiment is different from that of the first embodiment in the vicinity of the upper surface of the substrate W. Figure 10A to Figure 10C , a description is given of a situation in which the processing film 300 is removed from the substrate W when both the removal liquid and the protection liquid are pure water in the substrate processing according to the third embodiment.

[0397] Fig. 10A The state near the upper surface of the substrate W is shown immediately after the solid forming step (step S7) is completed. Fig. 10B The state of the upper surface of the substrate W when the processing film 300 is partially dissolved in the protective liquid film forming step (step S8) and the removing step (step S9) is shown. Fig. 10C The state near the upper surface of the substrate W when a physical force acts on the process film 300 in the removal step (step S9 ) is shown.

[0398] In the solid forming step performed in the process film forming step, as described above, the liquid film 101 on the substrate W is heated by the heat medium via the substrate W. Fig. 10A As shown, a processing film 300 holding the removal object 103 such as particles is formed.

[0399] Specifically, at least a portion of the solvent evaporates, so that the high-soluble substance contained in the solute of the treatment liquid forms a high-soluble solid 310 (high-soluble substance in a solid state), and the low-soluble substance contained in the solute of the treatment liquid forms a low-soluble solid 311 (low-soluble substance in a solid state). At least a portion of the solvent evaporates, so that the solubility enhancing substance contained in the solute of the treatment liquid forms a solubility enhancing solid 312 (solid solubility enhancing substance). The low-soluble substance, the high-soluble substance, and the solubility enhancing substance are all converted into a film.

[0400] In the processing film 300, the high-solubility solid 310, the low-solubility solid 311, and the solubility-enhancing solid 313 are mixed. The high-solubility solid 310, the low-solubility solid 311, and the solubility-enhancing solid 313 are not uniformly distributed throughout the processing film 300, and there are portions where the high-solubility solid 310 is concentrated and portions where the low-solubility solid 311 is concentrated in the processing film 300. The solubility-enhancing solid 312 is formed without omission throughout the processing film 300. In the processing film 300, there is also a case where the cavity 104 is formed between the first removal object 103A and the upper surface of the substrate W.

[0401] like Fig. 10B As shown, the solubility enhancing solid 312 in the processing film 300 is dissolved into the protection liquid supplied to the upper surface of the substrate W in the protection liquid film forming step and the removal liquid supplied to the upper surface of the substrate W in the removal step. The solubility enhancing solid 312 is dissolved in the protection liquid and the removal liquid to form an alkaline aqueous solution. As the protection liquid and the removal liquid become an alkaline aqueous solution, the solubility of the protection liquid and the removal liquid in dissolving the processing film 300 is enhanced, and the processing film 300 is partially dissolved.

[0402] Specifically, the high-soluble solid 310 is dissolved by using the protective liquid and the removing liquid with enhanced dissolving power, that is, the alkaline aqueous solution, so that the through hole 302 is formed in the portion where the high-soluble solid 310 is localized in the processing film 300 (through hole forming step). The through hole 302 is easily formed in the portion where the high-soluble solid 310 extends in the thickness direction D of the substrate W (also the thickness direction of the processing film 300). The through hole 302 has a diameter of, for example, several nanometers when viewed from above.

[0403] The alkaline aqueous solution reaches the vicinity of the upper surface of the substrate W through the through hole 302. A small amount of the low-soluble solid 311 is dissolved in the alkaline aqueous solution. Therefore, a small amount of the low-soluble solid 311 is dissolved near the upper surface of the substrate W. Fig. 10B As shown in the enlarged view of , the alkaline aqueous solution gradually dissolves the low-soluble solid 311 near the upper surface of the substrate W and enters the gap G3 between the processing film 300 and the upper surface of the substrate W (removal liquid entering step, protection liquid entering step).

[0404] In the process film 300, when the highly soluble solid 310 is dissolved in a localized portion, the solubility enhancing solid 312 existing in the portion and the solubility enhancing solid 312 existing in the portion surrounding the through hole 302 in the process film 100 are dissolved by the alkaline aqueous solution. Similarly, the solubility enhancing solid 312 existing in the portion near the upper surface of the substrate W in the process film 300 is dissolved by the protective liquid due to the entry of the protective liquid and the removal liquid into the gap G3. As a result, the concentration of the alkaline component in the alkaline aqueous solution is further increased. Therefore, the peeling of the low soluble solid 311 of the process film 300 is further promoted.

