Substrate processing method and substrate processing device

Abstract

This substrate processing method includes: a processing liquid supply step for supplying, to a pattern surface of a substrate, a processing liquid having a solute and a solvent; a processing film formation step for solidifying or curing the processing liquid, thereby forming a processing film; a solvent extract supply step for supplying, to the surface of the processing film, a solvent extract for extracting the solvent from the processing film; a solvent extract discharge step for discharging the solvent extract to the outside of the substrate; an evaporation promotion step for promoting evaporation of the solvent in the processing film; and a removal step for detaching the processing film from the pattern surface, thereby removing the processing film to the outside of the substrate. Furthermore, a residue removal step for removing a residue on the processing film may be included.

Description

Substrate processing method and substrate processing apparatus

[0001] This invention relates to a substrate processing method and a substrate processing apparatus. Substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for FPDs (Flat Panel Displays) such as organic EL (Electroluminescence) display devices, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, and substrates for solar cells.

[0002] Patent Document 1 discloses a method for forming a topcoat film by supplying a topcoat liquid to the surface of a substrate on which a pattern has been formed and allowing its volatile components to volatilize, and then using the tensile force during volume contraction of the topcoat liquid to detach particles attached to the pattern. The topcoat film is then dissolved with a removal solution and removed from the substrate.

[0003] Patent Document 1 describes a volatilization acceleration treatment to promote the volatilization of volatile components in the topcoat liquid, which involves supplying high-temperature N2 gas to the underside of the substrate, activating the topcoat liquid by irradiating it with ultraviolet light, heating it with a heating unit provided on an underplate facing the underside of the substrate, and reducing the pressure inside the chamber.

[0004] Japanese Patent Publication No. 2014-197717

[0005] When a processing liquid (solution) containing a solute and solvent is supplied to the patterned surface of a substrate (the main surface on which a raised and recessed pattern is formed), and the liquid film of the processing liquid is solidified or hardened on the patterned surface to form a processed film, evaporation from the surface of the liquid film tends to cause precipitation of the solute from the surface layer of the liquid film. As a result, a partial solidified or hardened layer is formed on the surface layer of the liquid film, and these solidified or hardened layers seal the solvent within the film. In this state, if the solvent is to be evaporated by heating or other means, the solvent changes from the liquid phase to the gas phase while remaining sealed, and its volume expands, which may cause voids to form in the processed film.

[0006] When voids form within a film, the mechanical strength of the treated film is reduced compared to cases without voids. This leads to a problem of reduced foreign matter removal performance.

[0007] Therefore, one embodiment of this invention provides a novel substrate processing method and substrate processing apparatus that can improve foreign matter removal performance.

[0008] A substrate processing method according to one embodiment of the present invention includes a processing liquid supply step of supplying a processing liquid having a solute and a solvent to the pattern surface of a substrate having a pattern surface on which an uneven pattern is formed. The substrate processing method includes a processing film forming step of solidifying or hardening the processing liquid on the pattern surface to form a processing film on the pattern surface. The substrate processing method includes a solvent extract supply step of supplying a solvent extract to the surface of the processing film to extract the solvent from the processing film. The substrate processing method includes a solvent extract discharge step of discharging the solvent extract to the outside of the substrate after the solvent extract supply step. The substrate processing method includes an evaporation acceleration step of accelerating the evaporation of the solvent in the processing film after the evaporation acceleration step. The substrate processing method includes a removal step of peeling the processing film from the pattern surface and removing it to the outside of the substrate after the evaporation acceleration step.

[0009] In one embodiment, the evaporation acceleration step includes a heating step of heating the treated film.

[0010] In one embodiment, the solvent extract is a liquid that has a lower affinity for the solute than the solvent and is compatible with the solvent.

[0011] Affinity for a solute may also be expressed by its solubility. In this case, the solubility of the solute in the solvent extract is lower than the solubility of the solute in the solvent.

[0012] In one embodiment, the solute comprises a polymer, the solvent is water-soluble, and the solvent extract comprises water. The solvent may also comprise PGME (propylene glycol monomethyl ether) or IPA (isopropyl alcohol).

[0013] In one embodiment, the solute comprises a polymer, the solvent is water-insoluble, and the solvent extract comprises an organic solvent (e.g., IPA). The solvent may also comprise PGMEA (propylene glycol monomethyl ether acetate) or cyclopentanol.

[0014] In one embodiment, the substrate processing method includes a residue removal step after the removal step, in which a residue removal liquid is supplied to the pattern surface to remove the residue of the processed film from the pattern surface.

[0015] The residue removal solution may contain at least one of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

[0016] A substrate processing apparatus according to one embodiment of the present invention includes a spin chuck for holding a substrate having a patterned surface on which an uneven pattern is formed in a horizontal position and rotating the substrate around a rotation axis passing through the center of the substrate. The substrate processing apparatus includes a processing liquid supply unit for supplying a processing liquid having a solute and a solvent to the patterned surface of the substrate held by the spin chuck in order to form a processing film on the patterned surface. The substrate processing apparatus includes a solvent extractant supply unit for supplying a solvent extractant for extracting the solvent from the processing film to the surface of the processing film formed on the patterned surface of the substrate held by the spin chuck. The substrate processing apparatus includes an evaporation acceleration unit for promoting the evaporation of the solvent in the processing film formed on the patterned surface of the substrate held by the spin chuck. The substrate processing apparatus includes a processing film removal unit for peeling the processing film formed on the patterned surface of the substrate held by the spin chuck from the patterned surface and removing it from the substrate.

[0017] In one embodiment, the substrate processing apparatus includes a controller that controls the spin chuck, the processing liquid supply unit, the solvent extract supply unit, the evaporation acceleration unit, and the processing film removal unit. The controller is programmed to perform a processing liquid supply step, in which the processing liquid is supplied from the processing liquid supply unit to the pattern surface while the substrate is rotated by the spin chuck. The controller is programmed to perform a processing film formation step, in which the processing liquid is solidified or hardened on the pattern surface by stopping the supply of the processing liquid by the processing liquid supply unit and rotating the substrate by the spin chuck, thereby forming the processing film on the pattern surface. After the processing film is formed, the controller is programmed to perform a solvent extract supply step, in which the solvent extract is supplied from the solvent extract supply unit to the surface of the processing film. The controller is programmed to perform a solvent extract discharge step, in which the solvent extract is discharged from the substrate by stopping the supply of the solvent extract by the solvent extract supply unit and rotating the substrate by the spin chuck. The controller is programmed to perform an evaporation acceleration step after the solvent extract discharge step, in which the evaporation acceleration unit accelerates the evaporation of the solvent in the processed film. The controller is programmed to perform a removal step after the evaporation acceleration step, in which the removal unit accelerates the removal of the processed film from the patterned surface and removes it from the substrate.

[0018] The evaporation acceleration unit may include a heating unit for heating the processed film formed on the patterned surface of the substrate held in the spin chuck.

[0019] The above-mentioned, or further, objectives, features, and effects of the present invention will be made clearer by the following description of embodiments with reference to the accompanying drawings.

[0020] FIG. 1 is a diagram for explaining an outline of a substrate processing method according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view for explaining an example of the structure of a pattern surface of a substrate. FIGS. 3A to 3C are cross-sectional views schematically showing enlarged views of the state of the pattern surface in each step. FIGS. 3D to 3E are cross-sectional views schematically showing enlarged views of the state of the pattern surface in each step. FIG. 4 is a micrograph of a sample in which voids have occurred in a processing film. FIG. 5 is a schematic plan view showing a layout of a substrate processing apparatus according to an embodiment of the present invention. FIG. 6 is a schematic diagram for explaining a configuration example of a processing unit provided in the substrate processing apparatus. FIG. 7 is a block diagram showing an electrical configuration of a main part of the substrate processing apparatus. FIG. 8 is a flowchart for explaining an example of substrate processing by the substrate processing apparatus. FIGS. 9A to 9B are schematic diagrams for explaining the state of each step of the substrate processing. FIGS. 9C to 9D are schematic diagrams for explaining the state of each step of the substrate processing. FIGS. 9E to 9F are schematic diagrams for explaining the state of each step of the substrate processing. FIGS. 9G to 9H are schematic diagrams for explaining the state of each step of the substrate processing. FIG. 9I is a schematic diagram for explaining the state of one step of substrate processing. FIGS. 10A to 10C are illustrative cross-sectional views for explaining the state when the processing film is peeled off from the substrate.

[0021] FIG. 1 is a diagram for explaining an outline of a substrate processing method according to an embodiment of the present invention.

[0022] This substrate processing method performs a foreign matter removal process for removing foreign matter (particles) attached to a pattern surface 165 (one of the main surfaces) of a substrate W having a pattern surface 165 on which an uneven pattern is formed. A typical example of the substrate W is a semiconductor wafer. In this case, the substrate processing method of this embodiment is mainly executed for the purpose of removing foreign matter from the main surface of the semiconductor wafer in the front end (FEOL (front-end-of-line), pre-process).

[0023] The substrate processing method includes a processing liquid supply step 171 of supplying a processing liquid 91 to the pattern surface 165 of the substrate W, and a processing film forming step 172 of solidifying or curing the processing liquid 91 on the pattern surface 165 to form a processing film 100 on the pattern surface 165. The processing liquid 91 supplied to the pattern surface 165 forms a processing liquid film 101 (a liquid film of the processing liquid 91) on the pattern surface 165, and the solvent component of the processing liquid film 101 evaporates, whereby the processing liquid film 101 solidifies or cures to form a semi-solidified or semi-cured processing film 100.

[0024] Also, the substrate processing method includes a solvent extraction liquid supply step 173 of supplying a solvent extraction liquid 92 to the surface of the processing film 100 on the pattern surface 165 after the processing film forming step 172, and thereafter, a solvent extraction liquid discharge step 174 of discharging the solvent extraction liquid 92 out of the substrate W. Further, the substrate processing method includes an evaporation promotion step 175 of promoting the evaporation of the solvent in the processing film 100 after the solvent extraction liquid discharge step 174. One typical example of the evaporation promotion step 175 is a heating step of heating the processing film 100. For example, the substrate W may be heated, and thereby, the processing film 100 on the substrate W may be heated.

[0025] The substrate processing method includes a removal step 176 of peeling the processing film 100 from the pattern surface and removing it out of the substrate W after the evaporation promotion step 175. The removal step 176 includes, for example, a peeling liquid supply step of supplying a peeling liquid 93 (removal liquid) for peeling the processing film 100 from the pattern surface 165 toward the pattern surface 165 of the substrate W. Further, the removal step 176 may include a gas spraying step of spraying a gas (typically an inert gas such as nitrogen gas) toward the processing film 100 to peel the processing film 100 from the substrate W.

[0026] In this example, the substrate processing method includes a residue removal step 177 of supplying a residue removal liquid 94 to the pattern surface 165 of the substrate W to remove the residue of the processing film 100 from the pattern surface after the removal step 176. The residue removal liquid 94 is preferably a liquid (typically an organic solvent) that can dissolve the processing film 100. The substrate processing method also includes a shaking-off drying treatment step 178 (typically a spin-dry step) for shaking off the liquid on the surface of the substrate W after the residue removal step 177.

[0027] Figure 2 is a schematic cross-sectional view illustrating an example of the structure of the patterned surface of a substrate.

