Substrate processing method and substrate processing apparatus

Abstract

This invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method includes: a processing liquid supply step, supplying a processing liquid to the patterned surface of a substrate having a patterned surface with unevenness; a processing film formation step, solidifying or hardening the processing liquid supplied to the patterned surface to form a processing film for holding a removable object on the patterned surface in a manner that follows the unevenness of the patterned surface; and a removal step, supplying a stripping liquid to the patterned surface to peel the processing film and the removable object together from the patterned surface, removing the processing film from the substrate while maintaining the removable object held by the processing film.

Description

[0001] This application is a divisional application of the invention patent application filed on May 30, 2019, with application number 201910467689.1 and title "Substrate Processing Method and Substrate Processing Apparatus".

[0002] Cross-references to related applications

[0003] This application claims priority based on Japanese Patent Application No. 2018-105632, filed May 31, 2018, and Japanese Patent Application No. 2018-234735, filed December 14, 2018, the entire contents of which are incorporated herein by reference. Technical Field

[0004] This invention relates to a substrate processing method and a substrate processing apparatus for processing substrates. The substrates to be processed include, for example, semiconductor wafers, substrates for liquid crystal display devices, substrates for FPD (Flat Panel Display) devices such as organic EL (Electroluminescence) display devices, substrates for optical discs, substrates for magnetic disks, substrates for optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like. Background Technology

[0005] In the manufacturing process of semiconductor devices, a cleaning process is performed to remove various contaminants, residues of processing solutions and photoresists used in previous processes, or various particles (hereinafter, sometimes collectively referred to as "objects to be removed") adhering to the substrate.

[0006] In the washing process, the target material is usually removed by the physical action of the washing liquid, such as deionized water (DIW), or by the chemical action of the washing liquid, such as by the supply of a chemical solution to the substrate that reacts with the target material.

[0007] However, the miniaturization and increasing complexity of the raised and recessed patterns formed on substrates are constantly advancing. As a result, it is becoming increasingly difficult to remove the target material using detergents or chemicals while suppressing damage to the raised and recessed patterns.

[0008] Therefore, in U.S. Patent Application Publication No. 2014 / 041685, a method was proposed to supply a processing liquid containing a solute and a volatile solvent to the upper surface of a substrate, to form a processing film obtained by solidifying or hardening the processing liquid, and then to dissolve and remove the processing film.

[0009] In this method, when the processing solution solidifies or hardens to form a processing film, the object to be removed is separated from the raised pattern. Furthermore, the separated object to be removed is retained within the processing film. Next, a dissolving processing solution is supplied to the upper surface of the substrate. As a result, the processing film is dissolved and removed on the substrate, thus allowing the object to be removed along with the dissolved product of the processing film from the upper surface of the substrate. Summary of the Invention

[0010] However, in the method disclosed in U.S. Patent Application Publication No. 2014 / 041685, the processing film is dissolved on the substrate. Therefore, the object to be removed detaches from the processing film on the substrate, and this detached object may re-adhere to the uneven pattern. Thus, it may not be possible to efficiently remove the object from the substrate.

[0011] Therefore, one object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can efficiently remove objects present on a raised or recessed pattern formed on a substrate.

[0012] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supply step, supplying processing liquid to the patterned surface of a substrate having a patterned surface with unevenness; a processing film formation step, solidifying or hardening the processing liquid supplied to the patterned surface to form a processing film for holding a removable object on the patterned surface in a manner following the unevenness of the patterned surface; and a removal step, supplying a stripping liquid to the patterned surface to peel the processing film and the removable object together from the patterned surface, removing the processing film from the substrate while maintaining the removable object held by the processing film.

[0013] According to this method, a treatment film is formed in a manner that follows the unevenness of the patterned surface. Therefore, the film thickness of the treatment film can be reduced across the entire area of ​​the patterned surface. Consequently, the stripping liquid becomes more readily permeable through the treatment film and more readily reaches the interface between the treatment film and the patterned surface throughout the entire area of ​​the patterned surface.

[0014] Furthermore, by reducing the thickness of the processed membrane, its strength can be reduced. Therefore, the energy from the stripping fluid flowing over the patterned surface can easily cause the processed membrane to split into sheets. Thus, the stripping fluid can quickly reach the interface between the split sheets and the patterned surface.

[0015] By rapidly delivering the stripping fluid to the interface between the treatment film and the patterned surface across the entire patterned area, the object to be removed can be efficiently peeled off from the patterned surface along with the treatment film. As a result, the object to be removed can be efficiently removed from the substrate.

[0016] In one embodiment of the present invention, the aforementioned processing film formation step includes forming the processing film such that the thickness of the processing film is thinner than the height of the unevenness of the patterned surface in the thickness direction of the substrate. Therefore, the distance between the surface of the processing film and the patterned surface can be reduced in the thickness direction of the substrate. Consequently, the stripping liquid can quickly reach the interface between the patterned surface and the processing film. As a result, the object to be removed and the processing film can be peeled off from the patterned surface more efficiently.

[0017] In one embodiment of the present invention, the aforementioned processing film formation step includes the step of forming the processing film in a recess within the aforementioned patterned surface, such that the surface of the processing film is located closer to the bottom side of the recess than the top of the protrusion adjacent to the recess. Therefore, compared to forming the processing film by filling the entire recess in the processing film formation step, the thickness of the processing film within the recess can be reduced. Consequently, the stripping liquid can quickly reach the interface between the bottom of the recess on the patterned surface and the processing film. As a result, the object to be removed and the processing film can be peeled off from the patterned surface more efficiently.

