Substrate processing method, substrate processing apparatus, and polymer-containing liquid

Abstract

To provide a substrate processing method, substrate processing apparatus and polymer-containing liquid, capable of reducing a usage amount of polymer-containing liquid containing a component working on metal foreign matter adhering to a principal plane of a substrate.SOLUTION: Polymer-containing liquid containing acid polymer and solvent dissolving the acid polymer is supplied to a principal surface of a substrate (polymer-containing liquid supply process: step S2). By rotating the substrate to which polymer-containing liquid adheres to the principal plane, a polymer film containing oxidizer and acid polymer is formed on the principal plane of the substrate (polymer film formation process: step S3). Rinse liquid for cleaning the principal plane of the substrate under a state where the polymer film is formed on the principal plane is supplied to the principal plane of the substrate (rinse process: step S5).SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method, a substrate processing apparatus for processing a substrate, and a polymer-containing liquid for processing a substrate.

[0002] Substrates to be processed include, for example, semiconductor wafers, substrates for FPDs (Flat Panel Displays) such as liquid crystal displays and organic EL (Electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells. [Background technology]

[0003] Metals used in the components used in substrate processing adhere to the main surface of the substrate as foreign matter. It is difficult to remove the metal foreign matter adhering to the main surface of the substrate using deionized water (DIW) or the like, which poses a problem of reduced yield of semiconductor products.

[0004] Patent Document 1 below discloses a substrate treatment method in which a substrate is immersed in a mixture of hydrogen peroxide and hydrochloric acid, called an HPM (Hydrochloric Hydrogen Peroxide Mixture), to remove metallic foreign matter adhering to the substrate. The HPM solution is also called an SC2 (Standard Clean 2) solution. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-72190 Summary of the Invention [Problem to be solved by the invention]

[0006] In the substrate processing of Patent Document 1, a bath filled with HPM liquid is used to immerse the substrate in the HPM liquid, which requires a large amount of HPM liquid to remove metallic foreign matter adhering to the substrate, which poses an environmental burden problem.

[0007] Therefore, one object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a polymer-containing liquid that can effectively remove metal foreign matter adhering to a substrate while reducing the environmental load. [Means for solving the problem]

[0008] One embodiment of the present invention provides a substrate processing method including: a polymer-containing liquid supplying step of supplying a polymer-containing liquid containing an acidic polymer and a solvent that dissolves the acidic polymer onto a main surface of a substrate; a polymer film forming step of rotating the substrate, on whose main surface the polymer-containing liquid is adhered, to spread the polymer-containing liquid and form a polymer film containing the acidic polymer on the main surface of the substrate; and a rinsing step of supplying, to the main surface of the substrate, a rinsing liquid that cleans the main surface of the substrate on which the polymer film has been formed.

[0009] According to this substrate processing method, a polymer film is formed by rotating a substrate to which a polymer-containing liquid is attached. Metallic foreign matter is pulled away from the main surface of the substrate and adsorbed onto the polymer film by the action of the acidic polymer in the polymer film. Therefore, by forming a polymer film using an amount of polymer-containing liquid sufficient to cover the entire main surface of the substrate, and then rinsing the main surface of the substrate with a rinse liquid to remove the polymer film, metallic foreign matter can be effectively removed from the main surface of the substrate without continuously supplying the polymer-containing liquid to the main surface of the substrate.

[0010] Therefore, the amount of polymer-containing liquid used can be reduced because the metal foreign matter can be sufficiently removed without immersing the substrate in the polymer-containing liquid, thereby reducing the environmental load.

[0011] In one embodiment of the present invention, the polymer-containing liquid further contains an oxidizing agent dissolved in the solvent. The polymer film formed in the polymer film-forming step further contains the oxidizing agent. Therefore, the action of the oxidizing agent in the polymer film can promote adsorption of metallic contaminants by the acidic polymer. This allows for more effective removal of metallic contaminants from the main surface of the substrate.

[0012] In one embodiment of the present invention, the polymer-containing liquid is a mixture of an acidic polymer liquid containing 10 wt % of the acidic polymer and a liquid oxidizing agent containing 30 wt % of the oxidizing agent at a volume ratio of 1:6, which allows the polymer film to more efficiently adsorb metallic foreign matter on the main surface of the substrate. In one embodiment of the present invention, the substrate processing method further includes a metal foreign matter adsorption step of detaching metal foreign matter adhering to the main surface of the substrate from the main surface of the substrate by the action of the acidic polymer in the polymer film and adsorbing the metal foreign matter onto the polymer film, and an adsorption promotion step of promoting adsorption of the metal foreign matter by the acidic polymer by the action of the oxidizing agent in the polymer film.

[0013] In one embodiment of the present invention, the polymer film forming step includes a step of forming the polymer film by evaporating a portion of the solvent in the polymer-containing liquid. Because the solvent remains in the polymer film, the solvent functions as a medium for the acidic polymer in the polymer film to exchange protons (hydrogen ions). Because the polymer film is formed by evaporating a portion of the solvent from the polymer-containing liquid, the acidic polymer in the polymer film has a higher concentration than in the polymer-containing liquid. The high concentration of acidic polymer can act on the metal foreign matter, allowing the metal foreign matter to be effectively adsorbed onto the polymer film. Therefore, by removing the polymer film with the adsorbed metal foreign matter using a rinse liquid, the metal foreign matter can be effectively removed from the main surface of the substrate.

[0014] In one embodiment of the present invention, the rinsing step includes a polymer film removing step of removing the polymer film from the main surface of the substrate. In one embodiment of the present invention, the substrate processing method further includes, after the polymer film forming step, a polymer film heating step of heating the polymer film.

[0015] According to this substrate processing method, the solvent is evaporated from the polymer film by heating the polymer film. This increases the concentration of the acidic polymer dissolved in the solvent in the polymer film. This allows the high-concentration acidic polymer to act on the metallic foreign matter. Therefore, by removing the polymer film with the adsorbed metallic foreign matter using a rinse solution, the metallic foreign matter can be effectively removed from the main surface of the substrate. In other words, the metallic foreign matter can be successfully removed from the main surface of the substrate.

[0016] Furthermore, by heating the polymer film at a temperature below the boiling point of the solvent, the solvent can be evaporated appropriately from the polymer film on the substrate, thereby increasing the concentration of the acidic polymer dissolved in the solvent in the polymer film and preventing the solvent from being completely evaporated and removed from the polymer film.

[0017] In one embodiment of the present invention, the polymer film heating process includes a fluid heating process in which the polymer film is heated through the substrate by supplying a heating fluid to the surface of the substrate opposite to the main surface while rotating the substrate.

[0018] This substrate processing method allows the substrate to be heated by a simple method of supplying a heated fluid to the opposite side of the substrate. The heated fluid supplied to the opposite side of the rotating substrate spreads evenly toward the periphery on the underside of the substrate due to the action of centrifugal force. This allows the entire substrate to be heated evenly, thereby allowing the solvent to evaporate evenly from the entire main surface of the substrate.

[0019] In one embodiment of the present invention, the substrate processing method further includes a substrate rotation stopping step of stopping the rotation of the substrate for a predetermined time after the polymer film forming step. By stopping the substrate rotation, excessive evaporation of the solvent from the polymer film on the main surface of the substrate can be suppressed. This prevents the polymer film from completely solidifying, while allowing the action of the acidic polymer in the polymer film to adsorb metal foreign matter to the polymer film.

[0020] In one embodiment of the present invention, the substrate processing method further includes a preparation step of storing the polymer-containing liquid in a polymer-containing liquid tank, and the polymer-containing liquid supply step includes a polymer-containing liquid discharge step of supplying the polymer-containing liquid from the polymer-containing liquid tank to a polymer-containing liquid nozzle and discharging the polymer-containing liquid from the polymer-containing liquid nozzle toward the main surface of the substrate.

[0021] According to this substrate processing method, the polymer-containing liquid is stored in the polymer-containing liquid tank, and therefore the acidic polymer and the oxidizing agent can be mixed before being supplied to the polymer-containing liquid nozzle, thereby enabling the ratio of the acidic polymer to the oxidizing agent in the polymer-containing liquid to be adjusted with high precision.

[0022] In one embodiment of the present invention, the polymer-containing liquid further contains a conductive polymer dissolved in the solvent. The polymer film formed in the polymer film-forming step further contains the conductive polymer. Therefore, the conductive polymer can promote ionization of the acidic polymer in the polymer film and ionization of metallic foreign matter. Therefore, the acidic polymer can effectively act on the metallic foreign matter.

[0023] Furthermore, the conductive polymer functions as a medium for the acidic polymer to release protons (hydrogen ions), similar to a solvent. Therefore, if a conductive polymer is contained in a polymer film, even if the solvent has completely disappeared from the polymer film and the polymer film is in a solid state, the acidic polymer can be ionized and the ionized acidic polymer can act on metallic foreign matter.

[0024] In one embodiment of the present invention, the substrate processing method further includes a solidified cleaning film forming step of forming a solid or semi-solid solidified cleaning film on the main surface of the substrate before the polymer-containing liquid supplying step, and a solidified cleaning film removing liquid supplying step of supplying, to the main surface of the substrate, a solidified cleaning film removing liquid that peels off the solidified cleaning film from the main surface of the substrate and removes it from the main surface of the substrate before the polymer-containing liquid supplying step.

[0025] According to this method, before the polymer-containing liquid supply step, the solidified cleaning film formed on the main surface of the substrate is peeled off from the main surface of the substrate by the solidified cleaning film removal liquid, and removed from the main surface of the substrate. Because the solidified cleaning film is solid or semi-solid, it can hold particulate foreign matter such as particles adhering to the main surface of the substrate. Since the solidified cleaning film is peeled off from the main surface of the substrate while holding the particulate foreign matter, the particulate foreign matter can be removed together with the solidified cleaning film. By holding the particulate foreign matter in the solidified cleaning film, the kinetic energy received from the solidified cleaning film removal liquid flowing over the main surface of the substrate is greater than the kinetic energy received from the solidified cleaning film removal liquid by particulate foreign matter not held by the solidified cleaning film. Therefore, the particulate foreign matter can be effectively removed from the main surface of the substrate. After the particulate foreign matter has been sufficiently removed by the solidified cleaning film, the polymer-containing liquid of It can be applied to a major surface of the substrate.

[0026] Another embodiment of the present invention provides a substrate processing apparatus including: a spin chuck that holds a substrate and rotates the substrate about a predetermined rotation axis; a polymer-containing liquid nozzle that supplies, to a main surface of the substrate held by the spin chuck, a polymer-containing liquid that contains an acidic polymer and a solvent that dissolves the acidic polymer, the polymer-containing liquid forming a polymer film containing the acidic polymer on the main surface of the substrate; and a rinse liquid nozzle that supplies a rinse liquid to the main surface of the substrate held by the spin chuck.

[0027] This substrate processing apparatus can form a polymer film on the main surface of a substrate held by a spin chuck by supplying a polymer-containing liquid to the main surface of the substrate. Specifically, the polymer film can be formed by rotating the substrate to which the polymer-containing liquid is attached to evaporate the solvent. The acidic polymer in the polymer film acts to pull metal foreign matter away from the main surface of the substrate and adsorb it onto the polymer film. Therefore, by supplying only the amount of polymer-containing liquid necessary to cover the entire main surface of the substrate, forming a polymer film with the polymer-containing liquid, and then cleaning the main surface of the substrate with a rinse liquid to remove the polymer film, the metal foreign matter can be removed without continuing to supply the polymer-containing liquid to the main surface of the substrate.

[0028] Therefore, the amount of polymer-containing liquid used can be reduced because the metal foreign matter can be sufficiently removed without immersing the substrate in the polymer-containing liquid, thereby reducing the environmental load. In one embodiment of the present invention, the polymer-containing liquid further contains an oxidizing agent dissolved in the solvent. The polymer-containing liquid may be a mixed liquid obtained by mixing an acidic polymer liquid containing 10 wt % of the acidic polymer and a liquid oxidizing agent containing 30 wt % of the oxidizing agent at a volume ratio of 1:6. In one embodiment of the present invention, the polymer-containing liquid further contains a conductive polymer dissolved in the solvent. In one embodiment of the present invention, the spin chuck rotates the substrate while the polymer-containing liquid supplied by the polymer-containing liquid nozzle is adhering to the main surface of the substrate, thereby forming the polymer film on the main surface of the substrate, and the rinse liquid nozzle supplies a rinse liquid to the substrate on which the polymer film has been formed, thereby removing the polymer film from the main surface of the substrate. In one embodiment of the present invention, due to the action of the acidic polymer in the polymer film, metallic foreign matter adhering to the main surface of the substrate is detached from the main surface of the substrate and adsorbed onto the polymer film. Yet another embodiment of the present invention provides a polymer-containing liquid containing an acidic polymer that removes metallic foreign matter adhering to a main surface of a substrate from the main surface of the substrate, an oxidizing agent that promotes the removal of the metallic foreign matter by the acidic polymer, and a solvent that dissolves the oxidizing agent and the acidic polymer.

[0029] According to this configuration, the oxidizing agent and the acidic polymer are dissolved in the solvent. Therefore, by applying the polymer-containing liquid to the main surface of the substrate and evaporating the solvent from the polymer-containing liquid, a film mainly composed of the acidic polymer and the oxidizing agent, i.e., a polymer film, can be formed on the main surface of the substrate. The action of the acidic polymer and the oxidizing agent in the polymer film allows the polymer film to adsorb metallic foreign matter. Therefore, by forming a polymer film using an amount of polymer-containing liquid necessary to cover the entire main surface of the substrate and removing the polymer film, metallic foreign matter can be removed from the main surface of the substrate without continuing to supply the polymer-containing liquid to the main surface of the substrate. of It can be removed.