[0028] A fine uneven pattern 160 is formed on one of the main surfaces of the substrate W. The uneven pattern 160 includes fine convex structures 161 formed on the upper surface of the substrate W and recesses (grooves) 162 formed between adjacent structures 161.

[0029] The surface of the uneven pattern 160, that is, the surface 161a of the structure 161 (protrusion) and the surface of the recess 162, form an uneven pattern surface 165. The surface 161a of the structure 161 is composed of a tip surface 161b (top) and a side surface 161c, and the surface of the recess 162 is composed of a bottom surface 162a (bottom). If the structure 161 is cylindrical, the recess will be formed on its interior side.

[0030] The structure 161 may include an insulating film or a conductive film. Furthermore, the structure 161 may be a laminated film formed by stacking multiple films.

[0031] The uneven pattern 160 is a fine pattern with an aspect ratio of 3 or more. The aspect ratio of the uneven pattern 160 is, for example, 10 to 50 (for example, 25). The width L1 of the structure 161 may be about 10 nm to 45 nm (for example, 20 nm), and the spacing L2 between the structures 161 may be about 10 nm to several μm (for example, 30 nm). The height of the structure 161 (pattern height T1) may be, for example, about 50 nm to 5 μm (for example, 500 nm). The pattern height T1 is the distance between the leading edge 161b of the structure 161 and the bottom surface 162a (bottom) of the recess 162.

[0032] Figures 3A to 3E are cross-sectional views illustrating the pattern surface at each stage of the process in an enlarged view.

[0033] Figure 3A shows the state immediately after the processing liquid 91 is supplied to the pattern surface 165 by the processing liquid supply process 171. The processing liquid 91 fills the recess 162, and the surface 101a of the processing liquid film 101 is located outside the recess 162, that is, above the tip surface 161b (top) of the structure 161 (protrusion). The processing liquid 91 is supplied, for example, by holding the substrate W in a horizontal position with the pattern surface 165 facing upward and rotating it around a rotation axis passing through its center. As a result, the processing liquid 91 spreads over the entire area of ​​the pattern surface 165, forming a processing liquid film 101 that covers the entire area of ​​the pattern surface 165.

[0034] Figure 3B shows the processing film formation process 172. Specifically, by rotating the substrate W with the supply of the processing liquid 91 stopped, the solvent in the processing liquid 91 evaporates from the surface 101a of the processing liquid film 101 into the atmosphere and dries, and the processing liquid 91 solidifies or hardens on the pattern surface 165, forming a processing film 100 on the pattern surface 165.

[0035] "Solidification" refers to the process where a solute solidifies due to forces acting between molecules or atoms, for example, as the solvent volatilizes (evaporates). "Hardening" refers to the process where a solute solidifies due to chemical changes such as polymerization or crosslinking. Therefore, "solidification or hardening" describes the process where a solute "solidifies" due to various factors.

[0036] The processed film 100 formed in the processed film formation step 172 is in a state where the solvent has evaporated to the extent that it does not flow on the substrate W, but it contains a relatively large amount of solvent within the film. In other words, the processed film 100 formed in the processed film formation step 172 is a film in which the processed liquid film 101 has been semi-cured or semi-solidified. Then, in the evaporation acceleration step 175 that is performed later, the solvent in the processed film 100 is further evaporated, resulting in the formation of a further cured or solidified processed film 100, that is, a completely cured or solidified processed film 100.

[0037] In the processing film formation step 172, the solvent evaporates from the surface of the processing liquid film 101, causing solute precipitation to begin from the surface layer of the processing liquid film 101 (the part close to the surface 101a), and a solidified layer 101b is formed on the surface layer of the processing liquid film 101. This solidified layer 101b inhibits the evaporation of the solvent 91a in the deeper parts of the processing liquid film 101 (the part farther from the surface 101a). Therefore, the formed processing film 100 has the solvent 91a sealed within the film by the solidified layer 101b on the surface. Figure 3B shows the state in which the solvent 91a remains in the recess 162.

[0038] If, in this state, an evaporation acceleration step 175 is performed to promote the evaporation of the solvent in the treated film 100, such as a heating step that heats the treated film 100, the sealed solvent 91a may change from the liquid phase to the gas phase and expand in volume, potentially causing voids to form in the treated film 100. As an example, Figure 4 shows a micrograph of a sample in which voids 100v have formed. Such voids in the film cause weakening of the treated film 100. This leads to a decrease in the foreign matter capture performance of the treated film 100 and a decrease in foreign matter removal performance.

[0039] Therefore, in this embodiment, as shown in Figure 3C, the solvent extract supply step 173 is performed before the evaporation acceleration step 175. For example, the substrate W is supported in a horizontal position with the pattern surface 165 facing upward, and the solvent extract 92 is supplied toward the pattern surface 165 of the substrate W while rotating it around a rotation axis passing through its center. That is, the solvent extract 92 is supplied to the surface 100a of the processed film 100 formed on the pattern surface 165. The solvent extract 92 spreads over the entire surface 100a of the processed film 100.

[0040] The solvent extract 92 is a liquid capable of extracting the solvent 91a from the processing membrane 100 to the outside of the processing membrane 100. More specifically, it is a liquid capable of extracting the solvent 91a to the outside of the processing membrane 100 without dissolving the solute in the processing membrane 100. The solvent extract 92 has a lower affinity for the solute in the processing solution 91 than for the solvent. In other words, the solubility of the solute in the solvent extract 92 is lower than the solubility of the solute in the solvent. Typically, the solute in the processing solution 91 is insoluble or sparingly soluble in the solvent extract 92. On the other hand, it is preferable that the solvent extract 92 is miscible with the solvent in the processing solution 91, that is, it is miscible and can dissolve infinitely. "Miscible" means that different liquids mix uniformly at the molecular level and form a transparent phase.

[0041] For example, if the solute contains a polymer and the solvent is water-soluble, the solvent extract may contain water (more specifically, deionized water). The water-containing solvent extract may be deionized water or an acid (diluted acid) at a dilution concentration (e.g., about 1 ppm to 100 ppm). The water-soluble solvent may be a liquid containing PGME (propylene glycol monomethyl ether) or IAP.

[0042] Furthermore, if the solute contains a polymer and the solvent is water-insoluble, the solvent extract may contain an organic solvent (e.g., IPA). The water-insoluble solvent may be a liquid containing PGMEA (propylene glycol monomethyl ether acetate) or cyclopentanol.

[0043] Examples of preferred combinations of the solute and solvent of the processing solution 91 and the solvent extract 92 are shown below.

[0044]

[0045] When the solvent extract 92 is supplied to the surface 100a of the processed film 100, as shown in Figure 3C, the solvent 91a in the processed film 100 diffuses toward the liquid layer of the solvent extract 92, moves outside the processed film 100 (into the liquid layer of the solvent extract 92) and is extracted. As a result, the concentration of solute increases in the deeper parts of the processed film 100 (typically within the recesses 162 of the pattern), and the solute precipitates. As the solvent 91a moves from the deeper parts of the processed film 100 toward the surface 100a, the concentration of solute increases in the deeper parts of the processed film 100, and decreases in the surface layer of the processed film 100. Typically, before the solvent extract supply step 173 is performed, the concentration distribution of solute in the processed film 100 is higher in the surface layer than in the deeper parts. Then, by performing the solvent extract supply step 173, the concentration distribution of solute in the processed film 100 changes to a distribution where the concentration is lower in the surface layer than in the deeper layers. In this way, the solvent extract supply step 173 can alleviate or eliminate the state in which the solvent 91a is sealed by the solidified layer 101b (see Figure 3B) on the surface of the processed film 100.

[0046] Figure 3D shows the solvent extract discharge step 174. The solvent extract discharge step 174 is achieved, for example, by stopping the supply of the solvent extract 92 and rotating the substrate W in a horizontal position around a rotation axis passing through its center. That is, the solvent extract 92 on the processed film 100 is discharged off the substrate W by centrifugal force.

[0047] Subsequently, as shown in Figure 3E, an evaporation acceleration step 175 is performed. A typical example of the evaporation acceleration step 175 is a heating step. The heating step may be a substrate heating step in which the substrate W is heated, thereby heating the processed film 100. The solvent extract supply step 173 has eased or eliminated the state in which the solvent is sealed within the processed film 100, and moreover, the processed film 100 is solvent-richer towards the surface. Therefore, by evaporation acceleration treatment such as heating, the solvent in the processed film 100 can be evaporated with almost no voids being generated in the processed film 100, and the processed film 100 can be substantially completely hardened or solidified. As a result, the processed film 100 has sufficient strength and can capture foreign matter on the pattern surface 165 with sufficient strength. Therefore, in the subsequent removal step 176 (see Figure 1), the processed film 100 is removed from the substrate W while retaining foreign matter with sufficient strength.

[0048] Figure 5 is a schematic plan view showing the layout of a substrate processing apparatus 1 according to one embodiment of the present invention.

[0049] The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates W, such as silicon wafers, one at a time. In this embodiment, the substrate W is a disc-shaped substrate. A fine uneven pattern 160 (see Figure 2) is formed on the surface (main surface) of the substrate W.

[0050] The substrate processing apparatus 1 includes a plurality of processing units 2 that process substrates W with fluid, a load port LP on which a carrier C that accommodates a plurality of substrates W processed by the processing units 2 is placed, transport robots IR and CR that transport substrates W between the load port LP and the processing units 2, and a controller 3 that controls the substrate processing apparatus 1.

[0051] The transport robot IR is an indexer robot that transports the substrate W between carrier C and transport robot CR. The transport robot CR is a main transport robot that transports the substrate W between transport robot IR and processing unit 2. Multiple processing units 2 have similar configurations, for example. As will be described in detail later, the processing fluid supplied to the substrate W within the processing unit 2 includes chemicals, rinsing solution, processing solution, solvent extractant, residue removal solution, stripping solution, heat transfer medium, inert gas, etc.

[0052] Each processing unit 2 comprises a chamber 4 and a processing cup 7 located inside the chamber 4, and performs processing on the substrate W within the processing cup 7. The chamber 4 has an entrance / exit (not shown) for loading and unloading the substrate W by a transport robot CR. The chamber 4 is equipped with a shutter unit (not shown) for opening and closing this entrance / exit.

[0053] Figure 6 is a schematic diagram illustrating an example of the configuration of the processing unit 2.

[0054] The processing unit 2 includes a spin chuck 5, an opposing member 6, a processing cup 7, a first moving nozzle 8, a second moving nozzle 9, a third moving nozzle 10, a central nozzle 11, and a bottom nozzle 12.

[0055] The spin chuck 5 holds the substrate W horizontally and rotates the substrate W around the rotation axis A1 (vertical axis). The rotation axis A1 is a vertical axis passing through the center of the substrate W. The spin chuck 5 includes a plurality of chuck pins 20, a spin base 21, a rotation axis 22, and a spin motor 23.

[0056] The spin base 21 has a disc shape that is aligned horizontally. Multiple chuck pins 20 for gripping the periphery of the substrate W are arranged on the upper surface of the spin base 21 at intervals in the circumferential direction of the spin base 21. The spin base 21 and the multiple chuck pins 20 constitute a substrate holding unit that holds the substrate W horizontally. The substrate holding unit is also called a substrate holder.