[0405] Finally, the treated film 300 is split into film pieces 307 starting from the periphery of the through hole 302 due to the physical force of the liquid droplet 106 of the removal liquid. Fig. 10C As shown, the film sheet 307 of the processing film 300 is peeled off from the substrate W while retaining the removal object 103 (splitting step, processing film peeling step). At the same time, the removal object 103 is peeled off from the upper surface of the substrate W by the physical force of the droplet 106 of the removal liquid (removal object peeling step). Therefore, even if the first removal object 103A having a radius R larger than the film thickness T of the processing film 300 exists on the upper surface of the substrate W, the first removal object 103A is peeled off from the upper surface of the substrate W.

[0406] When the processing film 300 is partially dissolved, the second removal object 103B held by the portion where the highly soluble solid 310 is localized in the processing film 300 may be separated from the processing film 300. Even in such a case, the second removal object 103B is peeled off from the upper surface of the substrate W by the physical force of the droplet 106 of the removal solution acting on the second removal object 103B.

[0407] Then, by continuously supplying the removal liquid, the processing film 300 converted into the film piece 307 is washed away (pushed to the outside of the substrate W) while holding the second removal object 103B, and is removed from the upper surface of the substrate W (removal step).

[0408] The first removal object 103A not sufficiently held by the processing film 300 and the second removal object 103B separated from the processing film 300 are also washed away (pushed out of the substrate W) by the continuous supply of the removal liquid and removed from the upper surface of the substrate W (removal step).

[0409] The third embodiment achieves the same effects as those of the first embodiment.

[0410] Furthermore, according to the third embodiment, the high-solubility solid 310 in the solid state in the processing film 300 is selectively dissolved by the removal liquid. Therefore, the strength of the processing film 300 is reduced. On the other hand, the low-solubility solid 311 in the processing film 300 is maintained in a solid state with the removal object 103. Therefore, in the state where the processing film 300 still retains the removal object 103 and the strength of the processing film 200 is reduced, the physical force of the droplet 106 of the removal liquid can be applied to the processing film 300 in the removal process. As a result, the processing film 300 is efficiently split and the processing film 300 is efficiently peeled off from the surface of the substrate.

[0411] Furthermore, according to the third embodiment, the solubility enhancing substance is dissolved from the processing film 300 into the protective liquid and the removing liquid, so that the solubility of the protective liquid and the removing liquid to dissolve the processing film 300 is enhanced. Therefore, the processing film 300 is partially dissolved by the protective liquid and the removing liquid. Therefore, even when a liquid with low solubility such as pure water is used as the removing liquid, the physical force of the droplets of the removing liquid can be applied to the processing film 300 while reducing the strength of the processing film 300. Thus, the processing film 300 can be efficiently split and the processing film 300 can be efficiently peeled off from the upper surface of the substrate W. As a result, the processing film 300 can be efficiently removed from the upper surface of the substrate W.

[0412] When an alkaline aqueous solution is used as the removing solution, even if the solubility enhancing substance is dissolved in the removing solution, the degree of enhancement of the solubility of the removing solution is lower than when the removing solution is a non-alkaline aqueous solution. The same is true when an alkaline aqueous solution is used as the protecting solution. That is, even if the solubility enhancing substance is dissolved in the protecting solution, the degree of enhancement of the solubility of the protecting solution is lower than when the protecting solution is a non-alkaline aqueous solution.

[0413] <Details of the Treatment Liquid, Removal Liquid, and Protection Liquid Used in the Third Embodiment>

[0414] Hereinafter, each component in the processing liquid, the removing liquid, and the protecting liquid used in the third embodiment will be described.