[0018] In one embodiment of the present invention, the aforementioned processing film formation step includes a step of forming the processing film by covering the aforementioned object to be removed with the processing film. This increases the contact area between the processing film and the object to be removed, thereby improving the holding force of the processing film in retaining the object to be removed. Consequently, the amount of object to be removed detached from the processing film is reduced. Therefore, most of the object to be removed can be removed from the substrate along with the processing film, thus efficiently removing the object to be removed from the substrate while preventing it from re-adhering to the substrate.

[0019] In one embodiment of the present invention, the aforementioned processing film formation step includes a step of forming the processing film such that the adhesion force between the processing film and the object to be removed is greater than the adhesion force between the object to be removed and the patterned surface. Therefore, when the processing film is peeled off from the patterned surface using a stripping liquid, the number of objects to be removed that remain on the patterned surface without being removed can be reduced. Therefore, most of the objects to be removed can be removed from the substrate along with the processing film, thus efficiently removing the objects to the substrate.

[0020] In one embodiment of the present invention, the aforementioned removal process includes a through-hole forming process, wherein the aforementioned stripping liquid is used to partially dissolve the aforementioned processed film to form through-holes on the aforementioned processed film. Therefore, the stripping liquid can quickly reach the vicinity of the interface between the processed film and the patterned surface through the through-holes. Thus, the stripping liquid can act on the interface between the processed film and the substrate, efficiently peeling the processed film off the substrate.

[0021] On the other hand, while the processing film is partially dissolved by the stripping solution to form through-holes, the remaining portion remains in a solid state. Therefore, the processing film, which has formed through-holes and retains the object to be removed, can be peeled off from the patterned surface. As a result, the object to be removed and the processing film can be efficiently removed together from the patterned surface.

[0022] In one embodiment of the present invention, the aforementioned removal process includes a stripping liquid entry process, wherein the stripping liquid enters between the treated film and the patterned surface through the aforementioned through-hole. Therefore, the stripping liquid can act on the interface between the treated film and the substrate, enabling more efficient stripping of the treated film from the patterned surface.

[0023] In one embodiment of the present invention, the aforementioned treatment liquid has a solute and a solvent for dissolving the aforementioned solute, wherein the aforementioned solute has a first component and a second component whose solubility in the aforementioned stripping liquid is lower than that of the aforementioned first component. Furthermore, the aforementioned treatment film forming step includes a step of forming the aforementioned treatment film having a first solid formed from the aforementioned first component and a second solid formed from the aforementioned second component.

[0024] According to this method, the first component has a higher solubility in the stripping solution than the second component. Therefore, the first solid formed from the first component is more soluble in the stripping solution than the second solid formed from the second component.

[0025] Therefore, while reliably forming through-holes by dissolving the first solid in the stripping solution, the second solid is not dissolved in the stripping solution, maintaining its solid state. Thus, the stripping solution can act on the interface between the second solid and the substrate while holding the object to be removed in the second solid. As a result, the processed film can be quickly peeled off from the patterned surface, and the object to be removed and the processed film can be efficiently removed together from the patterned surface.

[0026] In one embodiment of the present invention, the aforementioned 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 thereof.

[0027] In one embodiment of the present invention, the aforementioned first component is a crack-promoting component, which includes hydrocarbons, hydroxyl groups, and / or carbonyl groups.

[0028] In one embodiment of the present invention, the aforementioned first component is represented by at least any one of the following formulas (B-1), (B-2) and (B-3).

[0029] (B-1) is a compound comprising 1 to 6 of the following chemical formulas 1 as structural units, and each of the aforementioned structural units is connected by a linking group L1.

[0030] [Chemical Formula 1]

[0031]

[0032] Here, L1 is selected from single bonds and C. 1～6 At least one of the alkylene groups, wherein Cy1 is C 5～30 The hydrocarbon rings, where R1 is independently C1. 1～5 alkyl, n b1 n is 1, 2, or 3. b1’ It can be 0, 1, 2, 3, or 4.

[0033] (B-2) is a compound represented by the following chemical formula 2.

[0034] [Chemical Formula 2]

[0035]

[0036] Here, R 21 R 22 R 23 and R 24 Each is independently hydrogen or C 1～5 alkyl, L 21 and L 22 Each independently is C 1～20 alkylene, C 1～20 Cycloalkylene, C 2～4 imidene group, C 2～4 The ethynyl group, or C 6～20 arylene groups, these groups can be C 1～5 Alkyl or hydroxyl substitution, n b2 It can be 0, 1, or 2.

[0037] (B-3) is a polymer containing structural units represented by the following chemical formula 3 and having a weight-average molecular weight (Mw) of 500 to 10,000.

[0038] [Chemical Formula 3]

[0039]

[0040] R 25 It can be -H, -CH3, or -COOH.

[0041] In one embodiment of the present invention, the solubility of the aforementioned second component in 5.0% by mass ammonia water is less than 100 ppm, and the solubility of the aforementioned first component in 5.0% by mass ammonia water is more than 100 ppm.

[0042] In one embodiment of the present invention, the mass of the second component is 0.1 to 50% of the total mass of the aforementioned treatment liquid.

[0043] In one embodiment of the present invention, the weight-average molecular weight (Mw) of the aforementioned second component is 150 to 500,000.

[0044] In one embodiment of the present invention, the aforementioned substrate processing method further includes: a substrate rotation step, wherein the substrate is held horizontally and the substrate is rotated about a vertical axis passing through the center of the substrate. Furthermore, the aforementioned substrate rotation step includes: a first rotation step, wherein the substrate is rotated at a first speed from the start of supplying the processing liquid to the patterned surface until the formation of the processing film; and a second rotation step, wherein the rotation of the substrate is accelerated after the first rotation step until the formation of the processing film, causing the substrate to rotate at a second speed that is faster than the first speed.