[0030] Therefore, metallic foreign matter can be sufficiently removed without immersing the substrate in the polymer-containing liquid, and the amount of polymer-containing liquid used can be reduced. In one embodiment of the present invention, the polymer-containing liquid is a mixed liquid obtained by mixing an acidic polymer liquid containing 10 wt % of the acidic polymer and a liquid oxidizing agent containing 30 wt % of the oxidizing agent in a volume ratio of 1:6. In one embodiment of the present invention, the polymer-containing liquid further contains a conductive polymer, and the solvent dissolves the oxidizing agent, the acidic polymer, and the conductive polymer. [Brief explanation of the drawings]

[0031] [Figure 1] FIG. 1 is a plan view illustrating the configuration of a substrate processing apparatus according to a first embodiment of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view for explaining an example of the configuration of a processing unit provided in the substrate processing apparatus. [Figure 3] FIG. 3 is a block diagram for explaining an example of a configuration relating to control of the substrate processing apparatus. [Figure 4] FIG. 4 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus. [Figure 5A] FIG. 5A is a schematic diagram for explaining the state of the substrate when the example of the substrate processing is being performed. [Figure 5B] FIG. 5B is a schematic diagram for explaining the state of the substrate when the example of the substrate processing is being performed. [Figure 5C] FIG. 5C is a schematic diagram for explaining the state of the substrate when the example of the substrate processing is being performed. [Figure 5D] FIG. 5D is a schematic diagram for explaining the state of the substrate when the example of the substrate processing is being performed. [Figure 5E] FIG. 5E is a schematic diagram for explaining the state of the substrate when the example of the substrate processing is being performed. [Figure 6A] FIG. 6A is a schematic diagram for explaining how metallic foreign matter adhering to the main surface of the substrate is removed. [Figure 6B] FIG. 6B is a schematic diagram for explaining how metallic foreign matter adhering to the main surface of the substrate is removed. [Figure 6C]FIG. 6C is a schematic diagram for explaining how metallic foreign matter adhering to the main surface of the substrate is removed. [Figure 7] FIG. 7 is a flowchart illustrating another example of the substrate processing performed by the substrate processing apparatus. [Figure 8] FIG. 8 is a schematic view for explaining the state of a substrate when another example of substrate processing performed by the substrate processing apparatus is being performed. [Figure 9] FIG. 9 is a schematic view for explaining a first modified example of the substrate processing apparatus. [Figure 10] FIG. 10 is a schematic view for explaining a second modified example of the substrate processing apparatus. [Figure 11] FIG. 11 is a schematic cross-sectional view illustrating an example of the configuration of a processing unit provided in a substrate processing apparatus according to the second embodiment. [Figure 12] FIG. 12 is a schematic view for explaining the state of a substrate when an example of substrate processing is performed by the substrate processing apparatus according to the second embodiment. [Figure 13] FIG. 13 is a schematic cross-sectional view illustrating an example of the configuration of a processing unit provided in a substrate processing apparatus according to a third embodiment. [Figure 14] FIG. 14 is a schematic view for explaining a first modified example of the substrate processing apparatus according to the third embodiment. [Figure 15] FIG. 15 is a schematic view for explaining a second modified example of the substrate processing apparatus according to the third embodiment. [Figure 16] FIG. 16 is a schematic view for explaining a third modified example of the substrate processing apparatus according to the third embodiment. [Figure 17] FIG. 17 is a schematic view for explaining a fourth modified example of the substrate processing apparatus according to the third embodiment. [Figure 18] FIG. 18 is a schematic view for explaining an example of the configuration of a processing unit provided in a substrate processing apparatus according to a fourth embodiment. [Figure 19]FIG. 19 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus according to the fourth embodiment. [Figure 20] FIG. 20 is a graph showing the results of an experiment measuring the removal efficiency of metal foreign matter by a polymer membrane. [Figure 21] FIG. 21 is a graph showing the results of an experiment measuring the removal efficiency of metal foreign matter by a polymer membrane. DETAILED DESCRIPTION OF THE INVENTION

[0032] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.

[0033] <Configuration of the Substrate Processing Apparatus According to the First Embodiment> FIG. 1 is a plan view illustrating the configuration of a substrate processing apparatus 1 according to a first embodiment of the present invention.

[0034] The substrate processing apparatus 1 is a single-wafer processing apparatus that processes substrates W, such as silicon wafers, one by one. In this embodiment, the substrate W is a disk-shaped substrate. The substrate W has a pair of main surfaces, and is processed with one of the main surfaces facing upward. At least one of the pair of main surfaces is a device surface on which a circuit pattern is formed. One of the pair of main surfaces may also be a non-device surface on which no circuit pattern is formed.

[0035] The substrate processing apparatus 1 includes a plurality of processing units 2 that process substrates W with a fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W to be processed in the processing units 2 is placed, transport robots IR and CR that transport the substrates W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.

[0036] The transport robot IR transports the substrate W between the carrier C and the transport robot CR. The transport robot CR transports the substrate W between the transport robot IR and the processing unit 2. The processing units 2 have, for example, the same configuration. As will be described in detail later, examples of fluids supplied to the substrate W in the processing unit 2 include a polymer-containing liquid, a liquid oxidizing agent, a rinse liquid, a heating fluid, etc.

[0037] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed in the chamber 4, and performs processing on the substrate W in the processing cup 7. The chamber 4 is formed with an entrance / exit (not shown) through which the transfer robot CR loads and unloads the substrate W. The chamber 4 is provided with a shutter unit (not shown) that opens and closes this entrance / exit.

[0038] FIG. 2 is a schematic cross-sectional view for explaining an example of the configuration of the processing unit 2. As shown in FIG.

[0039] The processing unit 2 further includes a spin chuck 5 that rotates the substrate W about a rotation axis A1 (vertical axis) while holding the substrate W horizontally. The rotation axis A1 is a vertical line that passes through the center of the substrate W.

[0040] The spin chuck 5 includes a substrate holding unit 20 that holds the substrate W at a predetermined holding position, and a substrate rotation unit 21 that rotates the substrate holding unit 20 about a rotation axis A1. The holding position is the position of the substrate W shown in FIG. 2, where the substrate W is held in a horizontal position.

[0041] The substrate holding unit 20 includes a spin base 22 having a horizontally extending disk shape, and a plurality of chuck pins 23 that grip the substrate W above the spin base 22 and hold the substrate W in a holding position. The plurality of chuck pins 23 are arranged on the upper surface of the spin base 22 at intervals in the circumferential direction of the spin base 22. The substrate holding unit 20 is also called a substrate holder.

[0042] The substrate rotation unit 21 includes a rotation shaft 24 that extends vertically and whose upper end is connected to the spin base 22, and a spin motor 25 that rotates the rotation shaft 24 about its central axis (rotation axis A1). The spin motor 25 rotates the rotation shaft 24, causing the spin base 22 and the multiple chuck pins 23 to rotate about the rotation axis A1. As a result, the substrate W is rotated about the rotation axis A1 together with the spin base 22 and the multiple chuck pins 23.

[0043] The multiple chuck pins 23 can be opened and closed between a closed state in which they contact the peripheral edge of the substrate W to grip the substrate W, and an open state in which they are retracted from the peripheral edge of the substrate W. The multiple chuck pins 23 are opened and closed by an opening and closing unit 26. In the closed state, the multiple chuck pins 23 hold (clamp) the substrate W horizontally. In the open state, the multiple chuck pins 23 release their grip on the peripheral edge of the substrate W, while contacting the peripheral edge of the lower surface (lower main surface) of the substrate W to support the substrate W from below.

[0044] The opening / closing unit 26 includes, for example, a link mechanism housed inside the spin base 22 and a drive source disposed outside the spin base 22. The drive source includes an electric motor.

[0045] The spin chuck 5 is not limited to a gripping type, but may be, for example, a vacuum chuck of a vacuum suction type. The vacuum chuck holds the substrate W in a horizontal position by vacuum suctioning the lower surface of the substrate W, and further rotates the substrate W around a vertical rotation axis in that state.

[0046] The processing cup 7 receives liquid splashed from the substrate W held on the spin chuck 5. The processing cup 7 includes a plurality of guards 30 that receive liquid splashed outward from the substrate W held on the spin chuck 5, a plurality of cups 31 that receive liquid guided downward by the plurality of guards 30, and a cylindrical outer wall member 32 that surrounds the plurality of guards 30 and the plurality of cups 31. In this embodiment, an example is shown in which two guards 30 and two cups 31 are provided.

[0047] Each guard 30 has a substantially cylindrical shape. The upper end of each guard 30 is inclined inward toward the spin base 22. A plurality of cups 31 are disposed below each of the guards 30. The cups 31 form annular liquid-receiving grooves that receive the liquid guided downward by the guards 30.

[0048] The processing unit 2 includes a guard lifting unit 33 that individually raises and lowers the multiple guards 30. The guard lifting unit 33 positions the guards 30 at any position between the upper position and the lower position. FIG. 2 shows a state in which two guards 30 are both positioned at the upper position. The upper position is a position where the upper ends of the guards 30 are positioned above the holding position where the substrate W held by the spin chuck 5 is positioned. The lower position is a position where the upper ends of the guards 30 are positioned below the holding position.

[0049] The guard lifting unit 33 includes, for example, a plurality of ball screw mechanisms (not shown) respectively coupled to the plurality of guards 30, and a plurality of motors (not shown) that provide driving forces to the ball screw mechanisms. The guard lifting unit 33 is also called a guard lifter.

[0050] When liquid is supplied to the rotating substrate W, at least one guard 30 is positioned in the upper position. In this state, when liquid is supplied to the substrate W, the liquid is thrown outward from the substrate W. The thrown-off liquid collides with the inner surface of the guard 30 horizontally facing the substrate W, and is guided to the cup 31 corresponding to this guard 30. When the transfer robot CR (see FIG. 1) accesses the spin chuck 5 to load and unload the substrate W, all of the guards 30 are positioned in the lower position.

[0051] The processing unit 2 further includes a polymer-containing liquid nozzle 8 that ejects a polymer-containing liquid toward the upper surface (upper main surface) of the substrate W held on the spin chuck 5, and a rinse liquid nozzle 9 that ejects a rinse liquid such as DIW toward the upper surface of the substrate W held on the spin chuck 5.

[0052] The polymer-containing liquid contains a component (an acidic polymer, described later) that forms a solid or semi-solid film (polymer film). A semi-solid state is a state in which a solid component and a liquid component are mixed. A solid state is a state in which no liquid component is contained and which is composed only of a solid component. A polymer film in which the solvent remains is semi-solid, and a polymer film in which the solvent has completely disappeared is solid.

[0053] The polymer-containing liquid contains a solute and a solvent such as DIW to dissolve the solute in. The solute contains an oxidizing agent such as hydrogen peroxide and an acidic polymer such as polyacrylic acid.

[0054] The molecular weight of the acidic polymer is, for example, 1,000 or more and 100,000 or less. The acidic polymer has the function of adsorbing metallic foreign matter attached to the main surface of the substrate W. In an aqueous solvent such as DIW, the acidic polymer releases protons (hydrogen ions) and becomes negatively charged. Therefore, the acidic polymer severs the bonds between the metallic foreign matter and the main surface of the substrate, ionizes the metallic foreign matter, and adsorbs the ionized metallic foreign matter (cations) to separate it from the main surface of the substrate W.

[0055] Examples of metal foreign matter that may adhere to the main surface of the substrate W include aluminum (Al), potassium (K), titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), copper (Cu), calcium (Ca), manganese (Mn), cobalt (Co), zinc (Zn), hafnium (Hf), and tantalum (Ta).

[0056] The acidic polymer is not limited to polyacrylic acid. The pH of the polymer-containing liquid may be less than 7, preferably 5 or less. The acidic polymer is, for example, a carboxy group-containing polymer, a sulfo group-containing polymer, or a mixture thereof. The carboxylic acid polymer is, for example, polyacrylic acid, a carboxyvinyl polymer (carbomer), carboxymethyl cellulose, or a mixture thereof. The sulfo group-containing polymer is, for example, polystyrene sulfonic acid, polyvinyl sulfonic acid, or a mixture thereof.

[0057] The oxidizing agent has the function of promoting the adsorption of metallic foreign matter by the acidic polymer. The oxidizing agent is a substance with a higher oxidation-reduction potential than the metallic foreign matter. Therefore, the oxidizing agent removes electrons from the metallic foreign matter adhering to the main surface of the substrate W, promoting the ionization of the metallic foreign matter. The oxidizing agent contains, for example, at least one of hydrogen peroxide and ozone.

[0058] The oxidation-reduction potentials described below are those measured with a normal hydrogen electrode (NHE) as the reference. The oxidation-reduction potential of hydrogen peroxide is 1.776 V, and the oxidation-reduction potential of ozone is 2.067 V. In contrast, the oxidation-reduction potentials of copper, nickel, iron, and aluminum are 0.337 V, −0.250 V, −0.440 V, and −1.663 V, respectively. Therefore, when an oxidizing agent containing at least one of hydrogen peroxide and ozone is used as the oxidizing agent, it can remove electrons from metallic foreign matter and promote the ionization of the metallic foreign matter.