[0415] <Low soluble substances>

[0416] As the (A) low-soluble substance, the same substance as the low-soluble substance contained in the treatment liquid used in the second embodiment can be used. Preferably, the weight average molecular weight (Mw) of the (A) low-soluble substance used in the third embodiment is 150 to 500,000. The (A) low-soluble substance used in the third embodiment is 0.1 to 50% by mass compared to the total mass of the treatment liquid. In other words, the total mass of the treatment liquid is set to 100% by mass, and based on this, the (A) low-soluble substance used in the third embodiment is 0.1 to 50% by mass.

[0417] <Solubility enhancing substances>

[0418] The solubility enhancing substance (B) comprises at least one of a primary amine, a secondary amine, a tertiary amine and a quaternary ammonium salt (preferably a primary amine, a secondary amine and a tertiary amine), and the solubility enhancing substance (B) comprises a hydrocarbon. As a preferred embodiment, the solubility enhancing substance (B) remains in the treatment film 100 formed from the treatment liquid, and when the treatment film is peeled off by the removal liquid, the solubility enhancing substance (B) is dissolved into the removal liquid (F). Therefore, it is preferred that the boiling point of the alkaline component (B) at 1 atmosphere is 20 to 400°C.

[0419] Although the type of the solubility enhancing substance is not intended to be limited, preferred examples of (B) include N-benzylethanolamine, diethanolamine, monoethanolamine, 2-(2-aminoethylamino)ethanol, 4,4'-diaminodiphenylmethane, 2-(butylamino)ethanol, 2-anilinoethanol, triethanolamine, ethylenediamine, diethylenetriamine, tris(2-aminoethyl)amine, and tris[2-(dimethylamino)ethyl]amine.

[0420] Although the type of the solubility enhancing substance is not intended to be limited, preferred examples of (B) include N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and N,N,N',N'-tetraethylethylenediamine.

[0421] Although the type of the solubility enhancing substance is not intended to be limited, specific examples of (B) having a cage-type three-dimensional structure include 1,4-diazabicyclo[2.2.2]octane and hexamethylenetetramine. Although the present invention is not intended to be limited, preferred examples of (B) having a planar ring structure include 1,4,7,10-tetraazacyclododecane and 1,4,7,10,13,16-hexaazacyclooctadecane.

[0422] It goes without saying that, in the treatment liquid of the present invention, as the (B) solubility enhancing substance, it is also possible to include one or a combination of two or more of the above-mentioned preferred examples. For example, the (B) solubility enhancing substance may also include both N-benzylethanolamine and diethanolamine. In addition, the (B) solubility enhancing substance may also include both N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and 1,4-diazabicyclo[2.2.2]octane.

[0423] The molecular weight of the solubility enhancing substance (B) is preferably 50-500.

[0424] (B) The solubility enhancing substance can be synthesized or purchased. Examples of suppliers include Sigma-Aldrich and Tokyo Chemical Industry.

[0425] As one embodiment of the present invention, the mass ratio of the solubility enhancing substance (B) to the low-solubility substance (A) in the treatment liquid is preferably 1 to 100 mass %.

[0426] <Solvent>

[0427] Preferably, the (C) solvent contains an organic solvent. The (C) solvent is volatile. Volatile means that it is more volatile than water. Preferably, the boiling point of the (C) solvent at 1 atmosphere is 50 to 200°C. It is also allowed that the (C) solvent contains a small amount of pure water. Preferably, the pure water contained in the (C) solvent is 30% by mass or less compared to the (C) solvent as a whole. Not containing pure water (0% by mass) is also a preferred embodiment. Preferably, the pure water is DIW.

[0428] As a preferred embodiment of the present invention, the components (including additives) contained in the treatment liquid are dissolved in the (C) solvent. The treatment liquid using this embodiment is considered to have good embedding performance and film uniformity.

[0429] As the organic solvent contained in (C), alcohols such as isopropyl alcohol (IPA), ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactic acid methyl, lactic acid ethyl (EL) and other lactic acid esters, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, lactones such as γ-butyrolactone, etc. These organic solvents can be used alone or in combination of two or more.

[0430] As a preferred embodiment, the organic solvent contained in the solvent (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When the organic solvent is a combination of two, the volume ratio thereof is preferably 20:80 to 80:20.