[0057] The rotating shaft 22 extends vertically along the rotation axis A1. The upper end of the rotating shaft 22 is coupled to the center of the lower surface of the spin base 21. The spin motor 23 applies rotational force to the rotating shaft 22. The rotation of the rotating shaft 22 by the spin motor 23 causes the spin base 21 to rotate. As a result, the substrate W is rotated around the rotation axis A1. The spin motor 23 is an example of a substrate rotation unit that rotates the substrate W around the rotation axis A1.

[0058] The opposing member 6 faces the substrate W held by the spin chuck 5 from above. The opposing member 6 is formed in a disc shape with a diameter approximately the same as or greater than that of the substrate W. The opposing member 6 has an opposing surface 6a that faces the upper surface (upper main surface) of the substrate W. The opposing surface 6a is positioned above the spin chuck 5 and is arranged approximately along a horizontal plane.

[0059] A hollow shaft 60 is fixed to the opposing member 6 on the side opposite to the opposing surface 6a. In the opposing member 6, a communication hole 6b is formed in the portion that coincides with the rotation axis A1 in a plan view, penetrating the opposing member 6 vertically and communicating with the internal space 60a of the hollow shaft 60.

[0060] The opposing member 6 isolates the atmosphere in the space between the opposing surface 6a and the upper surface of the substrate W from the atmosphere outside that space. For this reason, the opposing member 6 is also called a shielding plate.

[0061] The processing unit 2 further includes an opposing member lifting unit 61 that drives the raising and lowering of the opposing member 6. The opposing member lifting unit 61 can position the opposing member 6 at any position (height) from the lower position to the upper position. The lower position is the position in the movable range of the opposing member 6 where the opposing surface 6a is closest to the substrate W. The upper position is the position in the movable range of the opposing member 6 where the opposing surface 6a is furthest from the substrate W.

[0062] The opposing member lifting unit 61 includes, for example, a ball screw mechanism (not shown) coupled to a support member (not shown) that supports a hollow shaft 60, and an electric motor (not shown) that provides driving force to the ball screw mechanism. The opposing member lifting unit 61 is also called an opposing member lifter (barrier plate lifter).

[0063] The processing cup 7 is housed within the chamber 4 (see Figure 5). The processing cup 7 includes a plurality of guards 71 ​​that receive liquid splashing outward from the substrate W held by the spin chuck 5, a plurality of cups 72 that receive liquid guided downward by the plurality of guards 71, and a cylindrical outer wall member 73 that surrounds the plurality of guards 71 ​​and the plurality of cups 72.

[0064] This embodiment shows an example in which two guards 71 ​​(first guard 71A and second guard 71B) and two cups 72 (first cup 72A and second cup 72B) are provided. Each of the first cup 72A and the second cup 72B has the form of an annular groove that is open upward. The first guard 71A is positioned to surround the spin base 21. The second guard 71B is positioned to surround the spin base 21 further outward in the rotational radial direction of the substrate W than the first guard 71A. The first guard 71A and the second guard 71B each have a substantially cylindrical shape, and the upper ends of each guard 71A, 71B are inclined inward toward the spin base 21. The first cup 72A receives liquid guided downward by the first guard 71A. The second cup 72B is formed integrally with the first guard 71A and receives liquid guided downward by the second guard 71B.

[0065] The processing unit 2 includes a guard lifting unit 74 that raises and lowers the first guard 71A and the second guard 71B separately. The guard lifting unit 74 raises and lowers the first guard 71A between a lower position and an upper position. The guard lifting unit 74 raises and lowers the second guard 71B between a lower position and an upper position. When both the first guard 71A and the second guard 71B are in the upper position, the liquid splashing from the substrate W is received by the first guard 71A. When the first guard 71A is in the lower position and the second guard 71B is in the upper position, the liquid splashing from the substrate W is received by the second guard 71B.

[0066] The guard lifting unit 74 includes, for example, a first ball screw mechanism (not shown) coupled to the first guard 71A, a first motor (not shown) that provides driving force to the first ball screw, a second ball screw mechanism (not shown) coupled to the second guard 71B, and a second motor (not shown) that provides driving force to the second ball screw mechanism. The guard lifting unit 74 is also called a guard lifter.

[0067] The first movable nozzle 8 is an example of a chemical supply unit that supplies (discharges) chemical solution toward the upper surface of the substrate W held by the spin chuck 5.

[0068] The first movable nozzle 8 is moved horizontally and vertically by the first nozzle moving unit 36. The first movable nozzle 8 can move between a center position and a home position (retracted position). When the first movable nozzle 8 is in the center position, it faces the rotation center of the upper surface of the substrate W. The rotation center of the upper surface of the substrate W is the point of intersection with the rotation axis A1 on the upper surface of the substrate W.

[0069] When the first movable nozzle 8 is in its home position, it does not face the upper surface of the substrate W, and in a plan view, it is located outside the processing cup 7. The first movable nozzle 8 can move closer to the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0070] The first nozzle moving unit 36 ​​includes, for example, a pivot shaft (not shown) along the vertical direction, an arm (not shown) coupled to the pivot shaft and extending horizontally, and a pivot shaft drive unit (not shown) for raising, lowering, and rotating the pivot shaft.

[0071] The pivot shaft drive unit causes the arm to swing by rotating the pivot shaft around a vertical pivot axis. Furthermore, the pivot shaft drive unit causes the arm to move up and down by raising and lowering the pivot shaft along the vertical direction. The first movable nozzle 8 is fixed to the arm. In response to the swinging and raising and lowering of the arm, the first movable nozzle 8 moves in the horizontal and vertical directions.

[0072] The first movable nozzle 8 is connected to a chemical solution piping 40 that guides the chemical solution. When a chemical solution valve 50 interposed in the chemical solution piping 40 is opened, the chemical solution is continuously discharged downward from the first movable nozzle 8.

[0073] The chemical solution discharged from the first mobile nozzle 8 is, for example, a solution containing at least one of the following: sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, hydrogen peroxide, organic acids (e.g., citric acid, oxalic acid, etc.), organic alkalis (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactants, and corrosion inhibitors. Examples of chemical solutions that are mixtures of these include SPM solution (sulfuric acid / hydrogen peroxide mixture) and SC1 solution (ammonia-hydrogen peroxide mixture).

[0074] The second moving nozzle 9 is an example of a processing liquid supply unit that supplies (discharges) processing liquid toward the upper surface of the substrate W held by the spin chuck 5.

[0075] The second movable nozzle 9 is moved horizontally and vertically by the second nozzle moving unit 37. The second movable nozzle 9 can move between a central position and a home position (retracted position). When the second movable nozzle 9 is in the central position, it faces the rotation center of the upper surface of the substrate W.

[0076] When the second movable nozzle 9 is in its home position, it does not face the upper surface of the substrate W, and in a plan view, it is located outside the processing cup 7. The second movable nozzle 9 can move closer to the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0077] The second nozzle moving unit 37 has the same configuration as the first nozzle moving unit 36. That is, the second nozzle moving unit 37 includes, for example, a pivot shaft (not shown) along the vertical direction, an arm (not shown) that is coupled to the pivot shaft and the second moving nozzle 9 and extends horizontally, and a pivot shaft drive unit (not shown) that raises and lowers the pivot shaft and rotates it.

[0078] The second movable nozzle 9 is connected to a processing liquid piping 41 that guides the processing liquid. When the processing liquid valve 51 interposed in the processing liquid piping 41 is opened, the processing liquid is continuously discharged downward from the second movable nozzle 9.

[0079] The processing liquid discharged from the second moving nozzle 9 contains a solute and a solvent. This processing liquid solidifies or hardens as at least a portion of the solvent volatilizes (evaporates). By solidifying or hardening on the substrate W, this processing liquid forms a processing film that holds the target objects (foreign matter) such as particles present on the substrate W.

[0080] Here, "solidification," as mentioned above, refers to the process by which a solute solidifies due to forces acting between molecules or atoms, for example, as a result of the volatilization (evaporation) of the solvent. "Hardening," on the other hand, refers to the process by which a solute solidifies due to chemical changes such as polymerization or crosslinking. Therefore, "solidification or hardening" refers to the process by which a solute "solidifies" due to various factors.

[0081] The solute in the processing liquid discharged from the second mobile nozzle 9 may contain, for example, a first component and a second component. For example, the amount (content) of the first component in the processing liquid is less than the amount (content) of the second component in the processing liquid.

[0082] The first and second components are, for example, synthetic resins with different properties. The solvent contained in the processing liquid discharged from the second moving nozzle 9 can be any liquid that dissolves the first and second components.

[0083] Examples of synthetic resins used as solutes include acrylic resins, phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, polyimides, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resins, acrylonitrile styrene resins, polyamides, polyacetals, polycarbonates, polyvinyl alcohols, modified polyphenylene ethers, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polysulfones, polyether ether ketones, and polyamide-imides.

[0084] Examples of solvents for dissolving synthetic resins include IPA, cyclopentanol, PGEE (propylene glycol monoethyl ether), PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), and EL (ethyl lactate).

[0085] The third movable nozzle 10 is an example of a stripping liquid supply unit that supplies (discharges) stripping liquid toward the upper surface of the substrate W held by the spin chuck 5, and is an example of a processed film removal unit that strips the processed film 100 on the substrate W by supplying the stripping liquid and removes it from the substrate W. In this embodiment, the third movable nozzle 10 is also an example of a solvent extractant supply unit that supplies (discharges) solvent extractant toward the upper surface of the substrate W held by the spin chuck 5. Of course, the stripping liquid supply unit and the solvent extractant supply unit may be equipped with separate nozzles.

[0086] The third movable nozzle 10 is moved horizontally and vertically by the third nozzle moving unit 38. The third movable nozzle 10 can move between a central position and a home position (retracted position).

[0087] When the third movable nozzle 10 is in its central position, it faces the rotation center of the upper surface of the substrate W. When the third movable nozzle 10 is in its home position, it does not face the upper surface of the substrate W, and in a plan view, it is located outside the processing cup 7. The third movable nozzle 10 can move closer to the upper surface of the substrate W or retract upward from the upper surface of the substrate W by moving in the vertical direction.

[0088] The third nozzle moving unit 38 has the same configuration as the first nozzle moving unit 36. That is, the third nozzle moving unit 38 includes, for example, a pivot shaft (not shown) along the vertical direction, an arm (not shown) that is coupled to the pivot shaft and the third moving nozzle 10 and extends horizontally, and a pivot shaft drive unit (not shown) that raises and lowers the pivot shaft and rotates it.

[0089] The third movable nozzle 10 is connected to an upper stripping liquid pipe 42 that guides the stripping liquid to the third movable nozzle 10. When the upper stripping liquid valve 52 interposed in the upper stripping liquid pipe 42 is opened, the stripping liquid is continuously discharged downward from the discharge port of the third movable nozzle 10.

[0090] The third movable nozzle 10 is also connected to a solvent extract piping 43 that guides the solvent extract to the third movable nozzle 10. When the solvent extract valve 53 interposed in the solvent extract piping 43 is opened, the solvent extract is continuously discharged downward from the discharge port of the third movable nozzle 10.