[0059] The solvent may be any substance that is liquid at room temperature (for example, a temperature of 5°C or higher and 25°C or lower, also referred to as room temperature), can dissolve the acidic polymer and the oxidizing agent, and evaporates (volatilizes) when the substrate W is rotated or heated. The solvent is not limited to DIW. The solvent is a component containing at least one of DIW, carbonated water, electrolytic ionized water, diluted hydrochloric acid water (for example, 1 ppm or higher and 100 ppm or lower), diluted ammonia water (for example, 1 ppm or higher and 100 ppm or lower), and reduced water (hydrogen water).

[0060] The polymer-containing liquid is preferably a liquid obtained by mixing a liquid oxidizing agent and an acidic polymer liquid at a volume ratio of 1:6. The liquid oxidizing agent is a liquid containing the above-mentioned solvent and oxidizing agent, and the mass percent concentration of the oxidizing agent in the liquid oxidizing agent is, for example, 30 mass percent (wt%). The acidic polymer liquid is a liquid containing the above-mentioned solvent and acidic polymer, and the mass percent concentration of the acidic polymer in the acidic polymer liquid is, for example, 10 mass percent (wt%).

[0061] The rinse liquid is a liquid that cleans the upper surface of the substrate W by removing a polymer film formed on the main surface of the substrate W. The rinse liquid dissolves the polymer film and removes it from the main surface of the substrate W. For this reason, the rinse liquid is also called a polymer film removal liquid.

[0062] The rinse liquid is not limited to DIW. The rinse liquid is a component containing at least one of DIW, carbonated water, electrolytic ion water, diluted hydrochloric acid water (for example, 1 ppm or more and 100 ppm or less), diluted ammonia water (for example, 1 ppm or more and 100 ppm or less), and reduced water (hydrogen water). In other words, the rinse liquid can be a liquid similar to the solvent for the polymer-containing liquid. If the same type of liquid (for example, DIW) is used as both the rinse liquid and the solvent for the polymer-containing liquid, the number of types of liquids (substances) used can be reduced.

[0063] In this embodiment, the polymer-containing liquid nozzle 8 is a scan nozzle that is movable in the horizontal direction. The polymer-containing liquid nozzle 8 is moved in the horizontal direction by the first nozzle moving unit 35. The polymer-containing liquid nozzle 8 can move in the horizontal direction between a central position and a home position (retracted position). When the polymer-containing liquid nozzle 8 is located at the central position, it faces a central region of the upper surface of the substrate W. The central region of the upper surface of the substrate W refers to a region on the upper surface of the substrate W that includes the center of rotation of the substrate W. When the polymer-containing liquid nozzle 8 is located at the home position, it does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view.

[0064] The first nozzle moving unit 35 includes an arm (not shown) connected to the polymer-containing liquid nozzle 8 and extending horizontally, and an arm moving unit (not shown) that moves the arm in the horizontal direction. The arm moving unit may include, for example, a rotation shaft (not shown) connected to the arm and extending along the vertical direction, and a rotation actuator (not shown) such as a motor that rotates the rotation shaft. The polymer-containing liquid nozzle 8 may be movable in the vertical direction. By moving in the vertical direction, the polymer-containing liquid nozzle 8 can approach the upper surface of the substrate W or retract above the upper surface of the substrate W.

[0065] The polymer-containing liquid nozzle 8 is connected to one end of a polymer-containing liquid pipe 40 that guides the polymer-containing liquid to the polymer-containing liquid nozzle 8. The other end of the polymer-containing liquid pipe 40 is connected to a polymer-containing liquid tank 80 that stores the polymer-containing liquid. The polymer-containing liquid pipe 40 is provided with a polymer-containing liquid valve 50 that opens and closes the flow path in the polymer-containing liquid pipe 40, and a polymer-containing liquid flow rate adjustment valve 51 that adjusts the flow rate of the polymer-containing liquid in the flow path.

[0066] The polymer-containing liquid tank 80 is replenished with the polymer-containing liquid, and the polymer-containing liquid is stored in the polymer-containing liquid tank 80 (preparation step). For example, a liquid oxidizing agent and an acidic polymer liquid are replenished to the polymer-containing liquid tank 80 via separate refill pipes 84, 85. Unlike the example shown in FIG. 2, the polymer-containing liquid may be replenished to the polymer-containing liquid tank 80 via a polymer-containing liquid refill pipe (not shown).

[0067] A pump 70 is provided in the polymer-containing liquid pipe 40. Therefore, when the polymer-containing liquid valve 50 is opened, the pump 70 sends the polymer-containing liquid in the polymer-containing liquid tank 80 to the polymer-containing liquid pipe 40. The polymer-containing liquid sent to the polymer-containing liquid pipe 40 is discharged downward as a continuous flow from the discharge port of the polymer-containing liquid nozzle 8 at a flow rate that corresponds to the opening of the polymer-containing liquid flow rate adjustment valve 51. When the polymer-containing liquid nozzle 8 is located at the central position and the polymer-containing liquid valve 50 is opened, the polymer-containing liquid is supplied to the central region of the upper surface of the substrate W.

[0068] In this way, the polymer-containing liquid nozzle 8, the polymer-containing liquid pipe 40, the polymer-containing liquid valve 50, the polymer-containing liquid flow rate control valve 51, and the pump 70 constitute a polymer-containing liquid supply unit 11 that supplies the polymer-containing liquid to the main surface (upper surface) of the substrate W.

[0069] In this embodiment, the rinse liquid nozzle 9 is a scan nozzle that is movable in the horizontal direction. The rinse liquid nozzle 9 is moved in the horizontal direction by the second nozzle movement unit 36. The rinse liquid nozzle 9 can move in the horizontal direction between a central position and a home position (retracted position). When located at the central position, the rinse liquid nozzle 9 faces a central region of the upper surface of the substrate W. When located at the home position, the rinse liquid nozzle 9 does not face the upper surface of the substrate W and is located outside the processing cup 7 in a plan view.

[0070] The rinse liquid nozzle 9 is connected to a rinse liquid pipe 41 that guides the rinse liquid to the rinse liquid nozzle 9. A rinse liquid valve 52 that opens and closes a flow path in the rinse liquid pipe 41, and a rinse liquid flow rate adjustment valve 53 that adjusts the flow rate of the rinse liquid in the flow path are provided in the rinse liquid pipe 41. When the rinse liquid valve 52 is opened, the rinse liquid is discharged downward in a continuous stream from the discharge port of the rinse liquid nozzle 9 at a flow rate that corresponds to the opening of the rinse liquid flow rate adjustment valve 53. When the rinse liquid nozzle 9 is located at the central position and the rinse liquid valve 52 is opened, the rinse liquid is supplied to a central region on the upper surface of the substrate W.

[0071] In this manner, the rinse liquid nozzle 9, the rinse liquid pipe 41, the rinse liquid valve 52, and the rinse liquid flow rate adjustment valve 53 constitute a rinse liquid supply unit 12 that supplies the rinse liquid to the upper surface of the substrate W.

[0072] Unlike this embodiment, the polymer-containing liquid nozzle 8 and the rinse liquid nozzle 9 may be fixed nozzles whose horizontal and vertical positions are fixed.

[0073] The processing unit 2 further includes a heating fluid nozzle 10 that ejects a heating fluid toward the lower surface (lower main surface, opposite surface) of the substrate W held by the spin chuck 5.

[0074] The heating fluid nozzle 10 is inserted into a through-hole 22a that opens in the center of the upper surface of the spin base 22. The outlet 10a of the heating fluid nozzle 10 is exposed from the upper surface of the spin base 22. The outlet 10a of the heating fluid nozzle 10 faces a central region of the underside of the substrate W from below. The central region of the underside of the substrate W is a region on the underside of the substrate W that includes the center of rotation of the substrate W.

[0075] A heating fluid pipe 42 that guides the heating fluid to the heating fluid nozzle 10 is connected to the heating fluid nozzle 10. A heating fluid valve 54 that opens and closes the flow path in the heating fluid pipe 42, and a heating fluid flow rate adjustment valve 55 that adjusts the flow rate of the heating fluid in the heating fluid pipe 42 are installed in the heating fluid pipe 42.

[0076] When the heating fluid valve 54 is opened, the heating fluid is discharged upward in a continuous flow from the discharge port 10a of the heating fluid nozzle 10 and supplied to the central region of the lower surface of the substrate W. By supplying the heating fluid to the lower surface of the substrate W, the polymer-containing liquid on the upper surface of the substrate W is heated through the substrate W.

[0077] In this way, the heating fluid nozzle 10, the heating fluid pipe 42, the heating fluid valve 54, and the heating fluid flow rate adjusting valve 55 are Bottom surface The heating fluid supply unit 13 supplies the heating fluid to the

[0078] The heating fluid discharged from the heating fluid nozzle 10 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 polymer-containing liquid. When the solvent contained in the polymer-containing liquid is DIW, for example, DIW having a temperature of 60°C or higher and lower than 100°C is used as the heating fluid. The heating fluid discharged from the heating fluid nozzle 10 is not limited to high-temperature DIW, and may be a high-temperature gas such as a high-temperature inert gas (such as high-temperature nitrogen gas) or high-temperature air having a temperature higher than room temperature and lower than the boiling point of the solvent contained in the polymer-containing liquid. Furthermore, the heating fluid may have a temperature equal to or higher than the boiling point of the solvent contained in the polymer-containing liquid.

[0079] 3 is a block diagram for explaining an example of a configuration related to control of the substrate processing apparatus 1. The controller 3 includes a microcomputer, and controls the control targets provided in the substrate processing apparatus 1 according to a predetermined control program.

[0080] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B that stores a control program. The controller 3 is configured to perform various controls for substrate processing by the processor 3A executing the control program.

[0081] In particular, the controller 3 is programmed to control the transfer robots IR and CR, the spin motor 25, the opening / closing unit 26, the first nozzle moving unit 35, the second nozzle moving unit 36, the guard lifting / lowering unit 33, the polymer-containing liquid valve 50, the polymer-containing liquid flow rate adjusting valve 51, the rinse liquid valve 52, the rinse liquid flow rate adjusting valve 53, the heating fluid valve 54, the heating fluid flow rate adjusting valve 55, and the pump 70. By controlling the valves with the controller 3, it is possible to control whether or not a fluid is discharged from the corresponding nozzle and the flow rate of the fluid discharged from the corresponding nozzle.

[0082] 3 shows representative components, but this does not mean that components not shown are not controlled by the controller 3, and the controller 3 can appropriately control each component included in the substrate processing apparatus 1. FIG. 3 also shows components that will be described in modified examples and embodiments, which will be described later, and these components are also controlled by the controller 3.

[0083] The following steps are executed by controlling these components with the controller 3. In other words, the controller 3 is programmed to execute the following steps.

[0084] <Example of Substrate Processing According to First Embodiment> Fig. 4 is a flow chart illustrating an example of substrate processing performed by the substrate processing apparatus 1. Fig. 4 mainly illustrates processing that is realized by the execution of a program by the controller 3. Figs. 5A to 5E are schematic diagrams illustrating the state of each step of the substrate processing performed by the substrate processing apparatus 1.

[0085] In substrate processing by the substrate processing apparatus 1, for example, as shown in FIG. 4, a substrate loading step (step S1), a polymer-containing liquid supply step (step S2), a polymer film forming step (step S3), a polymer film heating step (step S4), a rinsing step (step S5), a spin-drying step (step S6), and a substrate unloading step (step S7) are performed in this order.

[0086] The first substrate processing performed by the substrate processing apparatus 1 will be described below mainly with reference to Figures 2 and 4. Figures 5A to 5E will also be referenced as appropriate.

[0087] First, an unprocessed substrate W is carried from a carrier C into the processing unit 2 by the transport robots IR and CR (see FIG. 1), and then handed over to the substrate holding unit 20 of the spin chuck 5 (substrate carrying-in step: step S1). As a result, the substrate W is held horizontally by the substrate holding unit 20 (substrate holding step).

[0088] The substrate W is held by the substrate holding unit 20 until the spin dry process (step S6) is completed. From the start of the substrate holding process until the end of the spin dry process (step S6), the guard lifting unit 33 adjusts the height positions of the multiple guards 30 so that at least one guard 30 is located at the upper position.

[0089] Next, after the transport robot CR retreats to the outside of the processing unit 2, a polymer-containing liquid supplying step (step S2) is performed to supply the polymer-containing liquid onto the upper surface of the substrate W. Specifically, the first nozzle moving unit 35 moves the polymer-containing liquid nozzle 8 to a processing position. The processing position of the polymer-containing liquid nozzle 8 is, for example, a central position.

[0090] With the polymer-containing liquid nozzle 8 positioned at the processing position, the polymer-containing liquid valve 50 is opened. As a result, as shown in Fig. 5A, the polymer-containing liquid is supplied (discharged) from the polymer-containing liquid nozzle 8 toward the central region of the upper surface of the substrate W (polymer-containing liquid supplying step, polymer-containing liquid discharging step). The polymer-containing liquid discharged from the polymer-containing liquid nozzle 8 lands in the central region of the upper surface of the substrate W.

[0091] When the polymer-containing liquid is supplied to the upper surface of the substrate W, the substrate W is rotated at a low speed (for example, 10 rpm) (substrate rotation step, low-speed rotation step). Alternatively, when the polymer-containing liquid is supplied to the upper surface of the substrate W, the rotation of the substrate W is stopped. Therefore, the polymer-containing liquid supplied to the substrate W remains in the central region of the upper surface of the substrate W and forms a polymer-containing liquid core 100. The supply of the polymer-containing liquid from the polymer-containing liquid nozzle 8 continues for a predetermined time, for example, 2 to 4 seconds. The amount of the polymer-containing liquid supplied to the upper surface of the substrate W is about 2 cc.