[0431] (C) The solvent is 0.1 to 99.9% by mass based on the total mass of the treatment liquid.

[0432] <Highly soluble substances>

[0433] (D) The highly soluble substance contains hydrocarbons and further contains hydroxyl groups (-OH) and / or carbonyl groups (-C(=O)-). When the highly soluble substance (D) is a polymer, one of the structural units contains hydrocarbons and further contains hydroxyl groups and / or carbonyl groups per unit. Examples of the carbonyl group include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, and carboxylic acids are preferred.

[0434] As described above, the treatment liquid is dried, and the (D) highly soluble substance remains in the treatment film formed on the substrate. When the (F) removal liquid peels off the treatment film, the (D) highly soluble substance forms the portion where the treatment film peeling starts. Therefore, as the (D) highly soluble substance, it is preferred to use a substance that has a higher solubility in the (F) removal liquid than the (A) low soluble substance.

[0435] Examples of the highly soluble substance (D) that contains a ketone as a carbonyl group include cyclic hydrocarbons, and specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0436] Although not intended to limit the scope of the invention, preferred examples of (D) 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-naphthalene diol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These substances can also be obtained by polymerization or condensation.

[0437] Although not intended to limit the scope of the claims, preferred examples of (D) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. In another embodiment, 3-hexyne-2,5-diol, 1,4-butyne diol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol can also be mentioned as preferred examples of (D).

[0438] Although not intended to limit the scope of the invention, preferred examples of the polymer (D) include polymers of acrylic acid, maleic acid, or a combination thereof. Polyacrylic acid and maleic acid acrylic acid copolymers are further preferred examples.

[0439] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0440] It goes without saying that as (D) a highly soluble substance, the treatment liquid may also contain one or a combination of two or more of the above preferred examples. For example, (D) a highly soluble substance may also contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0441] The molecular weight of the highly soluble substance (D) is, for example, 80 to 10000. When the highly soluble substance (D) is a resin, a polymer or a polymer, the molecular weight is represented by a weight average molecular weight (Mw).

[0442] (D) Highly soluble substances can be synthesized or purchased. Examples of suppliers include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

[0443] As one embodiment of the present invention, the mass ratio of the (D) highly soluble substance to the (A) low soluble substance in the treatment liquid is preferably 1 to 100% by mass.

[0444] <Other additives>

[0445] The treatment liquid of the present invention may further contain (E) other additives. (E) Other additives may also include surfactants, antimicrobial agents, bactericides, preservatives, antifungal agents or alkalis (preferably surfactants), or any combination thereof.

[0446] The amount of (E) other additives (or the total amount thereof if there are two or more) is preferably 0 to 10% by mass relative to the mass of (A) low-soluble substance in the treatment liquid. The treatment liquid may not contain (E) other additives (0% by mass).

[0447] <Removal liquid, protection liquid>

[0448] The (F) removal solution and the protective solution are preferably neutral or weakly acidic. The (F) removal solution and the protective solution preferably have a pH of 4 to 7, more preferably 5 to 7, and even more preferably 6 to 7. In order to avoid the influence of dissolved carbon dioxide in the air, the pH is preferably measured in a degassed manner.

[0449] It is preferred that the (F) removal solution and the protective solution contain pure water. As described above, since the treatment solution of the present invention contains the (B) solubility enhancing substance, the substance is eluted into the (F) removal solution and the protective solution to increase the pH of the (F) removal solution and the protective solution, thereby enhancing the solubility of the removal solution and the protective solution. Therefore, the (F) removal solution and the protective solution may be mostly pure water.

[0450] The pure water contained in (F) is preferably 80 to 100 mass % relative to the total mass of the removing solution (F), more preferably 90 to 100 mass %, further preferably 95 to 100 mass %, and further preferably 99 to 100 mass %. It is also preferred that the removing solution (F) consists only of pure water (100 mass %).

[0451] The pure water contained in the protective solution preferably accounts for 80 to 100 mass %, more preferably 90 to 100 mass %, further preferably 95 to 100 mass %, and further preferably 99 to 100 mass % of the total mass of the protective solution. It is also preferred that the protective solution consists only of pure water (100 mass %).