[0045] According to this method, from the initial supply of the processing liquid to the patterned surface until the formation of the processing film, the substrate is rotated at a low first speed. Therefore, the processing liquid is thrown off by centrifugal force, and before the amount of processing liquid on the patterned surface is drastically reduced, the processing liquid enters the recesses of the patterned surface due to its own weight. Furthermore, after the first rotation step until the formation of the processing film, the rotation of the substrate is accelerated, and the processing liquid is expelled from the patterned surface of the substrate. Therefore, a sufficiently thin processing film can be formed with the processing liquid entering the recesses of the patterned surface due to its own weight.

[0046] Other embodiments of the present invention provide a substrate processing apparatus comprising: a processing liquid supply unit that supplies processing liquid to the patterned surface of a substrate having a patterned surface with unevenness; a solid forming unit that solidifies or hardens the processing liquid; a stripping liquid supply unit that supplies stripping liquid to the patterned surface; and a controller that controls the processing liquid supply unit, the solid forming unit, and the stripping liquid supply unit.

[0047] Moreover, the aforementioned controller is programmed in the following manner:

[0048] The following steps are performed: a processing liquid supply step, in which the processing liquid is supplied from the aforementioned processing liquid supply unit to the aforementioned patterned surface; a processing film formation step, in which the aforementioned processing liquid supplied to the aforementioned patterned surface is solidified or hardened in the aforementioned solid formation unit, thereby forming a processing film that retains the object to be removed on the aforementioned patterned surface in a manner that follows the unevenness of the patterned surface; and a removal step, in which stripping liquid is supplied from the aforementioned stripping liquid supply unit to the aforementioned patterned surface, thereby peeling the aforementioned processing film and the aforementioned object to be removed together from the aforementioned patterned surface, and removing the aforementioned processing film from the aforementioned substrate while maintaining the state in which the aforementioned object to be removed is held by the aforementioned processing film.

[0049] With the above configuration, the treatment film is formed in a manner that follows the unevenness of the patterned surface. Therefore, the film thickness of the treatment film can be reduced throughout the entire area of ​​the patterned surface. Consequently, the stripping liquid can easily pass through the treatment film and reach the interface between the treatment film and the patterned surface throughout the entire area of ​​the patterned surface.

[0050] Furthermore, by reducing the thickness of the processed membrane, its strength can be reduced. Therefore, the energy from the stripping fluid flowing over the patterned surface can easily cause the processed membrane to split into sheets. Thus, the stripping fluid can quickly reach the interface between the split sheets and the patterned surface.

[0051] By rapidly delivering the stripping fluid to the interface between the treatment film and the patterned surface across the entire patterned area, the object to be removed can be efficiently peeled off from the patterned surface along with the treatment film. As a result, the object to be removed can be efficiently removed from the substrate.

[0052] In other embodiments of the present invention, the aforementioned controller is programmed such that, during the aforementioned processing film formation process, the processing film is formed such that its thickness is thinner than the height of the unevenness of the patterned surface in the thickness direction of the substrate. Therefore, the distance between the surface of the processing film and the patterned surface can be reduced in the thickness direction of the substrate. Consequently, the stripping liquid can quickly reach the interface between the patterned surface and the processing film. As a result, the object to be removed and the processing film can be peeled off from the patterned surface more efficiently.

[0053] In other embodiments of the present invention, the aforementioned controller is programmed in such a way that, during the aforementioned processing film formation step, the processing film is formed in a position where the surface of the processing film is located further towards the bottom of the recess than the top of the protrusion adjacent to the recess. Therefore, compared to forming the processing film by filling the entire recess during the processing film formation step, the thickness of the processing film within the recess can be reduced. Consequently, the stripping liquid can quickly reach the interface between the bottom of the recess on the patterned surface and the processing film. As a result, the object to be removed and the processing film can be peeled off from the patterned surface more efficiently.

[0054] In other embodiments of the present invention, the aforementioned controller is programmed such that, in the aforementioned processing film formation step, the aforementioned processing film is formed such that it covers the aforementioned object to be removed. This increases the contact area between the processing film and the object to be removed, thereby improving the holding force of the processing film in retaining the object to be removed. Consequently, the amount of object to be removed detached from the processing film is reduced. Therefore, most of the object to be removed can be removed from the substrate along with the processing film, thus efficiently removing the object to be removed from the substrate while preventing it from re-attaching to the substrate.

[0055] In other embodiments of the present invention, the controller is programmed such that, during the processing film formation process, the processing film is formed such that the adhesion force between the processing film and the object to be removed is greater than the adhesion force between the object to be removed and the patterned surface. Therefore, when the processing film is peeled off from the patterned surface using a stripping liquid, the number of objects to be removed that remain on the patterned surface without being removed is reduced. Thus, most of the objects to be removed can be removed from the substrate along with the processing film, thereby efficiently removing the objects from the substrate.

[0056] In other embodiments of the present invention, the aforementioned controller is programmed to perform a via-hole forming step in the aforementioned removal step, wherein the aforementioned stripping liquid is used to partially dissolve the aforementioned processing film to form via-holes on the aforementioned processing film. Therefore, the stripping liquid can quickly reach the interface between the processing film and the patterned surface through the via-holes. Thus, the stripping liquid can act on the interface between the processing film and the substrate, efficiently peeling the processing film from the substrate.

[0057] On the other hand, while the processing film is partially dissolved by the stripping solution to form through-holes, the remaining portion remains in a solid state. Therefore, the processing film, which has formed through-holes and retains the object to be removed, can be peeled off from the patterned surface. As a result, the object to be removed and the processing film can be efficiently removed together from the patterned surface.

[0058] In other embodiments of the present invention, the aforementioned controller is programmed to perform a stripping liquid entry process during the aforementioned removal process, allowing the stripping liquid to enter between the aforementioned processed film and the aforementioned patterned surface through the aforementioned through-hole. Therefore, the stripping liquid can act on the interface between the processed film and the substrate, enabling more efficient stripping of the processed film from the raised / undulated pattern.