[0092] Next, as shown in Figures 5B and 5C, a polymer film formation process (step S3) is performed in which the substrate W having the polymer-containing liquid adhering to its upper surface is rotated to form a polymer film 101 (see Figure 5C) on the upper surface of the substrate W.

[0093] Specifically, the polymer-containing liquid valve 50 is closed, and then, as shown in FIG. 5B, the rotation of the substrate W is accelerated so that the rotation speed of the substrate W reaches a predetermined spin-off speed (rotation acceleration step). The spin-off speed is, for example, 1500 rpm. After the polymer-containing liquid valve 50 is closed, the first nozzle moving unit 35 moves the polymer-containing liquid nozzle 8 to its home position.

[0094] The centrifugal force caused by the rotation of the substrate W spreads the polymer-containing liquid constituting the polymer-containing liquid core 100 toward the peripheral edge of the upper surface of the substrate W, and the polymer-containing liquid is spread over the entire upper surface of the substrate W (coating step). A part of the polymer-containing liquid on the substrate W splashes from the peripheral edge of the substrate W to the outside of the substrate W, and the liquid film of the polymer-containing liquid (polymer-containing liquid core 100) on the substrate W is thinned (spin-off step). In the coating step, it is not necessary for the polymer-containing liquid to splash to the outside of the substrate W, as long as the entire upper surface of the substrate W is covered with the polymer-containing liquid.

[0095] The centrifugal force caused by the rotation of the substrate W acts not only on the polymer-containing liquid on the substrate W but also on the gas in contact with the polymer-containing liquid on the substrate W. Therefore, the centrifugal force creates an airflow that moves the gas from the center to the periphery of the substrate W. This airflow removes the gaseous solvent in contact with the polymer-containing liquid on the substrate W from the atmosphere in contact with the substrate W. This promotes evaporation (volatilization) of the solvent from the polymer-containing liquid on the substrate W. A polymer film 101 is formed by evaporating a portion of the solvent in the polymer-containing liquid (polymer film formation process). The substrate rotation unit 21 is an example of a polymer film formation unit that rotates the substrate W held by the substrate holding unit 20 to form the polymer film 101 from the polymer-containing liquid adhering to the upper surface (main surface) of the substrate W. The polymer film 101 contains less solvent than the polymer-containing liquid and therefore has a higher viscosity than the polymer-containing liquid. Therefore, despite the rotation of the substrate W, the polymer film 101 is not completely removed from the substrate W but remains on the substrate W. Rotation of the substrate W at the spin-off speed continues for, for example, 30 seconds.

[0096] Due to the action of the acidic polymer in the polymer film 101 formed on the substrate W, metallic foreign matter is pulled away from the upper surface of the substrate W and adsorbed onto the polymer film 101 (metallic foreign matter adsorption process). Due to the action of the oxidizing agent in the semi-solid polymer film 101, adsorption of the metallic foreign matter by the acidic polymer is promoted (adsorption promotion process).

[0097] Next, a polymer film heating step (step S4) is performed to heat the polymer film 101 on the substrate W. Specifically, the heating fluid valve 54 is opened. As a result, as shown in FIG. 5C, a heating fluid is supplied to the lower surface (opposite surface) of the substrate W, and the substrate W is heated by the heating fluid (substrate heating step, fluid heating step). The heating fluid supplied to the lower surface of the substrate W heats the polymer film 101 through the substrate W (polymer film heating step). While the heating fluid is being supplied to the lower surface of the substrate W, the substrate W is rotated at a predetermined fluid heating speed. The fluid heating speed is, for example, 800 rpm.

[0098] Heating evaporates the solvent in the polymer film 101, increasing the concentration of the acidic polymer in the polymer film 101 (polymer concentration step). This promotes the adsorption of metallic foreign matter to the polymer film 101 by the action of the acidic polymer. This allows the highly concentrated acidic polymer to act on the metallic foreign matter. This allows the metallic foreign matter to be effectively adsorbed from the main surface of the substrate W.

[0099] Unlike the first embodiment, in a method of removing metallic foreign matter from a substrate W by continuously supplying a liquid containing a volatile substance as an acidic component, such as a mixture of hydrochloric acid and hydrogen peroxide (HPM liquid, etc.), to the upper surface of the substrate W, the volatile substance, hydrogen chloride (an acidic component), volatilizes as the solvent in the liquid evaporates. Therefore, there is a risk that the evaporation of the solvent will not form a semi-solid or solid film or increase the concentration of the acidic component.

[0100] The temperature of the heating fluid used to heat the substrate W is below the boiling point of the solvent, which allows the solvent to evaporate appropriately from the polymer film 101 on the substrate W. This increases the concentration of the acidic polymer dissolved in the solvent in the polymer film 101, while preventing the solvent from evaporating completely and being completely removed from the polymer film 101.

[0101] In this embodiment, the substrate W is heated by a simple method of supplying a heating fluid to the lower surface (opposite surface) of the substrate W. The heating fluid supplied to the lower surface of the rotating substrate W spreads evenly toward the peripheral edge of the lower surface of the substrate W due to the action of centrifugal force. Therefore, the entire substrate W can be heated evenly, and the solvent can be evaporated evenly from the entire upper surface of the substrate W.

[0102] Next, a rinsing step (step S5) is performed in which the upper surface of the substrate W is washed with a rinsing liquid to remove the polymer film 101 on the substrate W. Specifically, the second nozzle moving unit 36 ​​moves the rinsing liquid nozzle 9 to a processing position. The processing position of the rinsing liquid nozzle 9 is, for example, a central position. With the rinsing liquid nozzle 9 positioned at the processing position, the rinsing liquid valve 52 is opened. As a result, as shown in FIG. 5D , the rinsing liquid is supplied (discharged) from the rinsing liquid nozzle 9 toward the central region of the upper surface of the substrate W on which the polymer film 101 is formed (rinsing liquid supply step, rinsing liquid discharge step). Before the supply of the rinsing liquid to the substrate W begins, the heating fluid valve 54 is closed, and the discharge of the heating fluid from the heating fluid nozzle 10 is stopped.

[0103] The rinse liquid supplied to the substrate W dissolves the polymer film 101 on the substrate W (polymer film dissolving step). By continuing to supply the rinse liquid to the substrate W, the polymer film 101 is removed from the upper surface of the substrate W (polymer film removing step), as shown in FIG. 5E. The polymer film 101 is removed from the upper surface of the substrate W by the dissolving action of the rinse liquid and the flow of rinse liquid formed by the continuous supply of the rinse liquid and the rotation of the substrate W. Therefore, the rinse liquid supply unit 12 and the substrate rotation unit 21 function as a polymer film removing unit that supplies the rinse liquid to the upper surface (main surface) of the substrate W to remove the polymer film 101 from the upper surface of the substrate W.

[0104] Next, a spin dry process (step S6) is performed in which the substrate W is rotated at high speed to dry the upper surface of the substrate W. Specifically, the rinse liquid valve 52 is closed. This stops the supply of the rinse liquid to the upper surface of the substrate W.

[0105] Then, the spin motor 25 accelerates the rotation of the substrate W, causing it to rotate at high speed. The substrate W is rotated at a drying speed, for example, 1500 rpm. As a result, a large centrifugal force acts on the rinse liquid on the substrate W, and the rinse liquid on the substrate W is scattered around the periphery of the substrate W.

[0106] Then, the spin motor 25 stops the rotation of the substrate W. The guard lifting unit 33 moves the multiple guards 30 to the lower position.

[0107] The transport robot CR enters the processing unit 2, scoops up the processed substrate W from the chuck pins 23 of the substrate holding unit 20, and carries it out of the processing unit 2 (substrate carrying-out step: step S7). The substrate W is handed over from the transport robot CR to the transport robot IR, and is stored in the carrier C by the transport robot IR.

[0108] <Removal of metal foreign matter> Next, a description will be given of how metallic foreign matter is removed from the main surface (the upper surface of the substrate W in the substrate processing described above) of the substrate W. Figures 6A to 6C are schematic views for explaining how metallic foreign matter 102 adhering to the main surface of the substrate W is removed.

[0109] 6A is a schematic diagram showing the state of the main surface of the substrate W before the polymer-containing liquid is supplied. Before the polymer-containing liquid is supplied, metallic foreign matter 102 adheres to the main surface of the substrate W. Specifically, the metallic foreign matter 102 is bonded to the main surface of the substrate W. More specifically, the metallic foreign matter 102 is bonded to a substance that constitutes a surface layer of the main surface of the substrate W. The surface layer of the main surface of the substrate W is constituted by, for example, an insulator layer such as a silicon oxide layer (SiO layer) or a silicon nitride layer (SiN layer), or a semiconductor layer such as a silicon layer.

[0110] FIG. 6B shows a state in which a polymer film 101 has been formed on the main surface of the substrate W.

[0111] As shown in Figure 6B, when the polymer film 101 is formed, the acidic polymer 105 in the polymer film 101 breaks the bond between the oxygen atom of the hydroxyl group (OH) exposed from the main surface of the substrate W and the metallic foreign matter 102. This ionizes the metallic foreign matter 102. The ionized metallic foreign matter 102 is adsorbed to the acidic polymer 105. Figure 6B shows an example in which the acidic polymer 105 is polyacrylic acid.

[0112] Specifically, the acidic polymer 105 releases protons to the solvent and is negatively charged. Therefore, the acidic polymer 105 adsorbs (attracts) the ionized foreign metal particles 102 (metal ions) by Coulomb force, and separates the foreign metal particles 102 from the substrate W (ion adsorption process, foreign metal particle adsorption process). As a result, the foreign metal particles 102 are adsorbed onto the polymer film 101 (foreign metal particle adsorption process). Because the solvent remains in the polymer film, the solvent functions as a medium for the acidic polymer to exchange ions (protons) within the polymer film.

[0113] The ionization of the metallic foreign matter 102 is promoted by an oxidizing agent (ionization promotion step). Specifically, the metallic foreign matter 102 is ionized by the action of the oxidizing agent. - ) is removed and becomes a metal ion (cation). Since the ionization of the foreign metal matter 102 is promoted by the oxidizing agent, the adsorption of the ionized foreign metal matter 102 by the acidic polymer 105 is promoted (adsorption promotion step).

[0114] In this way, the metal foreign matter 102 is ionized by the acidic polymer 105 in the polymer film 101 and is adsorbed onto the polymer film 101. Furthermore, the oxidizing agent in the polymer film 101 promotes the ionization of the metal foreign matter 102. Therefore, the synergistic effect of the oxidizing agent and the acidic polymer 105 allows the metal foreign matter 102 to be effectively adsorbed onto the polymer film 101.

[0115] Because the action of the polymer film 101 has separated the metallic foreign matter 102 from the main surface of the substrate W, as shown in FIG. 6C , by supplying a rinse liquid to the main surface of the substrate W, the polymer film 101 is dissolved in the rinse liquid and is discharged together with the rinse liquid outside the substrate W. The metallic foreign matter 102, together with the polymer film 101, is carried by the rinse liquid along the main surface of the substrate W and is eventually discharged outside the substrate W. This removes the metallic foreign matter 102 from the main surface of the substrate W (metallic foreign matter removal step). This cleans the main surface of the substrate W (rinsing step).

[0116] According to the first embodiment, the semi-solid polymer film 101 is formed by rotating the substrate W to which the polymer-containing liquid has been supplied. Due to the action of the acidic polymer in the semi-solid polymer film 101, the metallic foreign matter 102 is pulled away from the main surface of the substrate W and adsorbed onto the polymer film 101 (metallic foreign matter adsorption process). Then, due to the action of the oxidizing agent in the semi-solid polymer film 101, adsorption of the metallic foreign matter 102 by the acidic polymer is promoted (adsorption promotion process). Therefore, by forming the polymer film 101 with an amount of polymer-containing liquid sufficient to cover the entire main surface of the substrate W and then removing the polymer film 101 with a rinse liquid, the metallic foreign matter 102 can be successfully removed from the main surface of the substrate W without continuously supplying the polymer-containing liquid to the main surface of the substrate W.

[0117] Therefore, the amount of polymer-containing liquid used can be reduced because the metallic foreign matter 102 can be sufficiently removed without immersing the substrate W in the polymer-containing liquid, thereby reducing the environmental load.

[0118] According to the first embodiment, the polymer-containing liquid is a mixed liquid obtained by mixing an acidic polymer liquid containing 10 wt % of an acidic polymer and a liquid oxidizing agent containing 30 wt % of an oxidizing agent at a volume ratio of 1:6. Ratio of If the rate is high, the metallic foreign matter 102 can be removed from the main surface of the substrate W more efficiently.

[0119] According to the first embodiment, the polymer-containing liquid is stored in the polymer-containing liquid tank 80. Therefore, the acidic polymer and the oxidizing agent are mixed before being supplied from the polymer-containing liquid tank 80 to the polymer-containing liquid nozzle 8. Therefore, the ratio of the acidic polymer and the oxidizing agent in the polymer-containing liquid can be adjusted with high precision, compared to a configuration in which the acidic polymer and the oxidizing agent are mixed in the path from the polymer-containing liquid tank 80 to the polymer-containing liquid nozzle 8 or on the main surface of the substrate W.

[0120] In the above-described embodiment, the metallic foreign matter 102 is detached from the main surface of the substrate W by the action of the oxidizing agent and acidic polymer in the polymer film 101. However, the metallic foreign matter 102 can also be detached from the main surface of the substrate W by the action of the oxidizing agent and acidic polymer present in the polymer-containing liquid before the polymer film 101 is formed. However, as described above, the oxidizing agent and acidic polymer dissolved in the solvent in the polymer film 101 have higher concentrations than the oxidizing agent and acidic polymer in the polymer-containing liquid. Because the high concentration of acidic polymer can act on the metallic foreign matter 102, the metallic foreign matter 102 can be effectively adsorbed to the polymer film 101. Therefore, by forming the polymer film 101 on the main surface of the substrate W, the metallic foreign matter 102 can be effectively detached from the main surface of the substrate W. Furthermore, when the polymer film is removed with a rinse solution, the metallic foreign matter 102 can be further removed from the main surface of the substrate W.