[0452] <Other embodiments>

[0453] The present invention is not limited to the above-described embodiments, and can be implemented in other forms.

[0454] For example, the protective liquid film forming step (step S8) may be omitted, which is different from the substrate processing in the above-mentioned embodiment. In this case, in the removal step (step S9), Fig.11 As shown, the removal liquid is supplied from the third moving nozzle 10 to the unprotected surface of the processing film 100, and the protection liquid is supplied from the fourth moving nozzle 11. In this case, since the protection liquid film 105 is not formed before the removal liquid in the droplet state is supplied, the substrate processing time can be shortened.

[0455] In addition, the protection liquid parallel supply process can also be omitted in the removal process (step S9). In this case, in the removal process (step S9), Fig.12 As shown, the removal liquid is supplied from the third moving nozzle 10 to the process film 100 whose surface is protected by the protection liquid film 105 , but the protection liquid is not supplied from the fourth moving nozzle 11 .

[0456] At the start of the removal process, the protective liquid film 105 is sufficiently held on the upper surface of the substrate W. Therefore, at the start of the removal process, the physical force acting on the supply region S is particularly mitigated by the protective liquid film 105. In particular, when the movement of the third movable nozzle 10 in the removal process is started from the central position, the physical force acting on the central region of the upper surface of the substrate W can be mitigated.

[0457] In addition, the protective liquid film forming step (step S8) can be omitted, and the protective liquid parallel supply step in the removal step (step S9) can be omitted. Fig.13 As shown, the removal liquid is supplied from the third moving nozzle 10 to the treated film 100 whose surface is not protected, and the protection liquid is not supplied from the fourth moving nozzle 11 .

[0458] In this case, the droplets 106 of the removal liquid are supplied to the process film 100 while the surface of the process film 100 is not protected by the protection liquid, so that a strong physical force acts on the process film 100. The strong physical force can efficiently remove the removal object 103 from the upper surface of the substrate W, and is particularly useful when using a substrate W without a concavo-convex pattern. Even in this case, if the third movable nozzle 10 supplies the removal liquid to the process film 100 while moving between the central position and the peripheral position, the strong physical force can be applied to the entire process film 100 without omission.

[0459] In addition, unlike the substrate processing in the above-mentioned embodiment, the type of liquid supplied as the protective liquid to the upper surface of the substrate W in the protective liquid film forming step (step S8) may be different from the type of liquid supplied as the protective liquid to the upper surface of the substrate W in the protective liquid parallel supply step of the removal step (step S9). For example, pure water may be used as the protective liquid in the protective liquid film forming step, and an alkaline aqueous solution may be used as the protective liquid in the protective liquid parallel supply step.

[0460] For this purpose, for example, Fig.14 As shown, the substrate processing apparatus 1 may include the fifth movable nozzle 12 which is held by the nozzle holder 38B together with the fourth movable nozzle 11 and discharges the protection liquid.

[0461] The fifth movable nozzle 12 is held on the nozzle holder 38B, so the third movable nozzle 10 and the fourth movable nozzle 11 are moved integrally by the third nozzle moving unit 38. The fifth movable nozzle 12 is connected to the second protection liquid piping 49. The second protection liquid valve 59A and the second protection liquid flow regulating valve 59B are installed on the second protection liquid piping 49. The second protection liquid valve 59A and the second protection liquid flow regulating valve 59B are controlled by the controller 3 (see Figure 4 ).

[0462] Furthermore, unlike the substrate processing in the above-described embodiment, the chemical solution supplying step (step S2 ), the first rinsing step (step S3 ), and the first organic solvent supplying step (step S4 ) may be omitted.

[0463] In addition, in the substrate processing in the above-mentioned embodiment (see Figure 5 ), in the process film forming step (step S6 and step S7), the solvent of the process liquid is evaporated by heating the substrate W with a heat medium. However, the supply of the heat medium is not limited, and for example, the substrate W may be heated by a heater (not shown) built into the rotating base 21 or the opposing member 6. In this case, the heater functions as a substrate heating unit and an evaporation unit (evaporation promotion unit).