[0059] In other embodiments of the present invention, the aforementioned processing liquid has a first component, a second component whose solubility in the aforementioned stripping liquid is lower than that of the aforementioned first component, and a solvent for dissolving the aforementioned first component and the aforementioned second component. Moreover, the aforementioned controller is programmed in such a way that, in the aforementioned processing film forming step, a step of forming the aforementioned processing film having a first solid formed from the aforementioned first component and a second solid formed from the aforementioned second component is performed.

[0060] With the above configuration, the first component has a higher solubility in the stripping solution than the second component. Therefore, the first solid formed from the first component is more soluble in the stripping solution than the second solid formed from the second component.

[0061] Therefore, while reliably forming through-holes by dissolving the first solid in the stripping solution, the second solid is not dissolved in the stripping solution, maintaining its solid state. Thus, the stripping solution can act on the interface between the second solid and the substrate while holding the object to be removed in the second solid. As a result, the processed film can be quickly peeled off from the patterned surface, and the object to be removed and the processed film can be efficiently removed together from the patterned surface.

[0062] In other embodiments of the present invention, the aforementioned 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 thereof.

[0063] In other embodiments of the present invention, the aforementioned first component is a crack-promoting component, which includes hydrocarbons, hydroxyl groups, and / or carbonyl groups.

[0064] In other embodiments of the present invention, the aforementioned first component is represented by at least any one of the following formulas (B-1), (B-2) and (B-3).

[0065] (B-1) is a compound containing 1 to 6 chemical formulas 4 as structural units, and each of the aforementioned structural units is connected by a linking group L1.

[0066] [Chemical Formula 4]

[0067]

[0068] Here, L1 is selected from single bonds and C. 1～6 At least one of the alkylene groups, wherein Cy1 is C 5～30 The hydrocarbon rings, where R1 is independently C1. 1～5 alkyl, n b1 n is 1, 2, or 3. b1’ It can be 0, 1, 2, 3, or 4.

[0069] (B-2) is a compound represented by chemical formula 5.

[0070] [Chemical Formula 5]

[0071]

[0072] Here, R 21 R 22 R 23 and R 24 Each is independently hydrogen or C 1～5 alkyl, L 21 and L 22 Each independently is C 1～20 alkylene, C 1～20Cycloalkylene, C 2～4 imidene group, C 2～4 The ethynyl group, or C 6～20 arylene groups, these groups can be C 1～5 Alkyl or hydroxyl substitution, n b2 It can be 0, 1, or 2.

[0073] (B-3) is a polymer containing structural units represented by chemical formula 6 and having a weight-average molecular weight (Mw) of 500 to 10,000.

[0074] [Chemical Formula 6]

[0075]

[0076] R 25 It can be -H, -CH3, or -COOH.

[0077] In other embodiments of the present invention, the solubility of the aforementioned second component in 5.0% by mass ammonia water is less than 100 ppm, and the solubility of the aforementioned first component in 5.0% by mass ammonia water is more than 100 ppm.

[0078] In other embodiments of the present invention, the mass of the second component is 0.1 to 50% of the total mass of the aforementioned treatment liquid.

[0079] In other embodiments of the present invention, the weight-average molecular weight (Mw) of the aforementioned second component is 150 to 500,000.

[0080] In other embodiments of the present invention, the aforementioned substrate processing apparatus further includes: a substrate holding unit that holds the aforementioned substrate horizontally; and a substrate rotating unit that rotates the aforementioned substrate about a vertical axis passing through the central portion of the aforementioned substrate. Furthermore, the aforementioned controller is programmed in the following manner:

[0081] The following steps are performed: a first rotation step in which, from the start of supplying the aforementioned processing liquid to the aforementioned patterned surface until the formation of the aforementioned processing film, the aforementioned substrate held by the aforementioned substrate holding unit is rotated at a first speed using the aforementioned substrate rotation unit; and a second rotation step in which, after the aforementioned first rotation step until the formation of the aforementioned processing film, the rotation of the aforementioned substrate is accelerated using the aforementioned substrate rotation unit, so that the aforementioned substrate rotates at a second speed that is faster than the aforementioned first speed.

[0082] With the above configuration, from the initial supply of the processing liquid to the patterned surface until the formation of the processing film, the substrate is rotated at a relatively low first speed. Therefore, the processing liquid is thrown off by centrifugal force, and before the amount of processing liquid on the patterned surface is drastically reduced, the processing liquid enters the recesses of the patterned surface due to its own weight. Furthermore, after the first rotation step until the formation of the processing film, the rotation of the substrate is accelerated, and the processing liquid is expelled from the patterned surface of the substrate. Therefore, a sufficiently thin processing film can be formed with the processing liquid entering the recesses of the patterned surface due to its own weight.

[0083] Other objects, features, and effects of the present invention, whether above or further, will become clear from the description of the embodiments described below with reference to the accompanying drawings. Attached Figure Description

[0084] Figure 1 This is a schematic top view illustrating the layout of a substrate processing apparatus according to one embodiment of the present invention.

[0085] Figure 2 This is a schematic partial cross-sectional view illustrating the general configuration of the processing units included in the aforementioned substrate processing apparatus.

[0086] Figure 3 This is a block diagram illustrating the electrical configuration of the main parts of the aforementioned substrate processing apparatus.

[0087] Figure 4 This is a flowchart illustrating an example of substrate processing performed using the aforementioned processing unit.

[0088] Figure 5A This is a schematic diagram illustrating the process solution supply step (step S5) of the aforementioned substrate processing.

[0089] Figure 5B This is a schematic diagram illustrating the spin-off process (step S6) of the aforementioned substrate treatment.

[0090] Figure 5C This is a schematic diagram illustrating the heating process (step S7) of the aforementioned substrate treatment.