[0121] Because the polymer film 101 contains a solvent and is semi-solid, the acidic polymer acts more easily on the metallic foreign matter 102 than when the polymer film 101 is solid. Unlike the first embodiment, if the solvent completely evaporates immediately after the polymer film 101 is formed, turning it into a solid film, the acidic polymer is less likely to function as an acid. Therefore, the metallic foreign matter 102 is less likely to be adsorbed by the polymer film 101 than when the polymer film 101 is semi-solid. In the first embodiment, the polymer film 101 is maintained in a semi-solid state from the time it is formed until it is removed. Therefore, the metallic foreign matter 102 is effectively adsorbed by the polymer film 101.

[0122] <Another Example of Substrate Processing According to the First Embodiment> Fig. 7 is a flow chart illustrating another example of substrate processing performed by the substrate processing apparatus 1. Fig. 8 is a schematic diagram illustrating the state of a substrate when another example of substrate processing performed by the substrate processing apparatus 1 is being performed.

[0123] The main difference between this substrate processing and the substrate processing shown in Figures 4 and 5A to 5E is that, as shown in Figure 7, instead of the polymer film heating process (step S4), a substrate rotation stopping process (step S10, rotation stop maintenance process) is performed in which the rotation of the substrate W is kept stopped for a predetermined time without heating the polymer film 101.

[0124] More specifically, after the polymer film 101 is formed on the upper surface of the substrate W (after step S3), the spin motor 25 stops the rotation of the substrate W (substrate rotation stopping step), as shown in Fig. 8. Thereafter, the polymer film 101 is left standing without rotating the substrate W for a predetermined standing time (polymer film standing step). "Leaving the polymer film 101 standing" means leaving the polymer film 101 on the substrate W with the rotation of the substrate W stopped.

[0125] By employing this substrate processing method, excessive evaporation of the solvent from the polymer film 101 on the main surface of the substrate W can be suppressed by stopping the rotation of the substrate W. This prevents the polymer film 101 from completely solidifying, and allows the metal foreign matter 102 to be effectively adsorbed to the polymer film 101 by the action of the oxidizing agent and acidic polymer in the polymer film 101.

[0126] The solvent in the polymer film 101 evaporates while the polymer film 101 is left standing, and therefore the concentration (density) of the acidic polymer in the polymer film 101 increases (polymer concentration step).

[0127] <Modification of the substrate processing apparatus according to the first embodiment> Fig. 9 is a schematic diagram for explaining a first modified example of the substrate processing apparatus 1. Fig. 10 is a schematic diagram for explaining a second modified example of the substrate processing apparatus 1. In the first and second modified examples of the substrate processing apparatus 1, the method of supplying the polymer-containing liquid to the upper surface of the substrate W is different from the example shown in Fig. 2.

[0128] 9, a liquid oxidizing agent containing an oxidizing agent and a solvent and an acidic polymer liquid containing an acidic polymer and a solvent are mixed in a pipe to form a polymer-containing liquid, and the polymer-containing liquid formed in the pipe is discharged from a polymer-containing liquid nozzle 8 and supplied to the upper surface of the substrate W (polymer-containing liquid supplying step). The liquid oxidizing agent contains, for example, at least one of hydrogen peroxide water and ozone water.

[0129] In detail, the polymer-containing liquid supply unit 11 according to the first modified example includes a polymer-containing liquid nozzle 8 that discharges a polymer-containing liquid, a polymer-containing liquid piping 40 that guides the polymer-containing liquid to the polymer-containing liquid nozzle 8, a liquid oxidant piping 43 to which a liquid oxidant is supplied from a liquid oxidant tank 81 that stores the liquid oxidant, an acidic polymer liquid piping 44 to which an acidic polymer liquid is supplied from an acidic polymer liquid tank 82 that stores an acidic polymer liquid, and a mixing piping 45 that is connected to the liquid oxidant piping 43 and the acidic polymer liquid piping 44 and mixes the liquid oxidant and the acidic polymer liquid to form a polymer-containing liquid, and sends the polymer-containing liquid to the polymer-containing liquid piping 40.

[0130] The polymer-containing liquid supply unit 11 includes a liquid oxidant valve 56 interposed in the liquid oxidant pipe 43 and opening and closing the flow path within the liquid oxidant pipe 43, a liquid oxidant flow rate control valve 57 interposed in the liquid oxidant pipe 43 and adjusting the flow rate of the liquid oxidant within the liquid oxidant pipe 43, an acidic polymer liquid valve 58 interposed in the acidic polymer liquid pipe 44 and opening and closing the flow path within the acidic polymer liquid pipe 44, an acidic polymer liquid flow rate control valve 59 interposed in the acidic polymer liquid pipe 44 and adjusting the flow rate of the liquid oxidant within the acidic polymer liquid pipe 44, and a polymer-containing liquid valve 50 interposed in the polymer-containing liquid pipe 40 and opening and closing the flow path within the polymer-containing liquid pipe 40.

[0131] A liquid oxidizer pump 71 and an acidic polymer liquid pump 72 are provided in the liquid oxidizer pipe 43 and the acidic polymer liquid pipe 44, respectively. Therefore, when the liquid oxidizer valve 56 is opened, the liquid oxidizer in the liquid oxidizer tank 81 is pumped to the liquid oxidizer pipe 43 by the liquid oxidizer pump 71. When the acidic polymer liquid valve 58 is opened, the acidic polymer liquid in the acidic polymer liquid tank 82 is pumped to the acidic polymer liquid pipe 44 by the acidic polymer liquid pump 72. When the polymer-containing liquid valve 50 is opened, the polymer-containing liquid formed in the mixing pipe 45 is discharged downward in a continuous flow from the discharge port of the polymer-containing liquid nozzle 8 and supplied onto the upper surface of the substrate W (polymer-containing liquid supplying step). The ratio of the acidic polymer and the oxidizer in the polymer-containing liquid is adjusted by adjusting the apertures of the liquid oxidizer flow rate control valve 57 and the acidic polymer liquid flow rate control valve 59.

[0132] 10, in the second modification, a liquid oxidizing agent and an acidic polymer liquid are supplied from separate nozzles onto the upper surface of the substrate W, and the acidic polymer liquid and the liquid oxidizing agent are mixed together to form a polymer-containing liquid on the upper surface of the substrate W. The polymer-containing liquid is formed on the upper surface of the substrate W, and thereby the polymer-containing liquid is supplied to the upper surface of the substrate W (polymer-containing liquid supplying step).

[0133] More specifically, the polymer-containing liquid supply unit 11 according to the second modification includes a liquid oxidant nozzle 14 that discharges a liquid oxidant toward the upper surface of the substrate W held on the spin chuck 5, and an acidic polymer liquid nozzle 15 that discharges an acidic polymer liquid toward the upper surface of the substrate W held on the spin chuck 5. The liquid oxidant nozzle 14 is connected to the liquid oxidant pipe 43 of the first modification, and the acidic polymer liquid nozzle 15 is connected to the acidic polymer liquid pipe 44 of the first modification.

[0134] The polymer-containing liquid supply unit 11 according to the second modification further includes a liquid oxidant pipe 43, a liquid oxidant valve 56, a liquid oxidant flow rate control valve 57, an acidic polymer liquid pipe 44, an acidic polymer liquid valve 58, and an acidic polymer liquid flow rate control valve 59.

[0135] In this embodiment, the liquid oxidant nozzle 14 and the acidic polymer liquid nozzle 15 are scan nozzles that are movable in the horizontal direction. The liquid oxidant nozzle 14 and the acidic polymer liquid nozzle 15 are moved in the horizontal direction by a third nozzle movement unit 37 and a fourth nozzle movement unit 38, respectively. The third nozzle movement unit 37 and the fourth nozzle movement unit 38 have the same configuration as the first nozzle movement unit 35.

[0136] When the liquid oxidant valve 56 is opened, the liquid oxidant in the liquid oxidant tank 81 is pumped by the liquid oxidant pump 71 into the liquid oxidant pipe 43, and is then discharged downward in a continuous flow from the outlet of the liquid oxidant nozzle 14. When the acidic polymer liquid valve 58 is opened, the acidic polymer liquid in the acidic polymer liquid tank 82 is pumped by the acidic polymer liquid pump 72 into the acidic polymer liquid pipe 44, and is then discharged downward in a continuous flow from the outlet of the acidic polymer liquid nozzle 15. When both the liquid oxidant valve 56 and the acidic polymer liquid valve 58 are open, a polymer-containing liquid is supplied to the upper surface of the substrate W (polymer-containing liquid supplying step).

[0137] Furthermore, in the substrate processing apparatus 1 of the first modified example shown in FIG. 9 and the second modified example shown in FIG. 10, unlike the substrate processing described above, it is also possible to form a polymer-containing liquid on the substrate W by supplying a liquid oxidizing agent to the upper surface of the substrate W, and then supplying an acidic polymer liquid while continuing to supply the liquid oxidizing agent.

[0138] <Configuration of Substrate Processing Apparatus According to Second Embodiment> Fig. 11 is a schematic cross-sectional view for explaining an example of the configuration of a processing unit 2 provided in a substrate processing apparatus 1P according to the second embodiment. In Fig. 11, components equivalent to those shown in Figs. 1 to 10 described above are given the same reference numerals as in Fig. 1, etc., and descriptions thereof will be omitted. The same applies to Fig. 12 described later.

[0139] The substrate processing apparatus 1P according to the second embodiment is mainly different from the substrate processing apparatus 1 according to the first embodiment (see FIG. 2) in that a heater unit 6 is provided instead of the heating fluid supply unit 13.

[0140] The heater unit 6 is an example of a substrate heating unit that heats the entire substrate W. The heater unit 6 has the form of a disk-shaped hot plate. The heater unit 6 is disposed between the upper surface of the spin base 22 and the lower surface of the substrate W. The heater unit 6 has a facing surface 6a that faces the lower surface of the substrate W from below.

[0141] The heater unit 6 includes a plate body 61 and a heater 62. The plate body 61 is slightly smaller than the substrate W in a plan view. The upper surface of the plate body 61 forms the facing surface 6a. The heater 62 may be a resistor built into the plate body 61. The facing surface 6a is heated by passing electricity through the heater 62. The facing surface 6a is heated to, for example, 195°C. The temperature of the facing surface 6a may be a temperature equal to or higher than 60°C and lower than 100°C.

[0142] An elevator shaft 66 extending vertically along the rotation axis A1 is connected to the underside of the heater unit 6. The elevator shaft 66 passes through a through-hole 22a formed in the center of the spin base 22 and the hollow rotation shaft 24. A power supply line 63 passes through the elevator shaft 66.

[0143] The heater 62 is supplied with power from a heater power supply unit 64 via a power supply line 63. The heater power supply unit 64 is, for example, a power supply. The heater unit 62 is raised and lowered by a heater lifting unit 65.

[0144] The heater lifting unit 65 includes an actuator (not shown), such as an electric motor or an air cylinder, that drives the lifting shaft 66 to move up and down. The heater lifting unit 65 is also called a heater lifter. The heater lifting unit 65 raises and lowers the heater unit 6 via the lifting shaft 66. The heater unit 6 is raised and lowered by the heater lifting unit 65, and can be positioned at a lower position and an upper position. The heater lifting unit 65 can position the heater unit 6 not only at the lower position and the upper position, but also at any position between the lower and upper positions.

[0145] When the heater unit 6 is raised, it can receive the substrate W from the plurality of chuck pins 23 in the open state. The heater unit 6 can heat the substrate W by being positioned by the heater lifting unit 65 at a contact position where it contacts the lower surface of the substrate W or at a proximity position where it is close to the lower surface of the substrate W.

[0146] <Example of Substrate Processing According to Second Embodiment> FIG. 12 shows the substrate processing apparatus 1P according to the second embodiment. Substrate processing 5A to 5E are schematic diagrams illustrating the state of the substrate W when an example is being performed. The substrate processing apparatus 1P according to the second embodiment can perform the same substrate processing (FIGS. 4 to 5E) as the substrate processing apparatus 1 according to the first embodiment, except that the heating method in the polymer film heating step (step S4) is different.

[0147] As shown in FIG. 12, in the polymer film heating step (step S4) of the substrate processing according to the second embodiment, the heater unit 6 is disposed in a proximal position, whereby the substrate W is heated by radiant heat (substrate heating step, heater heating step). The heater unit 6 heats the polymer film 101 through the substrate W (polymer film heating step). While the heater unit 6 is disposed in proximity to the substrate W, the substrate W is rotated at a predetermined heater heating speed. The heater heating speed is, for example, 800 rpm. In the subsequent rinsing step (step S5), the heater unit 6 may be moved to the lower position, or may be disposed in the proximal position until the spin dry (step S6) is completed.

[0148] When the heater unit 6 is positioned in close proximity to heat the substrate W and the polymer film 101, the temperature of the opposing surface 6a is preferably set to a temperature that can be heated so that the temperature of the substrate W does not exceed the boiling point of the solvent in the polymer film 101, and the temperature of the opposing surface 6a is adjusted to a temperature higher than the boiling point of the solvent in the polymer film 101 (for example, 100°C or higher).