[0464] In addition, in the thin filming process (step S6), there is a case where the solvent evaporates when the liquid film 101 of the processing liquid is thinned to form the processing film 100. In this case, the thin filming process (step S6) and the solid forming process (step S7) are performed in parallel. In this case, the solid forming unit does not include the central nozzle 14 and the lower surface nozzle 15, and the solid forming unit is composed of the substrate rotating unit (rotation motor 23) and the central nozzle 14. In addition, it is also possible to omit only the heating process or only the gas supply process in the solid forming process (step S7).

[0465] In addition, in the above-mentioned substrate processing, the second rinsing process (step S10) is performed after the removal process (step S9). However, the second rinsing process may be omitted. Specifically, when the removal liquid supplied to the substrate W in the removal process is compatible with the organic solvent (residue removal liquid) supplied to the substrate W in the second organic solvent supply process (step S10) performed after the second rinsing process, the second rinsing process does not need to be performed.

[0466] In the above embodiment, a nozzle is used to eject the removal liquid in the form of droplets by applying a voltage. However, unlike the above embodiment, a two-fluid nozzle may be used, that is, an inert gas such as nitrogen gas is made to collide (mix) with the removal liquid near the ejection port to form droplets of the removal liquid, and the droplets of the removal liquid are supplied to the upper surface of the substrate W. In the two-fluid nozzle, the physical force of the droplets of the removal liquid can be adjusted by adjusting the flow rate of the liquid toward the ejection port and the flow rate of the gas toward the ejection port.

[0467] The embodiments of the present invention have been described in detail, but these embodiments are merely specific examples used to make the technical content of the present invention clear and easy to understand, and the present invention should not be limited to these specific examples. The scope of the present invention is limited only by the claims.

[0468] This application corresponds to Tokugan Application No. 2019-056285 filed with the Japan Patent Office on March 25, 2019, and all disclosed contents of the Japanese application are incorporated into this application by reference.

[0469] Description of Reference Numerals

[0470] 1: Substrate processing device

[0471] 1P: Substrate processing equipment

[0472] 3: Controller

[0473] 9: Second movable nozzle (processing liquid supply unit)

[0474] 10: 3rd movable nozzle (removal liquid supply unit)

[0475] 11: 4th moving nozzle (1st protection liquid supply unit, 2nd protection liquid supply unit)

[0476] 12: Fifth movable nozzle (first protection liquid supply unit, second protection liquid supply unit)

[0477] 14: Central nozzle (solid forming unit, solution supply unit)

[0478] 15: Lower surface nozzle (solid forming unit)

[0479] 23: Rotary motor (solid forming unit)

[0480] 100: Processing film

[0481] 102: Through hole

[0482] 103: Remove the object

[0483] 200: Processing membrane

[0484] 210: Highly soluble solids (highly soluble substances in solid state)

[0485] 211: Low-soluble solids (solid state low-soluble substances)

[0486] 300: Processing film

[0487] 310: Highly soluble solids (highly soluble substances in solid state)

[0488] 311: Low-soluble solids (solid state low-soluble substances)

[0489] 312: Solvent-enhanced solids (solid-state solvent-enhanced substances)

[0490] R: Radius

[0491] S: Supply area

[0492] T: Film thickness

[0493] W: substrate

Claims

1. A substrate processing method, comprising the following steps: a process liquid supplying step of supplying a process liquid containing a solute and a solvent to the surface of the substrate; a treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate for holding the removal object present on the surface of the substrate; and a removal step of supplying a removal liquid in a droplet state to the surface of the substrate so that the physical force of the droplets of the removal liquid acts on the processing film and the removal object, thereby removing the processing film and the removal object from the surface of the substrate, in, The removing step includes supplying the removing liquid in a droplet state to the surface of the substrate so that the processing film is partially dissolved in the removing liquid. The solute includes a highly soluble substance and a low soluble substance having a lower solubility in the removal liquid than the highly soluble substance. The process film forming step includes forming the process film having the high-solubility substance in a solid state and the low-solubility substance in a solid state. The removing step includes a step of selectively dissolving the highly soluble substance in a solid state in the treatment film in the removing liquid.