[0091] Figure 5D This is a schematic diagram illustrating the buffer process (step S8) of the aforementioned substrate treatment.

[0092] Figure 5E This is a schematic diagram illustrating the removal process (step S9) of the aforementioned substrate treatment.

[0093] Figure 5F This is a schematic diagram illustrating the second rinsing step (step S10) of the aforementioned substrate treatment.

[0094] Figure 5G This is a schematic diagram illustrating the second organic solvent supply process (step S11) of the aforementioned substrate treatment.

[0095] Figure 5H This is a schematic diagram illustrating the rotary drying process (step S12) of the aforementioned substrate treatment.

[0096] Figure 6 This is a schematic cross-sectional view illustrating an example of the structure of a patterned surface of a substrate processed by the aforementioned substrate processing apparatus.

[0097] Figure 7A This is a schematic cross-sectional view used to illustrate the situation near the aforementioned patterned surface after the aforementioned processing liquid supply process (step S5).

[0098] Figure 7B This is a schematic cross-sectional view used to illustrate the situation near the aforementioned patterned surface after the aforementioned rotational shedding process (step S6).

[0099] Figure 7C This is a schematic cross-sectional view used to illustrate the situation near the aforementioned patterned surface during the aforementioned removal process (step S9).

[0100] Figure 8A This is a schematic cross-sectional view used to illustrate the condition inside the treated membrane after the aforementioned heating process (step S7).

[0101] Figure 8B This is a schematic cross-sectional view used to illustrate the condition inside the treatment membrane during the aforementioned removal process (step S9).

[0102] Figure 8C This is a schematic cross-sectional view used to illustrate the condition inside the treatment membrane during the aforementioned removal process (step S9). Detailed Implementation

[0103] Figure 1 This is a schematic top view illustrating the layout of a substrate processing apparatus 1 according to one embodiment of the present invention.

[0104] The substrate processing apparatus 1 is a monolithic apparatus that processes substrates W, such as silicon wafers, one by one. In this embodiment, the substrate W is a disk-shaped substrate. Fine embossed patterns 160 (see later description) are formed on the surface (main surface) of the substrate W. Figure 6 ).

[0105] The substrate processing apparatus 1 includes: multiple processing units 2 for processing substrates W with fluid, a load port LP for holding and accommodating multiple substrates W to be processed by the processing units 2, a transport robot IR and CR for transporting substrates W between the load port LP and the processing units 2, and a controller 3 for controlling the substrate processing apparatus 1.

[0106] A transport robot IR transports substrate W between carrier C and transport robot CR. Transport robot CR transports substrate W between transport robot IR and processing unit 2. Multiple processing units 2 may have the same configuration. Details are described later; the processing fluids supplied to substrate W within processing unit 2 include pharmaceutical solutions, rinsing solutions, processing fluids, stripping fluids, heat transfer media, inactive gases, etc.

[0107] Each processing unit 2 includes a chamber 4 and a processing cup 7 disposed within the chamber 4, where processing of the substrate W is performed. An inlet / outlet (not shown) is formed in the chamber 4 for moving the substrate W in or out using a transport robot CR. A gate unit (not shown) is provided in the chamber 4 to open and close the inlet / outlet.

[0108] Figure 2 This is a schematic diagram illustrating an example of the configuration of the processing unit 2. The processing unit 2 includes a rotary chuck 5, a counter 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 lower surface nozzle 12.

[0109] The rotary chuck 5 keeps the substrate W horizontal while rotating the substrate W about the rotation axis A1 (vertical axis). The rotation axis A1 is a vertical axis passing through the center of the substrate W. The rotary chuck 5 includes multiple chuck pins 20, a rotating base 21, a rotating shaft 22, and a rotary motor 23.

[0110] The rotating base 21 has a disk shape in the horizontal direction. On the upper surface of the rotating base 21, a plurality of chuck pins 20 holding the periphery of the substrate W are arranged at intervals in the circumferential direction of the rotating base 21. The rotating base 21 and the plurality of chuck pins 20 constitute a substrate holding unit that holds the substrate W horizontally. The substrate holding unit is also referred to as a substrate holder.

[0111] A rotating shaft 22 extends vertically along the rotation axis A1. The upper end of the rotating shaft 22 is connected to the center of the lower surface of the rotating base 21. A rotary motor 23 applies rotational force to the rotating shaft 22. The rotating shaft 22 is rotated by the rotary motor 23, thereby causing the rotating base 21 to rotate. Consequently, the substrate W rotates about the rotation axis A1. The rotary motor 23 is an example of a substrate rotation unit that rotates the substrate W about the rotation axis A1.

[0112] The opposing member 6 is positioned above the substrate W, which is held by the rotating chuck 5. The opposing member 6 is formed in the shape of a disk having a diameter approximately the same as or larger than that of the substrate W. The opposing member 6 has an opposing surface 6a that faces the upper surface (main surface on the upper side) of the substrate W. The opposing surface 6a is positioned approximately horizontally above the rotating chuck 5.

[0113] In the opposing member 6, a hollow shaft 60 is fixed on the opposite side of the opposing surface 6a. In the opposing member 6, a connecting hole 6b is formed in the part that overlaps with the axis of rotation A1 when viewed from above, which is a through hole 6b that runs vertically through the opposing member 6 and communicates with the internal space 60a of the hollow shaft 60.

[0114] The opposing member 6 blocks the atmosphere in the space between the opposing surface 6a and the upper surface of the substrate W from the atmosphere outside the space. Therefore, the opposing member 6 is also referred to as a blocking plate.

[0115] The processing unit 2 also includes a relative member lifting unit 61 that drives the relative member 6 to rise and fall. The relative member lifting unit 61 can position the relative member 6 at any height, from a lower position to an upper position. The lower position refers to the position within the movable range of the relative member 6 where the relative surface 6a is closest to the substrate W. The upper position refers to the position within the movable range of the relative member 6 where the relative surface 6a is farthest from the substrate W.