[0149] 12, the polymer film heating step may be performed by placing the heater unit 6 at the contact position. When the heater unit 6 is at the contact position, rotation of the substrate W is restricted, so that the polymer film 101 on the substrate W remains stationary. When the heater unit 6 is at the contact position, the temperature of the facing surface 6a is preferably lower than the boiling point of the solvent in the polymer film 101. When the solvent is DIW, the temperature of the facing surface 6a is preferably 60°C or higher and lower than 100°C.

[0150] According to the second embodiment, the same effects as those of the first embodiment can be achieved. The same modifications as those of the first embodiment can also be applied to the second embodiment. That is, a liquid oxidizing agent and an acidic polymer liquid may be mixed in a pipe to form a polymer-containing liquid, and the polymer-containing liquid formed in the pipe may be ejected from the polymer-containing liquid nozzle 8. Alternatively, the liquid oxidizing agent and the acidic polymer liquid may be supplied to the upper surface of the substrate W from separate nozzles, and the acidic polymer liquid and the liquid oxidizing agent may be mixed on the upper surface of the substrate W to form the polymer-containing liquid.

[0151] <Configuration of the Substrate Processing Apparatus According to the Third Embodiment> Fig. 13 is a schematic cross-sectional view for explaining an example of the configuration of a processing unit 2 provided in a substrate processing apparatus 1Q according to a third embodiment. In Fig. 13, components equivalent to those shown in Figs. 1 to 12 described above are given the same reference numerals as in Fig. 1, etc., and descriptions thereof will be omitted. The same applies to Figs. 14 to 16 described below.

[0152] The substrate processing apparatus 1Q according to the third embodiment is mainly different from the substrate processing apparatus 1 according to the first embodiment (see FIG. 2) in that the polymer-containing liquid contains a conductive polymer such as polyacetylene in addition to a solvent, an acidic polymer, and an oxidizing agent.

[0153] The conductive polymer functions as a medium for the acidic polymer to release protons, similar to a solvent. The conductive polymer is not limited to polyacetylene. The conductive polymer is a conjugated polymer having conjugated double bonds. Examples of the conjugated polymer include aliphatic conjugated polymers such as polyacetylene, aromatic conjugated polymers such as poly(p-phenylene), mixed conjugated polymers such as poly(p-phenylenevinylene), heterocyclic conjugated polymers such as polypyrrole, polythiophene, and poly(3,4-ethylenedioxythiophene) (PEDOT), heteroatom-containing conjugated polymers such as polyaniline, double-chain conjugated polymers such as polyacenes, two-dimensional conjugated polymers such as graphene, and mixtures thereof.

[0154] The polymer-containing liquid tank 80 is replenished with, for example, a conductive polymer liquid, in addition to the liquid oxidizing agent and the acidic polymer liquid, via a refilling pipe 86. A plurality of refilling valves 87 for opening and closing the flow paths in the corresponding refilling pipes 84-86 are provided in the respective refilling pipes 84-86.

[0155] Unlike the example shown in Fig. 13, the polymer-containing liquid may be replenished through a polymer-containing liquid replenishment pipe (not shown). The conductive polymer liquid is a liquid containing the above-mentioned solvent and a conductive polymer.

[0156] <Example of Substrate Processing According to the Third Embodiment> By using the substrate processing apparatus 1Q according to the third embodiment, it is possible to perform substrate processing similar to that according to the first embodiment (see FIGS. 4 to 5E). That is, a polymer-containing liquid containing an acidic polymer, a liquid oxidizing agent, and a conductive polymer is stored in the polymer-containing liquid tank 80 (preparation step). Therefore, the polymer film 101 formed in the polymer film formation step (step S3) contains the conductive polymer in addition to the acidic polymer and the oxidizing agent.

[0157] Because the conductive polymer functions as a medium for the acidic polymer to release protons, the acidic polymer can be ionized by the action of the conductive polymer while the polymer film 101 is formed on the substrate W. Therefore, even when the solvent has completely disappeared from the polymer film 101 and the polymer film is in a solid state, the acidic polymer can be ionized and the ionized acidic polymer can effectively act on the metallic foreign matter 102.

[0158] <Modification of the Substrate Processing Apparatus According to the Third Embodiment> Fig. 14 is a schematic diagram illustrating a first modified example of the substrate processing apparatus 1Q. Fig. 15 is a schematic diagram illustrating a second modified example of the substrate processing apparatus 1Q. Fig. 16 is a schematic diagram illustrating a third modified example of the substrate processing apparatus 1Q. Fig. 17 is a schematic diagram illustrating a fourth modified example of the substrate processing apparatus 1Q.

[0159] In the first to fourth modified examples of the substrate processing apparatus 1Q, the method of supplying the polymer-containing liquid to the upper surface of the substrate W is different from the example shown in Fig. 13. In the modified examples shown in Figs. 14 to 17, for the sake of convenience, the processing cup 7 and the rinse liquid nozzle 9 are not shown. Although pumps, valves, nozzle movement units, etc. are not described, this does not mean that these components do not exist, and in reality, these components are provided in appropriate positions.

[0160] In the first modified example shown in FIG. 14, a liquid oxidizing agent, an acidic polymer liquid, and a conductive polymer liquid are mixed in a mixing pipe 45 to form a polymer-containing liquid, and the polymer-containing liquid formed in the mixing pipe 45 is ejected from a polymer-containing liquid nozzle 8 and supplied to the upper surface of the substrate W (polymer-containing liquid supplying step).

[0161] More specifically, a conductive polymer liquid pipe 46, which guides the conductive polymer liquid in the conductive polymer liquid tank 83 to the mixing pipe 45, is connected to the mixing pipe 45 along with the liquid oxidant pipe 43 and the acidic polymer liquid pipe 44, and the conductive polymer liquid, acidic polymer liquid, and liquid oxidant are mixed in the mixing pipe 45. In this modification, the mixing pipe 45 and the conductive polymer liquid pipe 46 are also included in the polymer-containing liquid supply unit 11.

[0162] 15 , an acidic polymer liquid and a conductive polymer liquid are mixed in a mixing tank 90 to form a mixed polymer liquid. The acidic polymer liquid and the conductive polymer liquid are supplied to the mixing tank 90 from two refill pipes 84 and 86, respectively. The mixed polymer liquid formed in the mixing tank 90 is supplied to the mixed polymer liquid nozzle 16 via the mixed polymer liquid piping 47. The mixed polymer liquid is ejected from the mixed polymer liquid nozzle 16 toward the upper surface of the substrate W and supplied to the upper surface of the substrate W (mixed polymer liquid supplying step).

[0163] In parallel with the supply of the mixed polymer liquid to the upper surface of the substrate W, a liquid oxidizing agent is supplied toward the upper surface of the substrate W from a nozzle (liquid oxidizing agent nozzle 14) different from the mixed polymer liquid nozzle 16, whereby the mixed polymer liquid and the liquid oxidizing agent are mixed to form a polymer-containing liquid on the upper surface of the substrate W. The polymer-containing liquid is formed on the upper surface of the substrate W, and thereby the polymer-containing liquid is supplied to the upper surface of the substrate W (polymer-containing liquid supplying step).

[0164] 16, an acidic polymer liquid supplied from an acidic polymer liquid pipe 44 and a conductive polymer liquid supplied from a conductive polymer liquid pipe 46 are mixed in a mixing pipe 45 to form a mixed polymer liquid. The mixed polymer liquid mixed in the mixing pipe 45 is supplied to a mixed polymer liquid nozzle 16 via a mixed polymer liquid pipe 47. The mixed polymer liquid is discharged from the mixed polymer liquid nozzle 16 and supplied to the upper surface of the substrate W (mixed polymer liquid supplying step).

[0165] In parallel with the supply of the mixed polymer liquid to the upper surface of the substrate W, a liquid oxidizing agent is supplied toward the upper surface of the substrate W from a nozzle (liquid oxidizing agent nozzle 14) different from the mixed polymer liquid nozzle 16, whereby the mixed polymer liquid and the liquid oxidizing agent are mixed to form a polymer-containing liquid on the upper surface of the substrate W. The polymer-containing liquid is formed on the upper surface of the substrate W, and thereby the polymer-containing liquid is supplied to the upper surface of the substrate W (polymer-containing liquid supplying step).

[0166] 17, an acidic polymer liquid, a liquid oxidizing agent, and a conductive polymer liquid are supplied onto the upper surface of the substrate W from separate nozzles, and these liquids are mixed on the upper surface of the substrate W to form a polymer-containing liquid on the upper surface of the substrate W. The polymer-containing liquid is formed on the upper surface of the substrate W, and the polymer-containing liquid is supplied onto the upper surface of the substrate W (polymer-containing liquid supplying step).

[0167] Specifically, the acidic polymer liquid is discharged from the acidic polymer liquid nozzle 15, and the liquid oxidizing agent is discharged from the liquid oxidizing agent nozzle 14. The conductive polymer liquid is discharged through the conductive polymer liquid pipe 46 connected to the conductive polymer liquid tank 83. of The conductive polymer liquid is supplied to the conductive polymer liquid nozzle 17 via the nozzle 17. The conductive polymer liquid is discharged from the conductive polymer liquid nozzle 17 and supplied onto the upper surface of the substrate W.

[0168] <Configuration of Substrate Processing Apparatus According to Fourth Embodiment> Fig. 18 is a schematic diagram for explaining a configuration example of a processing unit 2 provided in a substrate processing apparatus 1R according to a fourth embodiment. In Fig. 18, components equivalent to those shown in Figs. 1 to 17 described above are given the same reference numerals as in Fig. 1, etc., and descriptions thereof will be omitted. The same applies to Figs. 19 and 21 described below.

[0169] The substrate processing apparatus 1R according to the fourth embodiment is mainly different from the substrate processing apparatus 1 according to the first embodiment (see FIG. 2) in that the polymer-containing liquid discharged from the polymer-containing liquid nozzle 8 does not contain an oxidizing agent, and that a solidification cleaning liquid can be supplied to the substrate W. In the fourth embodiment, an acidic polymer liquid is used as the polymer-containing liquid.

[0170] The acidic polymer according to the fourth embodiment preferably has a higher acidity than the polymer-containing liquid containing an oxidizing agent, and the pH of the polymer-containing liquid is 1 or less. In this case, even if the acidic polymer does not contain an oxidizing agent, it can sufficiently remove metallic foreign matter from the upper surface of the substrate W. The acidic polymer is, for example, a carboxyl group-containing polymer, a sulfo group-containing polymer, or a mixture thereof. Details of the carboxyl group-containing polymer and the sulfo group-containing polymer are as described above.

[0171] The substrate processing apparatus 1R further includes an oxide film removal liquid nozzle 150 that sprays an oxide film removal liquid toward the upper surface of the substrate W held on the spin chuck 5, a solidification cleaning liquid nozzle 151 that sprays a solidification cleaning liquid toward the upper surface of the substrate W held on the spin chuck 5, a solidification cleaning film removal liquid nozzle 152 that sprays a solidification cleaning film removal liquid toward the upper surface of the substrate W held on the spin chuck 5, and an organic solvent nozzle 153 that sprays an organic solvent toward the upper surface of the substrate W held on the spin chuck 5.

[0172] The oxide film removal liquid discharged from the oxide film removal liquid nozzle 150 is a liquid that removes an oxide film (for example, a native oxide film) such as silicon oxide exposed from the upper surface of the substrate W. The oxide film removal liquid is, for example, hydrofluoric acid.

[0173] The oxide film removing liquid nozzle 150 is connected to one end of an oxide film removing liquid pipe 160 that guides the oxide film removing liquid to the oxide film removing liquid nozzle 150. The oxide film removing liquid pipe 160 is provided with an oxide film removing liquid valve 170A that opens and closes a flow path in the oxide film removing liquid pipe 160, and an oxide film removing liquid flow rate adjustment valve 170B that adjusts the flow rate of the oxide film removing liquid in the flow path. When the oxide film removing liquid valve 170A is opened, the oxide film removing liquid is discharged from the oxide film removing liquid nozzle 150 toward the top surface of the substrate W at a flow rate that corresponds to the opening of the oxide film removing liquid flow rate adjustment valve 170B.

[0174] The solidified cleaning liquid discharged from the solidified cleaning liquid nozzle 151 contains components that form a semi-solid or solid solidified cleaning film. The solidified cleaning liquid contains, for example, a low-solubility component, a high-solubility component that is more soluble in the removal liquid than the low-solubility component, and a solvent that dissolves the low-solubility component and the high-solubility component. The solvent is, for example, an organic solvent such as IPA (isopropanol).

[0175] The low-solubility component is, for example, a polymer. Specifically, the low-solubility component may include at least one of novolak, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof.

[0176] The highly soluble component is a crack-promoting component, and may contain a hydrocarbon and a hydroxyl group and / or a carbonyl group in its molecule. The highly soluble component may be a substance represented by at least one of the following (B-1), (B-2), and (B-3):

[0177] (B-1) is a compound containing 1 to 6 structural units of Chemical Formula 1, each of which is bonded via a linking group L1.

[0178] [ka]

[0179] where L1 is a single bond, and C 1~6 alkylene, and Cy1 is selected from at least one of C 5~30 R1 is a hydrocarbon ring of the formula C 1~5 is an alkyl of n b1 is 1, 2, or 3, and n b1’ is 0, 1, 2, 3 or 4.

[0180] (B-2) is a compound represented by chemical formula 2.