2. The substrate processing method according to claim 1, wherein: The solute has a solubility enhancing substance, The removal process includes the following process, namely, a process of enhancing the solubility of the removal solution supplied to the surface of the substrate to dissolve the treatment film by dissolving the solubility enhancing substance from the treatment film into the removal solution supplied to the surface of the substrate, and partially dissolving the treatment film in the removal solution with enhanced solubility.

3. A substrate processing method comprising the following steps: a process liquid supplying step of supplying a process liquid containing a solute and a solvent to the surface of the substrate; a treatment film forming step of solidifying or curing the treatment liquid supplied to the surface of the substrate to form a treatment film on the surface of the substrate for holding the removal object present on the surface of the substrate; and a removal step of supplying a removal liquid in a droplet state to the surface of the substrate so that the physical force of the droplets of the removal liquid acts on the processing film and the removal object, thereby removing the processing film and the removal object from the surface of the substrate, in, The removing step includes supplying the removing liquid in a droplet state to the surface of the substrate so that the processing film is partially dissolved in the removing liquid. The solute has a solubility enhancing substance, The removal process includes the following process, namely, a process of enhancing the solubility of the removal solution supplied to the surface of the substrate to dissolve the treatment film by dissolving the solubility enhancing substance from the treatment film into the removal solution supplied to the surface of the substrate, and partially dissolving the treatment film in the removal solution with enhanced solubility.

4. The substrate processing method according to any one of claims 1 to 3, wherein: The removal process comprises the following steps: a process film removal step of causing the physical force of the liquid droplets of the removal solution to act on the process film, thereby peeling the process film with the object to be removed from the surface of the substrate and splitting it to remove it from the surface of the substrate; and The removal object removing step removes the removal object from the surface of the substrate by causing a physical force of the droplets of the removing solution to act on the removal object.

5. The substrate processing method according to any one of claims 1 to 3, wherein: The processing film forming step includes the step of forming the processing film having a film thickness smaller than a radius of the removal object held by the processing film.

6. The substrate processing method according to any one of claims 1 to 3, wherein: The removal liquid is water or alkaline liquid.

7. The substrate processing method according to any one of claims 1 to 3, further comprising: The protective liquid film forming step is to supply the protective liquid to the surface of the substrate in a continuous flow before the removal step begins, thereby forming a liquid film of the protective liquid on the surface of the substrate covering the supply area where the removal liquid is supplied in the form of droplets in the removal step.

8. The substrate processing method according to any one of claims 1 to 3, further comprising: The protection liquid parallel supply step supplies the protection liquid to the surface of the substrate in a continuous flow while the removal liquid is supplied to the surface of the substrate in a droplet state in the removal step.

9. The substrate processing method according to claim 7, wherein: The protection liquid has a property of partially dissolving the treatment film.

10. The substrate processing method according to claim 7, wherein: The protective liquid is water or alkaline liquid.

11. The substrate processing method according to any one of claims 1 to 3, wherein: Further including: In the residue removing step, a dissolving liquid for dissolving the process film is supplied to the surface of the substrate to remove the residue of the process film remaining on the surface of the substrate after the removing step.

12. A substrate processing device, comprising: a processing liquid supply unit for supplying a processing liquid containing a solute and a solvent to the surface of the substrate; a solid forming unit that solidifies or hardens the treatment fluid; a removing liquid supply unit for supplying the removing liquid in a droplet state to the surface of the substrate; and a controller for controlling the processing liquid supply unit, the solid forming unit and the removal liquid supply unit, The controller is programmed to perform the following steps: a treatment liquid supplying step, in which the treatment liquid is supplied from the treatment liquid supplying unit to the surface of the substrate; a treatment film forming step, in which the treatment liquid supplied to the surface of the substrate is solidified or hardened by the solid forming unit, thereby forming a treatment film on the surface of the substrate for holding the removal object existing on the surface of the substrate; and a removal step, in which the removal liquid is supplied from the removal liquid supplying unit to the surface of the substrate in a droplet state so that the physical force of the droplets of the removal liquid acts on the treatment film and the removal object, thereby removing the treatment film and the removal object from the surface of the substrate, The controller executes, in the removing step, a step of supplying the removing liquid in a droplet state to the surface of the substrate so that the processing film is partially dissolved in the removing liquid, The solute includes a highly soluble substance and a low soluble substance having a lower solubility in the removal liquid than the highly soluble substance. the controller executes, in the process film forming step, a step of forming the process film having the high-solubility substance in a solid state and the low-solubility substance in a solid state, The controller executes a step of selectively dissolving the highly soluble substance in a solid state in the treatment film in the removal liquid in the removal step.