[0091] The stripping solution is a liquid used to peel the treated film on the substrate W from the upper surface of the substrate W. The stripping solution used is one that dissolves the first component of the solute in the treatment solution more readily than the second component in the solute of the treatment solution. In other words, the stripping solution used is one in which the solubility (solubility) of the first component in the stripping solution is higher than the solubility (solubility) of the second component in the stripping solution. It is preferable that the stripping solution is a liquid that is miscible (miscible) with the solvent contained in the treatment solution.

[0092] The stripping solution is, for example, an aqueous stripping solution. Examples of aqueous stripping solutions include DIW, carbonated water, electrolyzed ionized water, hydrogen water, ozonated water, and hydrochloric acid water and alkaline aqueous solutions at dilution concentrations (e.g., 10 ppm to 100 ppm). Examples of alkaline aqueous solutions include SC1 solution, ammonia aqueous solution, aqueous solutions of quaternary ammonium hydroxide such as TMAH, and choline aqueous solution.

[0093] As described above, the solvent extract is a liquid capable of extracting the solvent from the treatment film formed on the substrate W to the outside of the treatment film. More specifically, it is a liquid capable of extracting the solvent to the outside of the treatment film without dissolving the solute contained in the treatment solution. Typically, the solute in the treatment solution is insoluble or sparingly soluble in the solvent extract. On the other hand, it is preferable that the solvent extract is a liquid that is miscible with the solvent in the treatment solution, that is, has compatibility and can dissolve indefinitely.

[0094] For example, if the solute contains a polymer and the solvent is water-soluble, the solvent extract may contain water (more specifically, deionized water). The water-soluble solvent may be a liquid containing PGME (propylene glycol monomethyl ether) or IPA. Alternatively, if the solute contains a polymer and the solvent is water-insoluble, the solvent extract may contain an organic solvent (e.g., IPA). The water-insoluble solvent may be a liquid containing PGMEA (propylene glycol monomethyl ether acetate) or cyclopentanol.

[0095] Examples of solvent extractants include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid water at a dilution concentration (e.g., about 1 ppm to 100 ppm) (example of diluting acid), ammonia water at a dilution concentration (e.g., about 1 ppm to 100 ppm), reduced water (hydrogen water), IPA, etc.

[0096] Examples of preferred combinations of solute, solvent, and solvent extract are shown in Table 1 above.

[0097] The central nozzle 11 is housed in the internal space 60a of the hollow shaft 60 of the opposing member 6. The discharge port 11a provided at the tip of the central nozzle 11 faces the central region of the upper surface of the substrate W from above. The central region of the upper surface of the substrate W is the region on the upper surface of the substrate W that includes the center of rotation of the substrate W.

[0098] The central nozzle 11 includes a plurality of tubes 31-33 (first tube 31, second tube 32, and third tube 33) that discharge fluid downward, and a cylindrical casing 30 that surrounds the plurality of tubes 31-33. The plurality of tubes 31-33 and the casing 30 extend vertically along the axis of rotation A1. The discharge port 11a of the central nozzle 11 is also the discharge port of the plurality of tubes 31-33.

[0099] The first tube 31 is an example of a rinse liquid supply unit that supplies rinse liquid to the upper surface of the substrate W. The second tube 32 is an example of a gas supply unit that supplies gas between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6. The third tube 33 is an example of an organic solvent supply unit that supplies an organic solvent such as IPA to the upper surface of the substrate W.

[0100] The first tube 31 is connected to an upper rinse fluid pipe 44 that guides the rinse fluid into the first tube 31. When the upper rinse fluid valve 54, which is interposed in the upper rinse fluid pipe 44, is opened, the rinse fluid is continuously discharged from the first tube 31 (central nozzle 11) toward the central region of the upper surface of the substrate W.

[0101] Examples of rinsing solutions include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid water at a dilution concentration (for example, around 1 ppm to 100 ppm), ammonia water at a dilution concentration (for example, around 1 ppm to 100 ppm), reduced water (hydrogen water), etc.

[0102] The second tube 32 is connected to a gas pipe 45 that guides gas into the second tube 32. When a gas valve 55 interposed in the gas pipe 45 is opened, gas is continuously discharged downward from the second tube 32 (central nozzle 11).

[0103] The gas discharged from the second tube 32 is, for example, nitrogen gas (N ２ The gas discharged from the second tube 32 may be air. The term "inert gas" is not limited to nitrogen gas, but refers to any gas that is inert to the upper surface of the substrate W or to the pattern formed on the upper surface of the substrate W. Examples of inert gases include nitrogen gas and noble gases such as argon.

[0104] The third tube 33 is connected to an organic solvent piping 46 that guides the organic solvent into the third tube 33. When the organic solvent valve 56 interposed in the organic solvent piping 46 is opened, the organic solvent is continuously discharged from the third tube 33 (central nozzle 11) toward the central region of the upper surface of the substrate W.

[0105] The organic solvent discharged from the third tube 33 is a residue removal liquid that removes (for example, by dissolving) any residue remaining on the upper surface of the substrate W after the treatment film has been removed by the stripping liquid. Therefore, the third tube 33 is also an example of a residue removal liquid supply unit that supplies the residue removal liquid to the upper surface of the substrate W. It is preferable that the organic solvent discharged from the third tube 33 is compatible with the treatment liquid and the rinsing liquid.

[0106] Examples of organic solvents discharged from the third tube 33 include a liquid containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

[0107] Furthermore, the organic solvent discharged from the third tube 33 does not need to consist of only a single component, but may be a liquid mixture with other components. The organic solvent discharged from the third tube 33 may be, for example, a mixture of IPA and DIW, or a mixture of IPA and HFE.

[0108] The lower nozzle 12 is inserted into a through hole 21a that opens in the center of the upper surface of the spin base 21. The discharge port 12a of the lower nozzle 12 is exposed from the upper surface of the spin base 21. The discharge port 12a of the lower nozzle 12 faces the central region of the lower surface of the substrate W from below. The central region of the lower surface of the substrate W is the region on the lower surface of the substrate W that includes the center of rotation of the substrate W.

[0109] One end of a common pipe 80 is connected to the lower nozzle 12, which guides the rinsing liquid, stripping liquid, and heat transfer medium to the lower nozzle 12. The other end of the common pipe 80 is connected to a lower rinsing liquid pipe 81 that guides the rinsing liquid to the common pipe 80, a lower stripping liquid pipe 82 that guides the stripping liquid to the common pipe 80, and a heat transfer medium pipe 83 that guides the heat transfer medium to the common pipe 80.

[0110] When the lower rinse fluid valve 86, which is interposed in the lower rinse fluid pipe 81, is opened, the rinse fluid is continuously discharged from the lower nozzle 12 toward the central region of the lower surface of the substrate W. When the lower stripping fluid valve 87, which is interposed in the lower stripping fluid pipe 82, is opened, the stripping fluid is continuously discharged from the lower nozzle 12 toward the central region of the lower surface of the substrate W. When the heat transfer fluid valve 88, which is interposed in the heat transfer fluid pipe 83, is opened, the heat transfer fluid is continuously discharged from the lower nozzle 12 toward the central region of the lower surface of the substrate W.

[0111] The lower nozzle 12 is an example of a lower rinse liquid supply unit that supplies rinse liquid to the lower surface of the substrate W. The lower nozzle 12 is also an example of a lower stripping liquid supply unit that supplies stripping liquid to the lower surface of the substrate W. The lower nozzle 12 is also an example of a heat medium supply unit that supplies a heat medium to the substrate W for heating the substrate W. The lower nozzle 12 is also a heating unit that heats the substrate W, thereby heating the processing film on the substrate W. The heating unit is an example of an evaporation acceleration unit that promotes the evaporation of the solvent in the processing film.

[0112] The heat transfer medium discharged from the lower nozzle 12 is, for example, a high-temperature DIW with a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid (for example, 60°C to 80°C). The heat transfer medium discharged from the lower nozzle 12 is not limited to high-temperature DIW, and may be a high-temperature gas such as a high-temperature inert gas or high-temperature air with a temperature higher than room temperature and lower than the boiling point of the solvent contained in the processing liquid (for example, 60°C to 80°C).

[0113] Instead of heating the substrate W with a heat transfer medium, the substrate W may be heated by a heater 25. For example, the heater 25 may be an electric heater embedded in the spin base 21. Such a heater 25 is an example of a heating unit that heats the processing film on the substrate W, and therefore an example of an evaporation promoting unit that promotes the evaporation of the solvent in the processing film.

[0114] Figure 7 is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus 1.

[0115] The controller 3 is equipped with a microcomputer and controls the control target provided in the substrate processing device 1 according to a predetermined control program.

[0116] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B in which a control program is stored. The controller 3 is configured to perform various controls for board processing by having the processor 3A execute the control program.

[0117] In particular, the controller 3 is programmed to control the transport robots IR and CR, the spin motor 23, the first nozzle moving unit 36, the second nozzle moving unit 37, the third nozzle moving unit 38, the opposing member lifting unit 61, the guard lifting unit 74, the valves 50, 51, 52, 53, 54, 55, 56, 86, 87, 88, and the heater 25.

[0118] Figure 8 is a flowchart illustrating an example of substrate processing by the substrate processing apparatus 1. Figure 8 mainly shows the processing that is realized by the controller 3 executing a program. Figures 9A to 9I are schematic diagrams illustrating each step of the substrate processing.

[0119] In the substrate processing using the substrate processing apparatus 1, for example, as shown in Figure 8, the following steps are performed in this order: substrate loading step S1, chemical solution supply step S2, first rinsing step S3, first organic solvent supply step S4, processing liquid supply step S5, processing film formation step S6, solvent extract supply step S7, solvent extract discharge step S8, heating step S9 (evaporation acceleration step), removal step S10, second rinsing step S11, second organic solvent supply step S12 (residue removal step), spin drying step S13 (shake-off drying step), and substrate unloading step S14.

[0120] First, the unprocessed substrate W is transported from the carrier C to the processing unit 2 by the transport robots IR and CR (see Figure 5) and then passed to the spin chuck 5 (substrate loading process S1). The substrate W is then held horizontally by the spin chuck 5 (substrate holding process). The spin chuck 5 continues to hold the substrate W until the spin drying process S13 is completed. When the substrate W is loaded, the opposing member 6 is retracted to an upper position.

[0121] Next, after the transport robot CR moves out of the processing unit 2, the chemical supply process S2 is started. Specifically, the spin motor 23 rotates the spin base 21. This rotates the horizontally held substrate W (substrate rotation process). Then, the guard lifting unit 74 moves the first guard 71A and the second guard 71B to the upper position.

[0122] Then, the first nozzle moving unit 36 ​​moves the first moving nozzle 8 to the processing position. The processing position of the first moving nozzle 8 is, for example, the central position. Then, the chemical valve 50 is opened. As a result, the chemical is supplied (discharged) from the first moving nozzle 8 toward the central region of the upper surface of the rotating substrate W. In the chemical supply process S2, the substrate W is rotated at a predetermined chemical rotation speed, for example, 800 rpm.

[0123] The chemical solution supplied to the upper surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire upper surface of the substrate W. As a result, the upper surface of the substrate W is treated with the chemical solution. Discharge of the chemical solution from the first moving nozzle 8 continues for a predetermined time, for example, 30 seconds.

[0124] Next, the first rinsing step S3 is started. In the first rinsing step S3, the chemical solution on the substrate W is washed away by the rinsing solution.