[0116] The relative component lifting unit 61 includes, for example, a ball screw mechanism (not shown) connected to a support member (not shown) supporting the hollow shaft 60, and an electric motor (not shown) that applies driving force to the ball screw mechanism. The relative component lifting unit 61 is also referred to as a relative component lifter (blocking plate lifter).

[0117] The processing cup 7 is contained within chamber 4 (see...) Figure 1 The processing cup 7 includes a plurality of protective shields 71 ​​that block liquid from splashing outward from the substrate W held by the rotating chuck 5, a plurality of cups 72 that receive the liquid guided downward by the plurality of protective shields 71, and a cylindrical outer wall member 73 surrounding the plurality of protective shields 71 ​​and the plurality of cups 72.

[0118] In this embodiment, an example is shown that has two protective covers 71 (first protective cover 71A and second protective cover 71B) and two cups 72 (first cup 72A and second cup 72B).

[0119] Cup 1 (72A) and Cup 2 (72B) each have an upward-opening annular groove.

[0120] The first protective cover 71A is configured to surround the rotating base 21. The second protective cover 71B is configured to surround the rotating base 21 at a position further outward of the rotational radial direction than the first protective cover 71A on the substrate W.

[0121] The first protective cover 71A and the second protective cover 71B are respectively generally cylindrical in shape, and the upper end of each protective cover 71 is inclined inward toward the rotating base 21.

[0122] The first cup 72A receives the liquid guided downward by the first protective shield 71A. The second cup 72B is integral with the first protective shield 71A and receives the liquid guided downward by the second protective shield 71B.

[0123] The processing unit 2 includes a protective cover lifting unit 74 that allows the first protective cover 71A and the second protective cover 71B to be raised and lowered independently. The protective cover lifting unit 74 raises and lowers the first protective cover 71A between a lower position and an upper position. The protective cover lifting unit 74 raises and lowers the second protective cover 71B between a lower position and an upper position.

[0124] When both the first protective cover 71A and the second protective cover 71B are in the upper position, liquid splashed from the substrate W is received by the first protective cover 71A. When the first protective cover 71A is in the lower position and the second protective cover 71B is in the upper position, liquid splashed from the substrate W is received by the second protective cover 71B.

[0125] The protective cover lifting unit 74 includes, for example, a first ball screw mechanism (not shown) connected to the first protective cover 71A, a first electric motor (not shown) that imparts driving force to the first ball screw, a second ball screw mechanism (not shown) connected to the second protective cover 71B, and a second electric motor (not shown) that imparts driving force to the second ball screw mechanism. The protective cover lifting unit 74 is also referred to as a protective cover lifter.

[0126] The first movable nozzle 8 is an example of a liquid supply unit that supplies (ejects) liquid medicine to the upper surface of the substrate W held by the rotating chuck 5.

[0127] The first moving nozzle 8 is moved horizontally and vertically by the first nozzle moving unit 36. The first moving nozzle 8 can move between a central position and an initial position (retreat position). When the first moving nozzle 8 is in the central position, it is opposite to the rotation center of the upper surface of the substrate W. The rotation center of the upper surface of the substrate W refers to the position on the upper surface of the substrate W that intersects the rotation axis A1.

[0128] When the first moving nozzle 8 is in its initial position, it is not opposite to the upper surface of the substrate W, and when viewed from above, it is located outside the processing cup 7. The first moving nozzle 8 can approach or retract from the upper surface of the substrate W by moving vertically.

[0129] The first nozzle moving unit 36 ​​includes, for example, a rotating shaft (not shown) in the vertical direction, an arm (not shown) connected to the rotating shaft and extending in the horizontal direction, and a rotating shaft drive unit (not shown) for raising, lowering or rotating the rotating shaft.

[0130] The rotation shaft drive unit causes the arm to swing by rotating the rotation shaft around a vertical rotation axis. Furthermore, the rotation shaft drive unit moves the arm up and down by raising and lowering the rotation shaft in the vertical direction. The first movable nozzle 8 is fixed to the arm. Depending on the swinging and raising / lowering of the arm, the first movable nozzle 8 moves in both the horizontal and vertical directions.

[0131] The first movable nozzle 8 is connected to the liquid medicine piping 40 that guides the liquid medicine. When the liquid medicine valve 50 installed on the liquid medicine piping 40 is opened, the liquid medicine is continuously sprayed downward from the first movable nozzle 8.

[0132] The liquid sprayed from the first movable nozzle 8 is, for example, a liquid containing at least one of the following: sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia, hydrogen peroxide aqueous solution, organic acid (e.g., citric acid, oxalic acid, etc.), organic base (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactant, and corrosion inhibitor. Examples of liquids obtained by mixing these substances include SPM solution (sulfuric acid / hydrogen peroxide aqueous solution) and SC1 solution (ammonia-hydrogen peroxide aqueous solution).

[0133] The second moving nozzle 9 is an example of a processing liquid supply unit that supplies (ejects) processing liquid to the upper surface of the substrate W held by the rotating chuck 5.

[0134] The second moving nozzle 9 is moved horizontally and vertically by the second nozzle moving unit 37. The second moving nozzle 9 can move between a central position and an initial position (retreat position). When the second moving nozzle 9 is in the central position, it is opposite to the rotation center of the upper surface of the substrate W.

[0135] When the second moving nozzle 9 is in its initial position, it is not opposite to the upper surface of the substrate W, and when viewed from above, it is located outside the processing cup 7. The second moving nozzle 9 can approach or retract from the upper surface of the substrate W by moving vertically.