[0181] [ka]

[0182] where R 21 , R 22 , R 23 , and R 24 are each independently hydrogen or C 1~5 and L 21 and L 22 are each independently, C 1~20 Alkylene, C 1~20 Cycloalkylene, C 2~4 Alkenylene, C 2~4 Alkynylene of C 6~20 and these groups are C 1~5 may be substituted with alkyl or hydroxy, b2 is 0, 1 or 2.

[0183] (B-3) is a polymer containing a constitutional unit represented by chemical formula 3 and having a weight average molecular weight (Mw) of 500 to 10,000.

[0184] [ka]

[0185] R 25 is -H, -CH3, or -COOH.

[0186] Details of the low solubility component, high solubility component, and solvent contained in the solidification cleaning solution are disclosed, for example, in JP 2019-212889 A. The low solubility component, high solubility component, and solvent may be the "second component," the "first component," and the "solvent" disclosed in JP 2019-212889 A, respectively.

[0187] The solidification-cleaning liquid nozzle 151 is connected to one end of a solidification-cleaning liquid pipe 161 that guides the solidification-cleaning liquid to the solidification-cleaning liquid nozzle 151. A solidification-cleaning liquid valve 171A that opens and closes a flow path in the solidification-cleaning liquid pipe 161, and a solidification-cleaning liquid flow rate adjustment valve 171B that adjusts the flow rate of the solidification-cleaning liquid in the flow path are interposed in the solidification-cleaning liquid pipe 161. When the solidification-cleaning liquid valve 171A is opened, the solidification-cleaning liquid is discharged from the solidification-cleaning liquid nozzle 151 toward the upper surface of the substrate W at a flow rate that corresponds to the opening of the solidification-cleaning liquid flow rate adjustment valve 171B.

[0188] At least a part of the solvent in the solidified cleaning solution supplied to the upper surface of the substrate W evaporates (volatilizes), thereby forming a solid or semi-solid solidified cleaning film containing a low-solubility component and a high-solubility component.

[0189] The solidified cleaning film removal liquid discharged from the solidified cleaning film removal liquid nozzle 152 is a liquid that peels off and removes the solidified cleaning film from the main surface of the substrate W. The solidified cleaning film removal liquid is, for example, an alkaline liquid such as ammonia water.

[0190] When the solidified cleaning film removal liquid is supplied to the solidified cleaning film on the substrate W, highly soluble components in the solidified cleaning film are dissolved, and the dissolution of the highly soluble components triggers cracks in the solidified cleaning film. Continuing to supply the solidified cleaning film removal liquid thereafter causes the solidified cleaning film to break up into film fragments, which are then peeled off from the upper surface of the substrate W. The film fragments are removed from the upper surface of the substrate W together with the solidified cleaning film removal liquid. The film fragments are peeled off from the upper surface of the substrate W while retaining particulate foreign matter such as particles that had been adhering to the upper surface of the substrate W, and therefore the particulate foreign matter is removed from the upper surface of the substrate W. The particulate foreign matter may be composed of, for example, at least one of organic and inorganic matter.

[0191] This method of cleaning the main surface of the substrate W by solidifying the liquid (solidified cleaning liquid) adhering to the main surface of the substrate W to form a solid or semi-solid film (solidified cleaning film), and then removing the film by peeling is called solidification cleaning.

[0192] The solidified cleaning film removing liquid nozzle 152 is connected to one end of a solidified cleaning film removing liquid pipe 162 that guides the solidified cleaning film removing liquid to the solidified cleaning film removing liquid nozzle 152. A solidified cleaning film removing liquid valve 172A that opens and closes a flow path in the solidified cleaning film removing liquid pipe 162, and a solidified cleaning film removing liquid flow rate adjustment valve 172B that adjusts the flow rate of the solidified cleaning film removing liquid in the flow path are interposed in the solidified cleaning film removing liquid pipe 162. When the solidified cleaning film removing liquid valve 172A is opened, the solidified cleaning film removing liquid is discharged from the solidified cleaning film removing liquid nozzle 152 toward the top surface of the substrate W at a flow rate that corresponds to the opening of the solidified cleaning film removing liquid flow rate adjustment valve 172B.

[0193] The organic solvent discharged from the organic solvent nozzle 153 functions as a residue removal liquid that removes residues remaining on the main surface of the substrate W after the solidified cleaning film has been removed. The organic solvent is miscible with both the rinse liquid and the solidified cleaning liquid. The organic solvent is, for example, IPA, but is not limited to IPA.

[0194] Organic solvent nozzle 153 is connected to one end of organic solvent pipe 163, which guides the organic solvent to organic solvent nozzle 153. Organic solvent pipe 163 is provided with organic solvent valve 173A that opens and closes the flow path in organic solvent pipe 163, and organic solvent flow rate adjustment valve 173B that adjusts the flow rate of the organic solvent in the flow path. Organic solvent nozzle 153 may be configured to be able to eject an inert gas together with the organic solvent.

[0195] In this embodiment, the processing unit 2 includes a first scanning unit 180 that moves the polymer-containing liquid nozzle 8, the rinse liquid nozzle 9, and the oxide film removal liquid nozzle 150 horizontally at the same time, a second scanning unit 181 that moves the solidified cleaning liquid nozzle 151 and the solidified cleaning film removal liquid nozzle 152 horizontally at the same time, and a third scanning unit 182 that moves the organic solvent nozzle 153 horizontally.

[0196] The first scan unit 180 includes a first support member 180A that commonly supports the polymer-containing liquid nozzle 8, the rinse liquid nozzle 9, and the oxide film removal liquid nozzle 150, and a first drive mechanism 180B that drives the first support member 180A. The second scan unit 181 includes a second support member 181A that commonly supports the solidified cleaning liquid nozzle 151 and the solidified cleaning film removal liquid nozzle 152, and a second drive mechanism 181B that drives the second support member 181A. The third scan unit 182 includes a third support member 182A that supports the organic solvent nozzle 153, and a third drive mechanism 182B that drives the third support member 182A. In the substrate processing described below, the processing position where the nozzles that discharge fluids in each step are located is, for example, the central position.

[0197] <An example of substrate processing according to the fourth embodiment> FIG. 19 is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus 1R according to the fourth embodiment.

[0198] The substrate processing according to the fourth embodiment differs from the substrate processing according to the first embodiment (see FIG. 4) in that, between the substrate loading step (step S1) and the polymer-containing liquid supply step (step S2), an oxide film removal liquid supply step (step S20), a removal liquid removal step (step S21), a first substitution step (step S22), a solidified cleaning liquid supply step (step S23), a solidified cleaning film formation step (step S24), a solidified cleaning film removal step (step S25), a residue removal step (step S26), and a second substitution step (step S27) are performed in this order.

[0199] The substrate processing according to the fourth embodiment will be briefly described below. In the substrate processing according to the fourth embodiment, after the transport robot CR retreats to the outside of the processing unit 2, an oxide film removing liquid is supplied from the oxide film removing liquid nozzle 150 to the upper surface of the substrate W to remove the oxide film exposed on the upper surface of the substrate W (oxide film removing liquid supplying step: step S20). Thereafter, a rinse liquid is supplied to the upper surface of the substrate W from the rinse liquid nozzle 9, thereby removing the oxide film removing liquid from the upper surface of the substrate W (removing liquid removing step: step S21).

[0200] Thereafter, an organic solvent is supplied onto the upper surface of the substrate W from the organic solvent nozzle 153, thereby replacing the rinse liquid on the substrate W with the organic solvent (first replacement step: step S22). Further thereafter, a solidifying cleaning liquid is supplied onto the upper surface of the substrate W from the solidifying cleaning liquid nozzle 151 (solidifying cleaning liquid supply step: step S23). Thereafter, the supply of the solidifying cleaning liquid onto the upper surface of the substrate W is stopped, and the rotating substrate W is heated with a heating fluid, thereby solidifying the solidifying cleaning liquid on the substrate W and forming a solidifying cleaning film (solidifying cleaning film formation step: step S24). In the solidifying cleaning film formation step, it is not necessarily necessary to heat the substrate W, but heating the substrate W will promote the formation of the solidifying cleaning film.

[0201] After the solidified cleaning film is formed, a solidified cleaning film removal liquid is supplied from the solidified cleaning film removal liquid nozzle 152 to the upper surface of the substrate W (solidified cleaning film removal liquid supplying step), thereby peeling off and removing the solidified cleaning film from the upper surface of the substrate W (solidified cleaning film removing step: step S25). After the solidified cleaning film is removed from the upper surface of the substrate W, an organic solvent is supplied from the organic solvent nozzle 153 to the upper surface of the substrate W, thereby removing residues of the solidified cleaning film from the upper surface of the substrate W (residue removing step: step S26). Thereafter, a rinse liquid is supplied from the rinse liquid nozzle 9 to the upper surface of the substrate W, thereby replacing the organic solvent on the upper surface of the substrate W with the rinse liquid (second replacing step: step S27).

[0202] Thereafter, the polymer-containing liquid supplying step (step S2) to the substrate unloading step (step S7) are performed. According to the substrate processing apparatus 1R of the fourth embodiment, after the oxide film and particulate foreign matter are sufficiently removed from the upper surface of the substrate W, the action of the acidic polymer can further remove metallic foreign matter. Therefore, the upper surface of the substrate W can be cleaned more effectively.

[0203] 6A to 6C, according to the fourth embodiment, a semi-solid polymer film 101 is formed by rotating the substrate W to which the polymer-containing liquid has been supplied. Due to the action of the acidic polymer in the semi-solid polymer film 101, metallic foreign matter 102 is pulled away from the main surface of the substrate W and adsorbed onto the polymer film 101 (metallic foreign matter adsorption process). Therefore, by forming the polymer film 101 with an amount of polymer-containing liquid necessary to cover the entire main surface of the substrate W and then removing the polymer film 101 with a rinse liquid, the metallic foreign matter 102 can be successfully removed from the main surface of the substrate W without continuing to supply the polymer-containing liquid to the main surface of the substrate W.

[0204] Therefore, the amount of polymer-containing liquid used can be reduced because the metallic foreign matter 102 can be sufficiently removed without immersing the substrate W in the polymer-containing liquid, thereby reducing the environmental load.

[0205] According to the fourth embodiment, since the pH of the polymer-containing liquid is 1 or less, the metal foreign matter 102 can be sufficiently removed from the substrate W even if the polymer-containing liquid does not contain an oxidizing agent.

[0206] Furthermore, in the fourth embodiment, particulate foreign matter can be removed using a solidified cleaning film. Therefore, particulate foreign matter can be removed by using a quantity of solidified cleaning liquid that covers the upper surface of the substrate W, without continuously supplying a liquid for removing particulate foreign matter. This allows for a reduction in the amount of liquid used.

[0207] Furthermore, the solidified cleaning film formed on the upper surface of the substrate W is peeled off from the main surface of the substrate by the solidified cleaning film removal liquid, and is removed from the upper surface of the substrate W. Because the solidified cleaning film is solid or semi-solid, it can hold particulate foreign matter adhering to the upper surface of the substrate W. Because the solidified cleaning film is peeled off from the upper surface of the substrate W while still holding the foreign matter, the particulate foreign matter can be removed along with the solidified cleaning film. Because the particulate foreign matter is held by the solidified cleaning film, the kinetic energy that the solidified cleaning film removal liquid flowing over the upper surface of the substrate W receives is greater than the kinetic energy that particulate foreign matter not held by the solidified cleaning film receives from the solidified cleaning film removal liquid. Therefore, the particulate foreign matter can be effectively removed from the upper surface of the substrate W.

[0208] By carrying out solidification cleaning, it is possible to effectively remove particulate foreign matter having properties different from metallic foreign matter, which is difficult to remove from the substrate W by the action of the acidic polymer in the polymer film.

[0209] When using the substrate processing apparatus 1R according to the fourth embodiment, unlike the substrate processing shown in FIG. 19, it is also possible to perform a substrate rotation stopping step (step S10) (see FIG. 7) instead of the polymer film heating step (step S4).

[0210] <Removal efficiency measurement experiment> FIG. 20 is a graph showing the results of an experiment (first removal efficiency measurement experiment) measuring the metal removal efficiency (Metal removal efficiency [%]) of metal foreign matter by a polymer membrane.

[0211] In the first removal efficiency measurement experiment, 13 types of substrates were prepared, each with 13 types of metal foreign matter attached, and the removal efficiency of the metal foreign matter was measured for each type of substrate when three types of liquids were used: HPM liquid, acidic polymer liquid, and polymer-containing liquid (a mixture of acidic polymer liquid and hydrogen peroxide solution).

[0212] Specifically, in the first removal efficiency measurement experiment, the removal efficiency was measured after supplying HPM liquid, acidic polymer liquid, or polymer-containing liquid to the main surface of the substrate, rinsing the main surface with DIW, and drying the main surface. The removal efficiency was measured using total reflection X-ray fluorescence analysis (TXRF) to confirm the degree of removal (removal efficiency) of metal foreign matter. When an acidic polymer liquid or polymer-containing liquid was used, a process of forming a polymer film on the main surface of the substrate was carried out before rinsing with DIW.

[0213] The concentration of the acidic polymer liquid used in this experiment was 10% by mass (wt%). The concentration of the hydrogen peroxide solution used in this experiment was 30% by mass (wt%). The mixing ratio of the hydrogen peroxide solution to the acidic polymer liquid in the polymer-containing liquid was 1:6 by volume.

[0214] The experimental results showed that when the metal foreign matter was aluminum (Al), titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), copper (Cu), cobalt (Co), hafnium (Hf), or tantalum (Ta), the polymer-containing liquid had a higher removal efficiency than the HPM liquid. Even when the metal foreign matter was a different metal type, the polymer-containing liquid was found to have the same removal efficiency as the HPM liquid.