[0125] Specifically, the chemical solution valve 50 is closed. This stops the supply of the chemical solution to the substrate W. Then, the first nozzle moving unit 36 ​​moves the first moving nozzle 8 to the home position. Then, the opposing member lifting unit 61 moves the opposing member 6 to a processing position between the upper and lower positions. When the opposing member 6 is in the processing position, the distance between the upper surface of the substrate W and the opposing surface 6a is, for example, 30 mm. In the first rinsing step S3, the positions of the first guard 71A and the second guard 71B are maintained in the upper position.

[0126] Then, the upper rinse fluid valve 54 is opened. As a result, rinse fluid is supplied (discharged) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W. Also, the lower rinse fluid valve 86 is opened. As a result, rinse fluid is supplied (discharged) from the lower nozzle 12 toward the central region of the lower surface of the rotating substrate W. In the first rinsing step S3, the substrate W is rotated at a predetermined first rinsing rotation speed, for example, 800 rpm.

[0127] The rinse liquid supplied from the central nozzle 11 to the upper surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire upper surface of the substrate W. As a result, the chemical solution on the upper surface of the substrate W is washed away from the substrate W.

[0128] The rinsing liquid supplied to the underside of the substrate W from the lower nozzle 12 spreads radially due to centrifugal force, covering the entire underside of the substrate W. Even if chemical solution splashes from the substrate W during the chemical solution supply process S2 and adheres to the underside, the rinsing liquid supplied from the lower nozzle 12 washes away the chemical solution adhering to the underside. The discharge of rinsing liquid from the central nozzle 11 and the lower nozzle 12 continues for a predetermined time, for example, 30 seconds.

[0129] Next, the first organic solvent supply process S4 is started. In the first organic solvent supply process S4, the rinse solution on the substrate W is replaced with the organic solvent.

[0130] Specifically, the upper rinse fluid valve 54 and the lower rinse fluid valve 86 are closed. This stops the supply of rinse fluid to the upper and lower surfaces of the substrate W. Then, the guard lifting unit 74 moves the first guard 71A to the lower position while maintaining the second guard 71B in the upper position. The opposing member 6 is maintained in the processing position.

[0131] In the first organic solvent supply step S4, the substrate W is rotated at a predetermined first organic solvent rotation speed, for example, 300 rpm to 1500 rpm. The substrate W does not need to rotate at a constant rotation speed in the first organic solvent supply step S4. For example, the spin motor 23 may rotate the substrate W at 300 rpm when the supply of the organic solvent begins, and then accelerate the rotation of the substrate W until the rotation speed of the substrate W reaches 1500 rpm while supplying the organic solvent to the substrate W.

[0132] Then, the organic solvent valve 56 is opened. As a result, the organic solvent is supplied (discharged) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W.

[0133] The organic solvent supplied from the central nozzle 11 to the upper surface of the substrate W spreads radially due to centrifugal force, covering the entire upper surface of the substrate W. As a result, the rinsing liquid on the substrate W is replaced by the organic solvent. The discharge of the organic solvent from the central nozzle 11 continues for a predetermined time, for example, 10 seconds.

[0134] Next, the processing liquid supply process S5 is started. Specifically, the organic solvent valve 56 is closed. This stops the supply of organic solvent to the substrate W. Then, the opposing member lifting unit 61 moves the opposing member 6 to the upper position. Then, the guard lifting unit 74 moves the first guard 71A to the upper position. In the processing liquid supply process S5, the substrate W is rotated at a predetermined first rotation speed, for example, several tens of rpm to 200 rpm (first rotation process).

[0135] Then, as shown in Figure 9A, the second nozzle moving unit 37 moves the second moving nozzle 9 to the processing position. The processing position of the second moving nozzle 9 is, for example, the central position. Then, the processing liquid valve 51 is opened. As a result, the processing liquid is supplied (discharged) from the second moving nozzle 9 toward the central region of the upper surface of the rotating substrate W (processing liquid supply step, processing liquid discharge step). As a result, the organic solvent on the substrate W is replaced by the processing liquid, and a liquid film of the processing liquid (processing liquid film 101) is formed on the substrate W (processing liquid film formation step). The supply of processing liquid from the second moving nozzle 9 continues for a predetermined time, for example, 2 to 4 seconds.

[0136] Next, the processing film formation step S6 is performed. In the processing film formation step S6, the processing liquid on the substrate W is solidified or hardened to form a processing film 100 (see Figure 9C) on the upper surface of the substrate W.

[0137] In the processing film formation step S6, the processing liquid valve 51 is first closed. As a result, the supply of processing liquid to the substrate W is stopped, as shown in Figure 9B. Then, the second nozzle moving unit 37 moves the second moving nozzle 9 to the home position.

[0138] In the processing film formation step S6, the supply of processing liquid to the upper surface of the substrate W is stopped, and a portion of the processing liquid is removed (spin-off) from the upper surface of the substrate W by centrifugal force so that the thickness of the processing liquid film 101 on the substrate W becomes an appropriate thickness. In the processing film formation step S6, the opposing member 6, the first guard 71A, and the second guard 71B are maintained in the upper position.

[0139] In the processing film formation step S6, the spin motor 23 accelerates the rotation of the substrate W, changing the rotational speed of the substrate W to a predetermined second rotational speed (second rotation step). The second rotational speed is, for example, 1000 rpm to 1500 rpm. In the processing film formation step S6, the rotational speed of the substrate W may be kept constant within the range of 1000 rpm to 1500 rpm, or it may be appropriately changed within the range of 1000 rpm to 1500 rpm during the processing film formation step S6. The processing film formation step S6 is performed for a predetermined time, for example, 30 seconds.

[0140] During this processing film formation process S6, the solvent in the processing liquid film 101 evaporates from the surface of the processing liquid film 101, causing solute to precipitate on the surface layer of the processing liquid film 101, thereby forming a solidified layer 101b (see Figure 3B). In this way, a semi-solidified (semi-cured) processing film 100 is formed.

[0141] Next, the solvent extract supply step S7 is performed. In the solvent extract supply step S7, the substrate W is rotated at a predetermined liquid processing rotation speed, for example, several tens of rpm to 200 rpm.

[0142] Then, as shown in Figure 9C, the solvent extract valve 53 is opened. As a result, the solvent extract is supplied (discharged) from the third moving nozzle 10 toward the central region of the upper surface of the rotating substrate W. The solvent extract supplied to the upper surface of the substrate W spreads across the entire surface of the processed film 100 due to centrifugal force. The supply of the solvent extract to the surface of the processed film 100 continues for a predetermined time, for example, 5 to 10 seconds, after which the solvent extract valve 53 is closed and the supply of the solvent extract is stopped. Then, the third moving nozzle 10 is moved to the home position by the third nozzle moving unit 38. After the solvent extract has spread across the entire surface of the processed film 100 and a liquid layer has been formed, the rotation of the substrate W may be reduced to a low-speed rotation or stopped state, and the supply of the solvent extract may be stopped to perform a paddle process (liquid layering process) to maintain the liquid layer of the solvent extract on the substrate W (more specifically on the surface of the processed film 100).

[0143] When the solvent extract layer comes into contact with the processing film 100, the solvent within the processing film 100 moves into the solvent extract layer, thereby suppressing or preventing the sealing of the solvent within the processing film (see Figure 3C). It is preferable that the solvent extract supply step S7 is performed in such a way that the solvent extract layer remains in contact with the surface of the processing film 100 for the time required for the extraction of the solvent from the processing film 100.

[0144] Next, the solvent extract discharge step S8 is performed. In the solvent extract discharge step S8, as shown in Figure 9D, the supply of solvent extract to the upper surface of the substrate W is stopped, and the substrate W is rotated, causing the solvent extract to be removed from the upper surface of the substrate W by centrifugal force and discharged outside the substrate W. The opposing member 6, the first guard 71A, and the second guard 71B are maintained in the upper position.

[0145] In the solvent extract discharge step S8, the spin motor 23 accelerates the rotation of the substrate W to its maximum rotational speed. The maximum rotational speed is, for example, 1000 rpm to 1500 rpm. The solvent extract discharge step S8 is performed for a predetermined time, for example, 30 seconds.

[0146] Following the solvent extract discharge step S8, a heating step S9 is performed to heat the substrate W. In the heating step S9, the semi-solidified treatment film 100 on the substrate W is heated in order to volatilize (evaporate) a portion of the solvent in the treatment solution on the substrate W. In other words, the heating step S9 is an example of an evaporation acceleration step that promotes the evaporation of the solvent in the treatment film 100.

[0147] Referring to Figure 9E, specifically, the opposing member lifting unit 61 moves the opposing member 6 to a proximity position between the upper and lower positions. The proximity position may also be the lower position. The proximity position is, for example, a position where the distance from the upper surface of the substrate W to the opposing surface 6a is 1 mm. In the heating process S9, the first guard 71A and the second guard 71B are maintained in the upper position.

[0148] Then, the gas valve 55 is opened. This supplies gas to the space between the upper surface of the substrate W (the upper surface of the processing liquid film 101) and the opposing surface 6a of the opposing member 6 (gas supply step).

[0149] Then, the heat transfer valve 88 is opened. As a result, the heat transfer medium is supplied (discharged) from the bottom nozzle 12 toward the central region of the lower surface of the rotating substrate W (heat transfer medium supply step, heat transfer medium discharge step). The heat transfer medium supplied from the bottom nozzle 12 to the lower surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire lower surface of the substrate W. The supply of heat transfer medium to the substrate W is continued for a predetermined time, for example, 60 seconds. In the heating step S9, the substrate W is rotated at a predetermined heating rotation speed, for example, 1000 rpm.

[0150] A heat transfer medium is supplied to the lower surface of the substrate W, thereby heating the processing liquid film 101 on the substrate W via the substrate W. This promotes the evaporation of the solvent in the processing liquid film 101 (solvent evaporation step, solvent evaporation promotion step). As a result, the time required for the formation of the processing film 100 can be shortened. The lower nozzle 12 functions as an evaporation promotion unit that accelerates the evaporation of the solvent in the processing liquid.

[0151] The heating step S9 is performed to form a completely solidified or cured treatment film 100 on the substrate W. Thus, the substrate rotation unit (spin motor 23) and the lower nozzle 12 constitute a solid formation unit that solidifies or cures the treatment liquid to form a solid (treatment film 100). Although the thickness of the treatment film 100 is much thinner than the thickness of the substrate W, in Figure 9E and other figures, it is exaggerated (to be approximately the same thickness as the substrate W) for the sake of explanation. The same applies to Figures 9D and 9F.

[0152] In the heating step S9, it is preferable that the substrate W is heated so that the temperature of the processing solution on the substrate W is below the boiling point of the solvent. By heating the processing solution to a temperature below the boiling point of the solvent, an appropriate amount of solvent can be left in the processed film 100. As a result, compared to the case where no solvent remains in the processed film 100, in the subsequent removal step S10, the interaction between the solvent remaining in the processed film 100 and the stripping solution makes it easier for the stripping solution to adhere to the processed film 100. Therefore, it becomes easier to peel off the processed film 100 with the stripping solution.