[0136] 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 rotating shaft (not shown) in the vertical direction, an arm (not shown) connected to the rotating shaft and the second moving nozzle 9 and extending in the horizontal direction, and a rotating shaft drive unit (not shown) for raising, lowering or rotating the rotating shaft.

[0137] The second movable nozzle 9 is connected to the treatment fluid piping 41 that guides the treatment fluid. When the treatment fluid valve 51 installed on the treatment fluid piping 41 is opened, the treatment fluid is continuously sprayed downward from the second movable nozzle 9.

[0138] The processing liquid ejected from the second moving nozzle 9 contains a solute and a solvent. By evaporating at least a portion of the solvent, the processing liquid is solidified or hardened. With respect to the processing liquid, by solidification or hardening on the substrate W, a processing film is formed that retains particles or other objects to be removed that are present on the substrate W.

[0139] Here, "solidification" refers, for example, to the solidification of a solute through forces acting between molecules and atoms, accompanying the evaporation of the solvent. "Hardening," on the other hand, refers to the solidification of a solute through chemical changes such as polymerization or cross-linking. Therefore, "solidification or hardening" indicates that the solute "solidifies" through various factors.

[0140] The solute in the treatment liquid ejected from the second moving nozzle 9 contains both a first component and a second component. The amount (content) of the first component in the treatment liquid is less than the amount (content) of the second component in the treatment liquid.

[0141] The first and second components are, for example, synthetic resins with different properties. The solvent contained in the treatment liquid sprayed from the second movable nozzle 9 is simply a liquid that dissolves the first and second components.

[0142] Examples of synthetic resins that can be 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 resin, acrylonitrile styrene resin, polyamide, polyacetal, polycarbonate, polyvinyl alcohol, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polysulfone, polyetheretherketone, polyamide-imide, etc.

[0143] Examples of solvents that can dissolve synthetic resins include IPA, PGEE (propylene glycol monoethyl ether), PGMEA (propylene glycol 1-monomethyl ether 2-acetic acid ester), and EL (ethyl lactate).

[0144] The third moving nozzle 10 is an example of a stripping fluid supply unit that supplies (ejects) stripping fluid to the upper surface of the substrate W held by the rotating chuck 5. In this embodiment, it is also an example of a buffer supply unit that supplies (ejects) buffer solution to the upper surface of the substrate W held by the rotating chuck 5.

[0145] The third moving nozzle 10 is moved horizontally and vertically by the third nozzle moving unit 38. The third moving nozzle 10 can move between a center position and an initial position (retreat position).

[0146] When the third moving nozzle 10 is in the center position, it is opposite to the rotation center of the upper surface of the substrate W. When the third moving nozzle 10 is in the initial position, it is not opposite to the upper surface of the substrate W, and is located outside the processing cup 7 when viewed from above. The third moving nozzle 10 can approach or retract from the upper surface of the substrate W by moving in the vertical direction.

[0147] 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 rotating shaft (not shown) in the vertical direction, an arm (not shown) connected to the rotating shaft and the third moving nozzle 10 and extending in the horizontal direction, and a rotating shaft drive unit (not shown) for raising, lowering or rotating the rotating shaft.

[0148] The third movable nozzle 10 is connected to an upper stripping fluid pipe 42 that guides the stripping fluid to the third movable nozzle 10. When the upper stripping fluid valve 52 installed on the upper stripping fluid pipe 42 is open, the stripping fluid is continuously sprayed downward from the spray outlet of the third movable nozzle 10.

[0149] The third movable nozzle 10 is also connected to the upper buffer tubing 43 that guides the buffer solution to the third movable nozzle 10. When the upper buffer valve 53 installed on the upper buffer tubing 43 is open, the buffer solution is continuously sprayed downward from the outlet of the third movable nozzle 10.

[0150] The stripping solution is a liquid used to peel a processed film from the upper surface of a substrate W. As a stripping solution, a liquid that dissolves the first component in the solute of the processing solution more readily than the second component contained in the solute of the processing solution can be used. In other words, as a stripping solution, a liquid in which the solubility of the first component in the stripping solution is higher than that of the second component in the stripping solution can be used. The stripping solution is preferably a liquid that is miscible with the solvent contained in the processing solution.

[0151] The stripping fluid can be an aqueous solution. Examples of aqueous stripping fluids include DIW, carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and hydrochloric acid solutions and alkaline solutions with a dilution concentration (e.g., around 10 ppm to 100 ppm). Examples of alkaline solutions include SC1 solution, ammonia solution, aqueous solutions of quaternary ammonium hydroxides such as TMAH, and choline solution.

[0152] Buffer solution is a liquid used to buffer the stripping effect of the stripping solution on the treated membrane. By supplying buffer solution to the treated membrane before supplying the stripping solution, high concentrations of the stripping solution can be prevented from acting on a portion of the treated membrane. By pre-supplying buffer solution before supplying the stripping solution to the treated membrane, the stripping solution can be applied to the entire treated membrane without any omissions.

[0153] Examples of buffer solutions include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid at a dilution concentration (e.g., around 1 ppm to 100 ppm), ammonia at a dilution concentration (e.g., around 1 ppm to 100 ppm), and reduced water (hydrogen water).

[0154] The central nozzle 11 is housed within the internal space 60a of the hollow shaft 60 of the opposing member 6. The nozzle outlet 11a, located at the front end 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 refers to the area on the upper surface of the substrate W that contains the center of rotation of the substrate W.

[0155] The central nozzle 11 includes multiple tubes (first tube 31, second tube 32, and third tube 33) that eject fluid downwards, and a cylindrical outer casing 30 surrounding the multiple tubes. The multiple tubes and the outer casing 30 extend vertically along the axis of rotation A1. The outlet 11a of the central nozzle 11 is also the outlet of the first tube 31, the second tube 32, and the third tube 33.