[0215] Based on the first removal efficiency measurement experiment, it is inferred that the mixed solution of the acidic polymer solution and hydrogen peroxide solution, i.e., the polymer film formed from the polymer-containing solution, has a higher removal power for removing metal foreign matter than the HPM solution. More specifically, the high removal efficiency of the polymer-containing solution is thought to be due to the fact that the acidic polymer, which has a higher concentration than that in the polymer-containing solution due to the formation of the polymer film, acts on the metal foreign matter.

[0216] On the other hand, when the metal contaminants were aluminum (Al), titanium (Ti), iron (Fe), nickel (Ni), copper (Cu), cobalt (Co), hafnium (Hf), or tantalum (Ta), the removal efficiency of the metal contaminants using an acidic polymer solution was lower than that using an HPM solution. This result suggests that even when using an acidic polymer to remove metal contaminants, the synergistic effect with an oxidizing agent such as hydrogen peroxide is important.

[0217] FIG. 21 is a graph showing the results of an experiment (second removal efficiency measurement experiment) in which the removal efficiency of metal foreign matter was measured when an acidic polymer having a higher acidity than the acidic polymer used in the first removal efficiency measurement experiment shown in FIG. 20 was used.

[0218] More specifically, in the second removal efficiency measurement experiment, 12 types of substrates each with 12 types of metallic foreign matter attached were prepared, and the removal efficiency of metallic foreign matter was measured for each type of substrate when two types of liquids, HPM liquid and acidic polymer liquid, were used. The 12 types of metallic foreign matter were the 12 types of metallic foreign matter of the 13 types of metallic foreign matter used in the first removal efficiency measurement experiment, excluding tantalum.

[0219] The removal efficiency was measured by supplying an HPM solution or an acidic polymer solution to the main surface of the substrate, rinsing the main surface with DIW, and then drying the main surface. The removal efficiency was confirmed using TXRF. When an acidic polymer solution was used, a step of forming a polymer film on the main surface of the substrate was performed before rinsing with DIW. The pH of the acidic polymer solution used in the second removal efficiency measurement experiment was 1, and the pH of the acidic polymer solution used in the first removal efficiency measurement experiment was 3. The concentration of the acidic polymer solution used in this experiment was 10 mass percent (wt%).

[0220] The results of this experiment showed that, except for when the metal foreign matter was titanium (Ti), when an acidic polymer solution was used, the metal removal efficiency was comparable to that when an HPM solution was used, or even higher than that when an HPM solution was used. Based on the results of the second removal efficiency measurement experiment, it can be inferred that when the acidity of the acidic polymer is sufficiently high, the polymer film formed from the acidic polymer solution can sufficiently remove metal foreign matter.

[0221] <Other embodiments> The present invention is not limited to the above-described embodiment, and can be embodied in other forms.

[0222] For example, in the first embodiment, after the polymer film 101 is formed on the substrate W, the rotation of the substrate W may be stopped and the substrate W may be heated while the polymer film 101 on the substrate W is left standing.

[0223] Furthermore, the heating of the polymer film 101 on the substrate W is not limited to heating by the heated fluid supply unit 13 or heating by the heater unit 6. Specifically, the polymer film 101 on the substrate W may be heated by an infrared lamp facing the upper surface of the substrate W or a heater facing the upper surface of the substrate W.

[0224] Also, unlike the above-described embodiments, the polymer film 101 may be formed on the lower surface of the substrate W.

[0225] Furthermore, unlike the above-described embodiments, the polymer-containing liquid may contain an alkaline component such as ammonia. The presence of the alkaline component increases the pH of the polymer-containing liquid, suppressing the adsorptive power of the acidic polymer to metallic foreign matter. The suppression of the adsorptive power of the acidic polymer continues even after the polymer film 101 is formed. However, in the polymer film heating step, by heating the polymer film 101, the alkaline component in the polymer film 101 evaporates (volatilizes) together with the solvent, and the acidic polymer in the polymer film 101 begins to adsorb metallic foreign matter.

[0226] The alkaline component is not limited to ammonia, but may be any component that evaporates at the heating temperature (temperature of 60° C. or higher and lower than 150° C.) in the polymer film heating step and exhibits alkaline properties in the solvent. Specifically, the alkaline component includes, for example, ammonia, tetramethylammonium hydroxide (TMAH), dimethylamine, or a mixture thereof.

[0227] In the above-described embodiments, each component may be shown schematically as a block, but the shape, size, and positional relationship of each block do not indicate the shape, size, and positional relationship of each component.

[0228] In the above-described embodiments, the substrate processing apparatus 1, 1P, 1Q includes the transport robots IR, CR, a plurality of processing units 2, and a controller 3. However, the substrate processing apparatus 1, 1P, 1Q may be configured with a single processing unit 2 and a controller 3, and may not include the transport robots IR, CR. Alternatively, the substrate processing apparatus 1, 1P, 1Q may be configured with only a single processing unit 2. In other words, the processing unit 2 may be an example of the substrate processing apparatus.

[0229] Furthermore, in Figures 2, 9 to 11, and 13 to 18, not all pipes, pumps, valves, nozzle moving units, etc. are shown, and this does not prevent these components from being installed in appropriate positions.

[0230] In addition, various modifications can be made within the scope of the claims. [Explanation of symbols]

[0231] 1: Substrate processing equipment 1P: Substrate processing equipment 2: Processing unit (substrate processing device) 5: Spin chuck 8: Polymer-containing liquid nozzle 9: Rinse liquid nozzle 80: Polymer-containing liquid tank 101: Polymer film 102: Metallic foreign bodies 105: Acidic polymer W: Substrate

Claims

1. a polymer-containing liquid supplying step of supplying a polymer-containing liquid containing an acidic polymer and a solvent that dissolves the acidic polymer onto a main surface of a substrate; a polymer film forming step of spreading the polymer-containing liquid by rotating the substrate having the polymer-containing liquid attached to its main surface, thereby forming a polymer film containing the acidic polymer on the main surface of the substrate; a rinsing step of supplying a rinse liquid to the main surface of the substrate, the rinse liquid cleaning the main surface of the substrate having the polymer film formed thereon; the polymer-containing liquid further contains an oxidizing agent dissolved in the solvent; the polymer film formed in the polymer film forming step further contains the oxidizing agent, The substrate processing method, wherein the polymer-containing liquid is a mixed liquid obtained by mixing an acidic polymer liquid containing 10 wt % of the acidic polymer and a liquid oxidizing agent containing 30 wt % of the oxidizing agent in a volume ratio of 1:

6.

2. a metal foreign matter adsorption step of detaching metal foreign matters adhering to the main surface of the substrate from the main surface of the substrate by the action of the acidic polymer in the polymer film and adsorbing the metal foreign matters onto the polymer film; 2. The substrate processing method according to claim 1, further comprising an adsorption promotion step of promoting adsorption of the metallic foreign matter by the acidic polymer by the action of the oxidizing agent in the polymer film.

3. the polymer-containing liquid further contains a conductive polymer dissolved in the solvent, The substrate processing method according to claim 1 , wherein the polymer film formed in the polymer film forming step further contains the conductive polymer.

4. a solidified cleaning film forming step of forming a solid or semi-solid solidified cleaning film on the main surface of the substrate before the polymer-containing liquid supplying step; 4. The substrate processing method according to claim 1, further comprising: a solidified cleaning film removal liquid supplying step of supplying, to the main surface of the substrate, a solidified cleaning film removal liquid that peels off the solidified cleaning film from the main surface of the substrate and removes it from the main surface of the substrate, before the polymer-containing liquid supplying step.

5. A polymer-containing liquid supplying step of supplying a polymer-containing liquid containing an acidic polymer and a solvent that dissolves the acidic polymer onto a main surface of a substrate; a polymer film forming step of spreading the polymer-containing liquid by rotating the substrate having the polymer-containing liquid attached to its main surface, thereby forming a polymer film containing the acidic polymer on the main surface of the substrate; a rinsing step of supplying a rinse liquid to the main surface of the substrate, the rinse liquid cleaning the main surface of the substrate having the polymer film formed thereon; the polymer-containing liquid further contains a conductive polymer dissolved in the solvent, The substrate processing method, wherein the polymer film formed in the polymer film forming step further contains the conductive polymer.

6. a solidified cleaning film forming step of forming a solid or semi-solid solidified cleaning film on the main surface of the substrate before the polymer-containing liquid supplying step; 6. The substrate processing method according to claim 5, further comprising: a solidified cleaning film removal liquid supplying step of supplying, to the main surface of the substrate, a solidified cleaning film removal liquid that peels off the solidified cleaning film from the main surface of the substrate and removes it from the main surface of the substrate, before the polymer-containing liquid supplying step.

7. A polymer-containing liquid supplying step of supplying a polymer-containing liquid containing an acidic polymer and a solvent that dissolves the acidic polymer onto a main surface of a substrate; a polymer film forming step of spreading the polymer-containing liquid by rotating the substrate having the polymer-containing liquid attached to its main surface, thereby forming a polymer film containing the acidic polymer on the main surface of the substrate; a rinsing step of supplying a rinse liquid to the main surface of the substrate, the rinse liquid being used to clean the main surface of the substrate on which the polymer film is formed; a solidified cleaning film forming step of forming a solid or semi-solid solidified cleaning film on the main surface of the substrate before the polymer-containing liquid supplying step; a solidified cleaning film removal liquid supplying step of supplying, to the main surface of the substrate, a solidified cleaning film removal liquid that peels off the solidified cleaning film from the main surface of the substrate and removes it from the main surface of the substrate, before the polymer-containing liquid supplying step.

8. 8. The substrate processing method according to claim 1, wherein the polymer film forming step comprises the step of forming the polymer film by evaporating a part of the solvent in the polymer-containing liquid.

9. 9. The substrate processing method according to claim 1, wherein the rinsing step includes a polymer film removing step of removing the polymer film from the main surface of the substrate.

10. 10. The substrate processing method according to claim 1, further comprising, after the polymer film forming step, a polymer film heating step of heating the polymer film.

11. 11. The substrate processing method according to claim 10, wherein the polymer film heating step includes a fluid heating step of heating the polymer film through the substrate by supplying a heating fluid to a surface of the substrate opposite to a main surface while rotating the substrate.

12. 12. The substrate processing method according to claim 1, further comprising a substrate rotation stopping step of stopping the rotation of the substrate for a predetermined time after the polymer film forming step.

13. The method further includes a preparation step of storing the polymer-containing liquid in a polymer-containing liquid tank, 13. The substrate processing method according to claim 1, wherein the polymer-containing liquid supplying step includes a polymer-containing liquid discharge step of supplying the polymer-containing liquid from the polymer-containing liquid tank to a polymer-containing liquid nozzle and discharging the polymer-containing liquid from the polymer-containing liquid nozzle toward the main surface of the substrate.

14. a spin chuck that holds a substrate and rotates the substrate around a predetermined rotation axis; a polymer-containing liquid nozzle that supplies a polymer-containing liquid containing an acidic polymer and a solvent that dissolves the acidic polymer onto a main surface of the substrate held by the spin chuck, the polymer-containing liquid forming a polymer film containing the acidic polymer on the main surface of the substrate; a rinse liquid nozzle that supplies a rinse liquid to a main surface of the substrate held by the spin chuck, the polymer-containing liquid further contains an oxidizing agent dissolved in the solvent; The substrate processing apparatus, wherein the polymer-containing liquid is a mixed liquid obtained by mixing an acidic polymer liquid containing 10 wt % of the acidic polymer and a liquid oxidizing agent containing 30 wt % of the oxidizing agent at a volume ratio of 1:

6.

15. A spin chuck that holds a substrate and rotates the substrate about a predetermined rotation axis; a polymer-containing liquid nozzle that supplies a polymer-containing liquid containing an acidic polymer and a solvent that dissolves the acidic polymer onto a main surface of the substrate held by the spin chuck, the polymer-containing liquid forming a polymer film containing the acidic polymer on the main surface of the substrate; a rinse liquid nozzle that supplies a rinse liquid to a main surface of the substrate held by the spin chuck, The substrate processing apparatus, wherein the polymer-containing liquid further contains a conductive polymer dissolved in the solvent.

16. the spin chuck rotates the substrate while the polymer-containing liquid supplied by the polymer-containing liquid nozzle is adhering to the main surface of the substrate, thereby forming the polymer film on the main surface of the substrate; 16. The substrate processing apparatus according to claim 14, wherein the rinse liquid nozzle supplies a rinse liquid to the substrate on which the polymer film is formed, thereby removing the polymer film from the main surface of the substrate.

17. The substrate processing apparatus according to any one of claims 14 to 16, wherein metal foreign matter adhering to the main surface of the substrate is detached from the main surface of the substrate and adsorbed onto the polymer film by the action of the acidic polymer in the polymer film.

18. an acidic polymer that adsorbs metallic foreign matter adhering to the main surface of the substrate; an oxidizing agent that promotes adsorption of the metal foreign matter by the acidic polymer; a polymer-containing liquid containing the oxidizing agent and a solvent that dissolves the acidic polymer, The polymer-containing liquid is a mixed liquid obtained by mixing an acidic polymer liquid containing 10 wt % of the acidic polymer and a liquid oxidizing agent containing 30 wt % of the oxidizing agent in a volume ratio of 1:

6.

19. An acidic polymer that adsorbs metal foreign matter adhering to a main surface of a substrate; an oxidizing agent that promotes adsorption of the metal foreign matter by the acidic polymer; a conductive polymer; a polymer-containing liquid containing the oxidizing agent, the acidic polymer, and a solvent capable of dissolving the conductive polymer;

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