[0153] The heat transfer medium scattered outside the substrate W by centrifugal force is received by the first guard 71A. The heat transfer medium received by the first guard 71A may bounce back from the first guard 71A. However, since the opposing member 6 is close to the upper surface of the substrate W, it can protect the upper surface of the substrate W from the heat transfer medium bounced back from the first guard 71A. Therefore, the adhesion of the heat transfer medium to the upper surface of the processed film 100 can be suppressed, and thus the generation of particles caused by the heat transfer medium bouncing back from the first guard 71A can be suppressed.

[0154] Furthermore, the supply of gas from the central nozzle 11 creates an airflow F in the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W, which moves from the central region of the upper surface of the substrate W toward the periphery of the upper surface of the substrate W. By creating an airflow F that moves from the central region of the upper surface of the substrate W toward the periphery of the upper surface of the substrate W, the heat transfer medium that has bounced back from the first guard 71A can be pushed back toward the first guard 71A. Therefore, the adhesion of the heat transfer medium to the upper surface of the processed film 100 can be further suppressed.

[0155] In addition, in the heating step S9, instead of heating with a heat transfer medium, the substrate W may be heated by a heater 25 provided on the spin base 21.

[0156] Here, the processing liquid supplied to the upper surface of the substrate W in the processing liquid supply step S5 shown in Figure 9A may flow along the periphery of the substrate W and wrap around to the lower surface of the substrate W. Also, processing liquid scattered from the substrate W may bounce off the first guard 71A and adhere to the lower surface of the substrate W. Even in such cases, by performing the heating step S9 using a heat transfer medium, as shown in Figure 9E, the heat transfer medium is supplied to the lower surface of the substrate W, and the flow of the heat transfer medium can remove the processing liquid from the lower surface of the substrate W.

[0157] Next, the removal process S10 is performed. In the removal process S10, the substrate W is rotated at a predetermined removal rotation speed, for example, 800 rpm. Then, as shown in Figure 9F, the upper stripping liquid valve 52 is opened. As a result, the stripping liquid is supplied (discharged) from the third moving nozzle 10 toward the central region of the upper surface of the rotating substrate W (upper stripping liquid supply process, upper stripping liquid discharge process). The stripping liquid supplied to the upper surface of the substrate W spreads across the entire upper surface of the substrate W due to centrifugal force. The supply of the stripping liquid to the upper surface of the substrate W is continued for a predetermined time, for example, 60 seconds.

[0158] When a stripping solution is supplied to the upper surface of the substrate W, the treated film 100 is peeled off from the upper surface of the substrate W. As the treated film 100 is peeled off from the upper surface of the substrate W, it breaks apart into film fragments. These fragments of the broken treated film 100 are then subjected to centrifugal force due to the rotation of the substrate W and are removed from the substrate W along with the stripping solution. In this way, the treated film 100 and the object to be removed are removed from the upper surface of the substrate W.

[0159] As a result of the processing liquid supply step S5, the processing liquid adhering to the lower surface of the substrate W may solidify or harden, forming a solid. Even in such cases, as shown in Figure 9F, while the stripping liquid is being supplied to the upper surface of the substrate W in the removal step S10, the stripping liquid can be opened and the stripping liquid can be supplied (discharged) from the lower nozzle 12 to the lower surface of the substrate W, thereby allowing the solid to be removed from the lower surface of the substrate W (lower stripping liquid supply step, lower stripping liquid discharge step).

[0160] Next, the second rinsing step S11 is performed. Specifically, the upper stripping liquid valve 52 and the lower stripping liquid valve 87 are closed. This stops the supply of stripping liquid to the upper and lower surfaces of the substrate W. Then, the third nozzle moving unit 38 moves the third moving nozzle 10 to the home position. Then, as shown in Figure 9G, the opposing member lifting unit 61 moves the opposing member 6 to the processing position. In the second rinsing step, the substrate W is rotated at a predetermined second rinsing rotation speed, for example, 800 rpm. The first guard 71A and the second guard 71B are maintained in the upper position.

[0161] Then, the upper rinse liquid valve 54 is opened. As a result, rinse liquid is supplied (discharged) from the central nozzle 11 toward the central region of the upper surface of the rotating substrate W (second upper rinse liquid supply step, second upper rinse liquid discharge step). The rinse liquid supplied to the upper surface of the substrate W is subjected to centrifugal force and spreads radially, covering the entire upper surface of the substrate W. As a result, the stripping liquid adhering to the upper surface of the substrate W is washed away by the rinse liquid.

[0162] Then, the lower rinse liquid valve 86 is opened. As a result, rinse liquid is supplied (discharged) from the lower nozzle 12 toward the central region of the lower surface of the rotating substrate W (second lower rinse liquid supply step, second lower rinse liquid discharge step). This washes away any stripping liquid adhering to the lower surface of the substrate W with the rinse liquid. The supply of rinse liquid to the upper and lower surfaces of the substrate W is continued for a predetermined time, for example, 35 seconds.

[0163] Next, the second organic solvent supply step S12 (residue removal step) is performed. Specifically, as shown in Figure 9H, the guard lifting unit 74 moves the first guard 71A to the lower position. The opposing member 6 is then maintained in the processing position. In the second organic solvent supply step S12, the substrate W is rotated at a predetermined second organic solvent rotation speed, for example, 300 rpm.

[0164] Then, the upper rinse fluid valve 54 and the lower rinse fluid valve 86 are closed. This stops the supply of rinse fluid to the upper and lower surfaces of the substrate W. Then, as shown in Figure 9H, the organic solvent valve 56 is opened. This allows the organic solvent to be supplied (discharged) from the central nozzle 11 towards the central region of the upper surface of the rotating substrate W (second organic solvent supply step, second organic solvent discharge step, residue removal fluid supply step). The supply of organic solvent to the upper surface of the substrate W continues for a predetermined time, for example, 30 seconds.

[0165] The organic solvent supplied to the upper surface of the substrate W spreads radially due to centrifugal force, covering the entire upper surface of the substrate W. As a result, the rinsing liquid on the upper surface of the substrate W is replaced with the organic solvent. The organic solvent supplied to the upper surface of the substrate W dissolves the residue of the treatment film 100 remaining on the upper surface of the substrate W, and then, due to centrifugal force, is discharged from the periphery of the upper surface of the substrate W to the outside of the substrate W (residue removal step).

[0166] Next, the spin-drying process S13 is performed. Specifically, the organic solvent valve 56 is closed. This stops the supply of organic solvent to the upper surface of the substrate W. Then, as shown in Figure 9I, the opposing member lifting unit 61 moves the opposing member 6 to a drying position below the processing position. When the opposing member 6 is in the drying position, the distance between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 55 is opened. This supplies gas to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6.

[0167] Then, the spin motor 23 accelerates the rotation of the substrate W, causing the substrate W to rotate at high speed. In the spin-drying process, the substrate W is rotated at a drying speed, for example, 1500 rpm. The spin-drying process is performed for a predetermined time, for example, 30 seconds. This generates a large centrifugal force that acts on the organic solvent on the substrate W, causing the organic solvent on the substrate W to be swept away around the substrate W. In the spin-drying process, the evaporation of the organic solvent is promoted by supplying gas to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6.

[0168] Then, the spin motor 23 stops the rotation of the substrate W. The guard lifting unit 74 moves the first guard 71A and the second guard 71B to the lower position. The gas valve 55 is closed. The opposing member lifting unit 61 moves the opposing member 6 to the upper position.

[0169] Subsequently, the transport robot CR enters the processing unit 2, scoops up the processed substrate W from the chuck pin 20 of the spin chuck 5, and transports it out of the processing unit 2 (substrate transport process S14). The substrate W is then passed from the transport robot CR to the transport robot IR, and the transport robot IR places it in the carrier C.

[0170] Next, with reference to Figures 10A to 10C, the process of peeling the processed film 100 from the substrate W will be described. Figure 10A shows the area near the top surface of the substrate W after the heating step S9. Figures 10B and 10C show the area near the top surface of the substrate W during the removal step S10.

[0171] In the heating step S9, as described above, the treatment film 100 on the substrate W is heated through the substrate W. As a result, as shown in Figure 10A, a treatment film 100 is formed that holds the objects to be removed 103 (foreign matter), such as particles. Specifically, as at least a portion of the solvent evaporates, the first component contained in the solute of the treatment liquid forms the first solid 110, and the second component contained in the solute of the treatment liquid forms the second solid 111.

[0172] Then, referring to Figure 10B, in the removal step S10, the processed film 100 is partially dissolved. When the stripping solution is supplied to the upper surface of the substrate W, the first solid 110, which is formed by the first component having higher solubility in the stripping solution than the second component, is mainly dissolved. As a result, through holes 102 (paths for the stripping solution) are formed in the parts of the processed film 100 where the first solid 110 is unevenly distributed (through hole formation step). The through holes 102 are particularly likely to be formed in the parts where the first solid 110 extends in the thickness direction T of the substrate W (which is also the thickness direction of the processed film 100). In plan view, the through holes 102 are, for example, several nanometers in diameter.

[0173] The second solid 111 is also dissolved in the stripping solution. However, since the solubility of the second component in the stripping solution is lower than that of the first component, only the surface of the second solid 111 is slightly dissolved by the stripping solution. Therefore, the stripping solution that reaches the vicinity of the upper surface of the substrate W through the through-hole 102 slightly dissolves the portion of the second solid 111 near the upper surface of the substrate W. As a result, as shown in the enlarged view of Figure 10B, the stripping solution gradually dissolves the second solid 111 near the upper surface of the substrate W and enters the gap G1 between the processed film 100 and the upper surface of the substrate W (stripping solution entry step).

[0174] Then, for example, the processed film 100 splits starting from the periphery of the through hole 102 to form film fragments, and as shown in Figure 10C, the film fragments of the processed film 100 are peeled off the substrate W while holding the object to be removed 103 (processed film splitting step, peeling step). Then, the object to be removed 103, while being held by the processed film 100, is pushed out of the substrate W together with the processed film 100 and removed from the upper surface of the substrate W (removal step).

[0175] In some cases, the stripping solution may not dissolve the second solid 111 at all. Even in this case, the stripping solution penetrates the small gap G1 between the treated film 100 and the upper surface of the substrate W, causing the treated film 100 to be peeled off from the substrate W.

[0176] This invention is not limited to the embodiments described above, and can be implemented in other forms.

[0177] For example, in the substrate processing apparatus 1, substrate processing may be performed in which the chemical solution supply step S2, the first rinsing step S3, and the first organic solvent supply step S4 are omitted.

[0178] Furthermore, in the substrate processing described above, the processed film 100 is heated by heating the substrate W with a heat transfer medium or a heater 25 provided on the spin base 21 to promote the evaporation of the solvent. However, the processed film 100 may also be heated by a heater (electric heater, lamp, etc.) built into the opposing member 6. In this case, the heater functions as a heating unit (evaporation promotion unit). Also, the heat transfer medium is not limited to a liquid, but may be a high-temperature gas. Moreover, an evaporation promotion unit may be used that promotes the evaporation of the solvent in the processed film not only by heating, but also by reduced pressure or irradiation with ultraviolet light.

[0179] Furthermore, in each of the embodiments described above, the components of the solute contained in the processing solution (the first and second components) are synthetic resins. However, the components of the solute do not necessarily have to be synthetic resins; they just need to be dissolved by the solvent contained in the processing solution, and the solubility of the first component in the stripping solution is higher than that of the second component. In that case, the components of the solute may be, for example, metals or salts.