13. A substrate processing device, comprising: a processing liquid supply unit for supplying a processing liquid containing a solute and a solvent to the surface of the substrate; a solid forming unit that solidifies or hardens the treatment fluid; a removing liquid supply unit for supplying the removing liquid in a droplet state to the surface of the substrate; and a controller for controlling the processing liquid supply unit, the solid forming unit and the removal liquid supply unit, The controller is programmed to perform the following steps: a treatment liquid supplying step, in which the treatment liquid is supplied from the treatment liquid supplying unit to the surface of the substrate; a treatment film forming step, in which the treatment liquid supplied to the surface of the substrate is solidified or hardened by the solid forming unit, thereby forming a treatment film on the surface of the substrate for holding the removal object existing on the surface of the substrate; and a removal step, in which the removal liquid is supplied from the removal liquid supplying unit to the surface of the substrate in a droplet state so that the physical force of the droplets of the removal liquid acts on the treatment film and the removal object, thereby removing the treatment film and the removal object from the surface of the substrate, The controller executes, in the removing step, a step of supplying the removing liquid in a droplet state to the surface of the substrate so that the processing film is partially dissolved in the removing liquid, The solute has a solubility enhancing substance, The controller performs the following process in the removal process, namely, a process of enhancing the solubility of the removal solution supplied to the surface of the substrate to dissolve the treatment film by dissolving the solubility enhancing substance from the treatment film into the removal solution supplied to the surface of the substrate, and partially dissolving the treatment film in the removal solution with enhanced solubility.

14. The substrate processing apparatus according to claim 12 or 13, wherein: The controller is programmed to perform the following steps in the removal step: a process film removal step of causing a physical force of liquid droplets of the removal liquid to act on the process film, thereby peeling the process film in a state where the removal object is retained from the surface of the substrate and splitting it so as to be removed from the surface of the substrate; and a removal object removing step of causing a physical force of droplets of the removing solution to act on the removal object, thereby removing the removal object from the surface of the substrate.

15. The substrate processing apparatus according to claim 12 or 13, wherein: The controller is programmed to form the processing film having a film thickness smaller than a radius of the removal object held by the processing film in the processing film forming step.

16. The substrate processing apparatus according to claim 12 or 13, further comprising a first protection liquid supply unit for supplying the protection liquid to the surface of the substrate in a continuous flow, The controller is programmed to perform the following protective liquid film formation process, that is, before the removal process begins, the protective liquid is supplied from the first protective liquid supply unit to the surface of the substrate in a continuous flow, thereby forming a liquid film of the protective liquid on the surface of the substrate covering the supply area to which the removal liquid is supplied in a droplet state in the removal process.

17. The substrate processing apparatus according to claim 12 or 13, further comprising a second protection liquid supply unit for supplying the protection liquid to the surface of the substrate in a continuous flow, The controller is programmed to execute the following protection liquid parallel supply process, that is, while the removal liquid is supplied to the surface of the substrate in a droplet state in the removal process, the protection liquid is supplied to the surface of the substrate from the second protection liquid supply unit in a continuous flow.

18. The substrate processing apparatus according to claim 16, wherein: The protection liquid has a property of partially dissolving the treatment film.

19. The substrate processing apparatus according to claim 12 or 13, further comprising a dissolving liquid supply unit for supplying a dissolving liquid for dissolving the processing film to the surface of the substrate, The controller is programmed to perform a residue removal process of supplying the dissolving solution from the dissolving solution supply unit to remove residues of the processing film remaining on the surface of the substrate after the removal process.

Images