[0180] Furthermore, in the embodiments described above, the solute contained in the processing solution includes a first component and a second component. However, the solute may be configured to contain a single component, or it may contain three or more components with different solubility in the stripping solution.

[0181] Furthermore, the processing liquid and stripping liquid described in each of the embodiments described above will also produce the same effects as those described below.

[0182] Below, "C ｘ～ｙ "C ｘ～ C ｙ " and "C ｘ The notation, such as "...", refers to the number of carbon atoms in the molecule or substituent. For example, C １～６ Alkyl refers to an alkyl chain having 1 to 6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, and hexyl).

[0183] In the following, if a polymer has multiple types of repeating units, these repeating units copolymerize. Unless otherwise specified, these copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When polymers and resins are shown in structural formulas, n, m, etc., in parentheses indicate the number of repeating units.

[0184] <Processing Solution> The processing solution contains (A) a second component which is an insoluble or sparingly soluble solute, (B) a first component which is a soluble solute, and (C) a solvent. The processing solution is dropped onto a substrate and dried to remove (C) the solvent, (A) the second component which forms a film, and (B) the first component which remains on the substrate as a film, after which the film is removed from the substrate by a stripping solution. Preferably, (A) the second component is insoluble or sparingly soluble in the stripping solution. Also preferably, (B) the first component is soluble in the stripping solution. The above "solute" is not limited to being dissolved in (C) the solvent, but a suspended state is also acceptable. In one preferred embodiment, the solute, components and additives contained in the processing solution are dissolved in (C) the solvent. A processing solution in this embodiment is considered to have good embedding performance or film uniformity.

[0185] Here, preferably, "together as a film" means that they coexist within a single film, and not that each forms a separate layer. One form of "film formation" is "solidification." The film obtained from the processing liquid only needs to be firm enough to hold particles, and it is not necessary for the (C) solvent to be completely removed (e.g., by vaporization). The processing liquid gradually shrinks as the (C) solvent evaporates, forming a film. "Remaining on the substrate as a film" means that it is permissible for a very small amount to be removed relative to the whole (e.g., by evaporation, volatilization). For example, it is permissible for 0 to 10% by mass (preferably 0 to 5% by mass, more preferably 0 to 3% by mass, even more preferably 0 to 1% by mass, and even more preferably 0 to 0.5% by mass) to be removed relative to the original amount.

[0186] There is no intention to limit the scope of rights, and we are not bound by theory, but it is thought that the aforementioned film holds particles on the substrate and is removed by peeling it off with a stripping solution. Furthermore, since component (B) first remains on the film, it is thought that a point is created that triggers the peeling of the film.

[0187] <Second Component> (A) The second component comprises at least one of novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and copolymers of combinations thereof. Preferably, (A) the second component may comprise at least one of novolac, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and copolymers of combinations thereof. More preferably, (A) the second component may comprise at least one of novolac, polyhydrostyrene, polycarbonate, and copolymers of combinations thereof. The novolac may be phenol novolac.

[0188] Needless to say, the processing solution may contain one or more of the above preferred examples in combination as component (A). For example, component (A) may contain both novolac and polyhydroxystyrene.

[0189] (A) In a preferred embodiment, the second component (A) forms a film upon drying, and the film is peeled off with the peeling solution described later, while retaining the particles, without being largely dissolved. However, an embodiment in which a very small portion of the second component (A) is dissolved by the peeling solution is acceptable.

[0190] Preferably, (A) the second component does not contain fluorine and / or silicon, and more preferably neither.

[0191] The copolymerization is preferably random copolymerization or block copolymerization.

[0192] While there is no intention to limit the scope of rights, (A) specific examples of the second component include the compounds shown in Chemical Formulas 1 to 7 below.

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] (A) The weight-average molecular weight (Mw) of the second component is preferably 150 to 500,000, more preferably 300 to 300,000, even more preferably 500 to 100,000, and even more preferably 1,000 to 50,000.

[0200] (A) The second component can be obtained by synthesis. It can also be purchased. When purchasing, the following are examples of suppliers. The suppliers can also synthesize the polymer (A). Novolac: Showa Chemicals Co., Ltd., Asahi Organic Chemicals Co., Ltd., Gun-ei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd. Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Industry Co., Ltd. Polyacrylic acid derivative: Nippon Shokubai Co., Ltd. Polycarbonate: Sigma-Aldrich Polymethacrylic acid derivative: Sigma-Aldrich Compared to the total mass of the treatment solution, the second component (A) is 0.1 to 50% by mass, preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass. In other words, with the total mass of the treatment solution being 100% by mass, the second component (A) is 0.1 to 50% by mass based on this. That is, "compared to" can be rephrased as "based on". Unless otherwise specified, the same applies below.

[0201] Solubility can be evaluated by known methods. For example, under conditions of 20°C to 35°C (more preferably 25±2°C), 100 ppm of (A) or (B) described below is added to 5.0% by mass aqueous ammonia in a flask, the lid is closed, and the flask is shaken for 3 hours with a shaker to determine whether (A) or (B) has dissolved. Shaking may also be done by stirring. Dissolution can also be judged visually. If it does not dissolve, the solubility is less than 100 ppm; if it dissolves, the solubility is 100 ppm or more. Solubility less than 100 ppm is insoluble or sparingly soluble, and solubility 100 ppm or more is soluble. In a broad sense, soluble includes slightly soluble. Solubility decreases in the order of insoluble, sparingly soluble, and soluble. In a narrow sense, slightly soluble has lower solubility than soluble and higher solubility than sparingly soluble.

[0202] The aforementioned 5.0% by mass aqueous ammonia may be replaced with a stripping solution used in a later process. The solution used for solubility evaluation and the stripping solution do not need to be the same; it is sufficient if components with different solubility are present together. The first component (B) present in the processed film (particle-retaining layer) formed from the processing solution dissolves when exposed to the stripping solution, providing an opportunity for the processed film to peel off from the substrate. Therefore, if a portion of the first component (B) can dissolve in the stripping solution, it can provide an opportunity for the processed film to peel off. For this reason, the stripping solution may be less alkaline than the solution used for solubility evaluation.

[0203] <Component 1> (B) Component 1 is (B') a crack-promoting component. (B') The crack-promoting component contains hydrocarbons and further contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). If (B') the crack-promoting component is a polymer, each constituent unit contains a hydrocarbon and further has a hydroxyl group and / or a carbonyl group. Examples of carbonyl groups include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and enones, with carboxylic acids being preferred.

[0204] There is no intention to limit the scope of rights, and the theory is not binding, but it is thought that when the processing solution dries and forms a processing film on the substrate, and the stripping solution peels off the processing film, component (B) first creates a point that triggers the peeling of the processing film. For this reason, it is preferable that component (B) first has higher solubility in the stripping solution than component (A) second. Examples of embodiments in which component (B') crack-promoting component contains a ketone as a carbonyl group include cyclic hydrocarbons. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0205] More specifically, (B) the first component is represented by at least one of the following (B-1), (B-2), and (B-3). (B-1) consists of 1 to 6 (preferably 1 to 4) constituent units of the following chemical formula 8, and each constituent unit is a linking group L １ It is a compound that is bonded together.

[0206] Here, L１ is selected from at least one of a single bond and C １～６ alkylene. The C １～６ alkylene links the structural units as a linker and is not limited to a divalent group. Preferably, it is divalent to tetravalent. The C １～６ alkylene may be either linear or branched. L ９ is preferably a single bond, methylene, ethylene, or propylene.

[0207] Cy １ is a hydrocarbon ring of C ５～３０ , preferably phenyl, cyclohexane, or naphthyl, and more preferably phenyl. As a preferred embodiment, the linker L １ links a plurality of Cy １ .

[0208] R １ are]]are each independently C １～５ alkyl, preferably methyl, ethyl, propyl, or butyl. The C １～５ alkyl may be either linear or branched.

[0209] n ｂ１ is 1, 2, or 3, preferably 1 or 2, and more preferably 1. n ｂ１’ is 0, 1, 2, 3, or 4, preferably 0, 1, or 2.

[0210] Although there is no intention to limit the scope of rights, preferred examples of (B-1) include 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. These may be obtained by polymerization or condensation.

[0211] As an example, we will discuss 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, shown in chemical formula 9. This compound has three constituent units of chemical formula 8 in (B-1), and the constituent unit is L １ It is bonded with (methylene). ｂ１ = n ｂ１’ = 1, R １ It is methyl.

[0212] (B-2) is represented by the following chemical formula 10.

[0213] R ２１ , R ２２ , R ２３ , and R ２４ Each is independently either hydrogen or C １～５ The alkyl group is preferably hydrogen, methyl, ethyl, t-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

[0214] L ２１ and L ２２ Each of them independently, C １～２０ Alkylene, C １～２０ Cycloalkylene, C ２～４ Alkenylene, C ２～４ Alkynylene, or C ６～２０ These are arylenes. These groups are C １～５ It may be substituted with alkyl or hydroxy. Here, alkenylene means a divalent hydrocarbon having one or more double bonds, and alkylylene means a divalent hydrocarbon group having one or more triple bonds. ２１ and L ２２ Preferably C ２～４ Alkylene, acetylene (C ２ It is an alkynylene (or phenylene), more preferably C ２～４ The alkylene or acetylene, more preferably acetylene.

[0215] n ｂ２is 0, 1, or 2, preferably 0 or 1, more preferably 0.

[0216] While there is no intention to limit the scope of rights, preferred examples of (B-2) include 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyne-2,5-diol. Another preferred example of (B-2) is 3-hexyne-2,5-diol, 1,4-butynediol, 2,4-hexadiyne-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzenedimethanol.

[0217] (B-3) is a polymer comprising a constituent unit represented by the following chemical formula 11, with a weight-average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, and more preferably 700 to 3,000.

[0218] Here, R ２５ H is -H, -CH ３ , or -COOH, preferably -H, or -COOH. A single (B-3) polymer may also comprise two or more constituent units, each represented by chemical formula 8.

[0219] While there is no intention to limit the scope of rights, preferred examples of (B-3) polymers include polymers of acrylic acid, maleic acid, acrylic acid, or combinations thereof. Polyacrylic acid and maleic acid acrylic acid copolymers are even more preferred examples.

[0220] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0221] As an example, let us explain using the maleate acrylic acid copolymer shown in chemical formula 12. This copolymer is included in (B-3) and has two types of constituent units represented by chemical formula 8, and in one constituent unit R ２５ is -H, and in another constituent unit R ２５ It is -COOH.

[0222] Needless to say, the processing solution may contain one or more of the above preferred examples in combination as component (B) first. For example, component (B) first may contain both 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0223] (B) The first component may have a molecular weight of 80 to 10,000. Preferably, the first component has a molecular weight of 90 to 5,000, and more preferably 100 to 3,000. (B) When the first component is a resin, polymer, or polymer, the molecular weight is expressed as the weight-average molecular weight (Mw).

[0224] (B) The first component can be obtained either through synthesis or purchase. Suppliers include Sigma-Aldrich, Tokyo Chemical Industry, and Nippon Shokubai.

[0225] In the processing solution, component (B) first is preferably 1 to 100% by mass, and more preferably 1 to 50% by mass, compared to the mass of component (A) second. In the processing solution, component (B) first is even more preferably 1 to 30% by mass, compared to the mass of component (A) second.

[0226] <Solvent> (C) The solvent preferably contains an organic solvent. (C) The solvent may be volatile. Volatility means that it is more volatile than water. For example, the boiling point of (C) the solvent at 1 atmosphere is preferably 50 to 250°C. The boiling point of the solvent at 1 atmosphere is more preferably 50 to 200°C, and even more preferably 60 to 170°C. The boiling point of the solvent at 1 atmosphere is even more preferably 70 to 150°C. (C) The solvent may also contain a small amount of pure water. The amount of pure water contained in (C) the solvent is preferably 30% by mass or less, compared to the total amount of (C) the solvent. The amount of pure water contained in the solvent is more preferably 20% by mass or less, and even more preferably 10% by mass or less. The amount of pure water contained in the solvent is even more preferably 5% by mass or less. It is also a preferred form that the solvent does not contain pure water (0% by mass). Pure water is preferably DIW.

[0227] Examples of organic solvents include alcohols such as isopropanol (IPA) and cyclopentanol; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE); propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; lactic acid esters such as methyl lactate and ethyl lactate (EL); aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone; amides such as N,N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. These organic solvents can be used individually or in combination of two or more.

[0228] In a preferred embodiment, the organic solvent contained in solvent (C) is selected from IPA, cyclopentanol, PGME, PGEE, EL, PGMEA, or any combination thereof. When the organic solvents are a combination of two types, their volume ratio is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30.

[0229] Compared to the total mass of the processing solution, the amount of solvent (C) is 0.1 to 99.9% by mass. Compared to the total mass of the processing solution, the amount of solvent (C) is preferably 50 to 99.9% by mass, more preferably 75 to 99.5% by mass. Compared to the total mass of the processing solution, the amount of solvent (C) is even more preferably 80 to 99% by mass, and even more preferably 85 to 99% by mass.

[0230] <Other Additives> The treatment solution of the present invention may further contain (D) other additives. In one embodiment of the present invention, (D) other additives include surfactants, acids, bases, antibacterial agents, disinfectants, preservatives, or antifungal agents (preferably surfactants), and may include any combination thereof.

[0231] In one aspect of the present invention, the amount of (D) other additives (if there are multiple, their sum) in the treatment solution is 0 to 100 by mass (preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass) compared to the mass of (A) the second component in the treatment solution. Another aspect of the present invention is that the treatment solution does not contain (D) other additives (0% by mass).

[0232] <Removal Solution> As mentioned above, the treatment solution is dropped onto the substrate and dried, removing the solvent (C) and forming a film of the second component (A). As a result, the second component (A), along with the first component (B), remains on the substrate as a treatment film, and the treatment film (particle-holding layer) is then removed from the substrate by the removal solution. The treatment film is capable of holding particles present on the substrate and is removed by the removal solution while retaining them.

[0233] The stripping solution may be alkaline, neutral, or acidic, but it is preferably alkaline. The pH of the stripping solution is preferably 7 to 13. More specifically, the pH of the stripping solution is preferably 8 to 13, more preferably 10 to 13, and even more preferably 11 to 12.5. To avoid the influence of dissolved carbon dioxide in the air, it is preferable to measure the pH after degassing.

[0234] While there is no intention to limit the scope of rights, specific examples of the stripping solution include ammonia water, SC-1 cleaning solution, TMAH aqueous solution, choline aqueous solution, or any combination thereof (preferably ammonia water). The majority of the solvent in the stripping solution is pure water. The proportion of pure water in the solvent of the stripping solution is 50 to 100% by mass (preferably 70 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and even more preferably 99 to 100% by mass). The concentration of the solute in the stripping solution is 0.1 to 10% by mass (preferably 0.2 to 8% by mass, even more preferably 0.3 to 6% by mass). By adding the above-mentioned alkaline component to the processing solution, it is also possible to use pure water (solute concentration 0.0% by mass, preferably 0.00% by mass) as the stripping solution.

[0235] The formation of the treated film and the peeling of the treated film from the substrate can also be described as follows.

[0236] The processing solution consists of (A) a second component, (B') a crack-promoting component (first component), and (C) a solvent. By dropping the processing solution of the present invention onto a substrate and drying it, (A) the second component forms a film. The formation of a processing film is achieved by the film-forming of (A) the second component. Subsequently, by supplying a stripping solution to the processing film, the crack-promoting component dissolves into the stripping solution. As the crack-promoting component dissolves into the stripping solution, traces (voids) where the crack-promoting component has dissolved are created in the processing film. These traces promote the peeling of the particle layer and its removal from the substrate. Cracks spread starting from these traces. As the cracks spread, the fragmented processing film is removed from the substrate while retaining the particles.

[0237] When the stripping solution removes the treated film (e.g., by peeling), it is thought that the first component (B) remaining in the film creates a point where the treated film can peel off. Therefore, it is preferable that the first component (B) has higher solubility in the stripping solution than the second component (A). It is preferable that the treated film is removed from the substrate without being completely dissolved by the stripping solution, while retaining the particles. It is thought that the treated film is removed in a state where it is finely broken down by, for example, the aforementioned "point where peeling can be initiated".

[0238] In this specification, unless otherwise specifically stated, the singular form includes the plural form, and “one” or “that” means “at least one.” Unless otherwise specifically stated, an element of a concept can be expressed by multiple types, and if a quantity (e.g., mass %) or mole %) is given, that quantity means the sum of those multiple types.

[0239] "and / or" includes all combinations of elements, as well as their use individually.

[0240] In this specification, when numerical ranges are indicated using "~" or "-", unless otherwise specifically stated, these include both endpoints and the units are common. For example, 5~25 mol% means 5 mol% or more and 25 mol% or less.

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

[0242] 1: Substrate processing device 2: Processing unit 3: Controller 5: Spin chuck 8: First moving nozzle 9: Second moving nozzle 10: Third moving nozzle 11: Central nozzle 12: Bottom nozzle 23: Spin motor 25: Heater 31: First tube 32: Second tube 33: Third tube 40: Chemical piping 41: Processing liquid piping 42: Upper stripping liquid piping 43: Solvent extract liquid piping 44: Upper rinsing liquid piping 45: Gas piping 46: Organic solvent piping 50: Chemical valve 51: Processing liquid valve 52: Upper stripping liquid valve 53: Solvent extract liquid valve 54: Upper rinsing liquid valve 55: Gas valve 56: Organic solvent valve 80: Common piping 81: Lower rinsing liquid piping 82: Lower stripping liquid piping 83: Heat transfer fluid piping 86: Lower rinsing liquid valve 87: Lower stripping liquid valve 88: Heat transfer fluid valve 91: Processing liquid 91a: Solvent 92: Solvent extract 93: Stripping liquid 94: Residue removal liquid 100: Processing film 100a: Surface 100v: Void 101: Processing liquid film 101a: Surface 101b: Solidified layer 160: Uneven pattern 165: Patterned surface 171: Processing liquid supply process 172: Processing film formation process 173: Solvent extract supply process 174: Solvent extract discharge process 175: Evaporation acceleration process 176: Removal process 177: Residue removal process 178: Shake-off drying process A1: Rotation axis W : circuit board

Claims

1. A substrate processing method comprising: a processing liquid supply step of supplying a processing liquid having a solute and a solvent to the patterned surface of a substrate having a patterned surface on which an uneven pattern is formed; a processing film forming step of solidifying or hardening the processing liquid on the patterned surface to form a processing film on the patterned surface; a solvent extract supply step of supplying a solvent extract to the surface of the processing film for extracting the solvent from the processing film; a solvent extract discharge step of discharging the solvent extract to the outside of the substrate after the solvent extract supply step; an evaporation acceleration step of promoting the evaporation of the solvent in the processing film after the solvent extract discharge step; and a removal step of peeling the processing film from the patterned surface and removing it to the outside of the substrate after the evaporation acceleration step.

2. The substrate processing method according to claim 1, wherein the evaporation acceleration step includes a heating step of heating the processed film.

3. The substrate processing method according to claim 1 or 2, wherein the solvent extract is a liquid having a lower affinity for the solute than the solvent and being compatible with the solvent.

4. The substrate processing method according to any one of claims 1 to 3, wherein the solute contains a polymer, the solvent is water-soluble, and the solvent extract contains water.

5. The substrate treatment method according to claim 4, wherein the solvent comprises PGME (propylene glycol monomethyl ether) or IPA (isopropyl alcohol).

6. The substrate processing method according to any one of claims 1 to 3, wherein the solute contains a polymer, the solvent is water-insoluble, and the solvent extract contains an organic solvent.

7. The substrate processing method according to claim 6, wherein the solvent comprises PGMEA (propylene glycol monomethyl ether acetate) or cyclopentanol.

8. A substrate processing method according to any one of claims 1 to 7, further comprising a residue removal step of supplying a residue removal liquid to the pattern surface after the removal step to remove residue of the processed film from the pattern surface.

9. The substrate treatment method according to claim 8, wherein the residue removal solution comprises at least one of IPA (isopropyl alcohol), HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

10. A substrate processing apparatus comprising: a spin chuck for holding a substrate having a patterned surface on which an uneven pattern is formed in a horizontal position and rotating the substrate around a rotation axis passing through the center of the substrate; a processing liquid supply unit for supplying a processing liquid having a solute and a solvent to the patterned surface of the substrate held by the spin chuck in order to form a processing film on the patterned surface; a solvent extractant supply unit for supplying a solvent extractant for extracting the solvent from the processing film to the surface of the processing film formed on the patterned surface of the substrate held by the spin chuck; an evaporation acceleration unit for promoting the evaporation of the solvent in the processing film formed on the patterned surface of the substrate held by the spin chuck; and a processing film removal unit for peeling the processing film formed on the patterned surface of the substrate held by the spin chuck from the patterned surface and removing it from the substrate.

11. Further includes a controller for controlling the spin chuck, the processing liquid supply unit, the solvent extract supply unit, the evaporation acceleration unit, and the processing film removal unit, The substrate processing apparatus according to claim 10, wherein the controller is programmed to perform: a processing liquid supply step of supplying the processing liquid from the processing liquid supply unit to the pattern surface while rotating the substrate with the spin chuck; a processing film formation step of stopping the supply of the processing liquid by the processing liquid supply unit and rotating the substrate with the spin chuck to solidify or harden the processing liquid on the pattern surface and form the processing film on the pattern surface; a solvent extract supply step of supplying the solvent extract to the surface of the processing film from the solvent extract supply unit after the processing film has been formed; a solvent extract discharge step of stopping the supply of the solvent extract by the solvent extract supply unit and rotating the substrate with the spin chuck to discharge the solvent extract to the outside of the substrate; an evaporation acceleration step of promoting the evaporation of the solvent in the processing film with the evaporation acceleration unit after the solvent extract discharge step; and a removal step of peeling the processing film from the pattern surface and removing it from the substrate with the removal unit after the evaporation acceleration step.

12. The substrate processing apparatus according to claim 10 or 11, wherein the evaporation acceleration unit includes a heating unit for heating the processing film formed on the pattern surface of the substrate held in the spin chuck.

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