[0156] The first tube 31 is an example of a rinsing solution supply unit that supplies rinsing solution 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 organic solvents such as IPA to the upper surface of the substrate W.

[0157] The first pipe 31 is connected to the upper rinse fluid pipe 44, which guides the rinse fluid to the first pipe 31. When the upper rinse fluid valve 54 installed on the upper rinse fluid pipe 44 is opened, the rinse fluid is continuously sprayed from the first pipe 31 (central nozzle 11) to the central region of the upper surface of the substrate W.

[0158] Examples of rinsing solutions include DIW, carbonated water, electrolyzed ionized water, hydrochloric acid at a dilution concentration (e.g., approximately 1 ppm to 100 ppm), ammonia at a dilution concentration (e.g., approximately 1 ppm to 100 ppm), and reduced water (hydrogen water). In other words, the same liquid as the buffer solution can be used as the rinsing solution. Since the rinsing solution is the same liquid as the buffer solution, tube 31 is also an example of a buffer supply unit.

[0159] The second pipe 32 is connected to a gas pipe 45 that directs gas to the second pipe 32. When the gas valve 55 installed on the gas pipe 45 is open, gas is continuously ejected downward from the second pipe 32 (central nozzle 11).

[0160] The gas ejected from the second tube 32 is, for example, an inactive gas such as nitrogen (N2). The gas ejected from the second tube 32 can also be air. Inactive gases are not limited to nitrogen; they refer to gases that are inactive relative to the upper surface of the substrate W and to the pattern formed on the upper surface of the substrate W. Examples of inactive gases, besides nitrogen, include rare gases such as argon.

[0161] The third tube 33 is connected to an organic solvent pipe 46 that directs the organic solvent into the third tube 33. When the organic solvent valve 56 installed on the organic solvent pipe 46 is open, the organic solvent is continuously sprayed from the third tube 33 (central nozzle 11) into the central region of the upper surface of the substrate W.

[0162] The organic solvent sprayed from the third tube 33 is a residue removal liquid that removes residue remaining on the upper surface of the substrate W after the treated film has been removed with a stripping solution. The organic solvent sprayed from the third tube 33 preferably has compatibility with the treated solution and the rinsing solution.

[0163] Examples of organic solvents ejected from the third tube 33 include liquids containing at least one of IPA, HFE (hydrofluoroether), methanol, ethanol, acetone, and trans-1,2-dichloroethylene.

[0164] Furthermore, the organic solvent sprayed from the third tube 33 does not need to consist of a single component; it can also be a liquid mixed with other components. For example, the organic solvent sprayed from the third tube 33 can be a mixture of IPA and DIW, or a mixture of IPA and HFE.

[0165] The lower surface nozzle 12 is inserted into a through hole 21a that opens at the center of the upper surface of the rotating base 21. The nozzle outlet 12a of the lower surface nozzle 12 protrudes from the upper surface of the rotating base 21. The nozzle outlet 12a of the lower surface nozzle 12 is opposite to the central region of the lower surface of the substrate W from below. The central region of the lower surface of the substrate W refers to the region of the lower surface of the substrate W that includes the rotation center of the substrate W.

[0166] The lower surface nozzle 12 is connected to one end of a common piping 80 that shares the rinsing fluid, stripping fluid, and heat medium to the lower surface nozzle 12. The other end of the common piping 80 is connected to a lower rinsing fluid piping 81 that shares the rinsing fluid with the common piping 80, a lower stripping fluid piping 82 that shares the stripping fluid with the common piping 80, and a heat medium piping 83 that shares the heat medium with the common piping 80.

[0167] When the lower rinse fluid valve 86, installed on the lower rinse fluid piping 81, is open, rinse fluid is continuously sprayed from the lower surface nozzle 12 into the central region of the lower surface of the substrate W. When the lower stripping fluid valve 87, installed on the lower stripping fluid piping 82, is open, stripping fluid is continuously sprayed from the lower surface nozzle 12 into the central region of the lower surface of the substrate W. When the heat medium valve 88, installed on the heat medium piping 83, is open, heat medium is continuously sprayed from the lower surface nozzle 12 into the central region of the lower surface of the substrate W.

[0168] The lower surface nozzle 12 is an example of a lower-side rinsing fluid supply unit that supplies rinsing fluid to the lower surface of the substrate W. Since the liquid that can be used as rinsing fluid can also be used as a buffer solution, the lower surface nozzle 12 is also an example of a lower-side buffer solution supply unit.

[0169] Furthermore, the lower surface nozzle 12 is an example of a lower stripping fluid supply unit that supplies stripping fluid to the lower surface of the substrate W. Additionally, the lower surface nozzle 12 is an example of a heat medium supply unit that supplies a heat medium for heating the substrate W. The lower surface nozzle 12 is also a substrate heating unit for heating the substrate W.

[0170] The heat medium ejected from the lower surface nozzle 12 is, for example, a high-temperature DIW at a temperature above room temperature and below the boiling point of the solvent contained in the treatment liquid (e.g., 60°C to 80°C). The heat medium ejected from the lower surface nozzle 12 is not limited to high-temperature DIW, but may also be a high-temperature inactive gas, high-temperature air, or other high-temperature gas at a temperature above room temperature and below the boiling point of the solvent contained in the treatment liquid (e.g., 60°C to 80°C).

[0171] Figure 3 This is a block diagram showing the electrical configuration of the main parts of the substrate processing apparatus 1. The controller 3 is equipped with a microcomputer and controls the controlled objects in the substrate processing apparatus 1 according to a prescribed control program.

[0172] Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B storing a control program. The controller 3 is configured to implement various controls for substrate processing by causing the processor 3A to execute the control program.

[0173] In particular, the controller 3 is programmed in the following manner to control the handling robot IR, CR, rotary motor 23, first nozzle moving unit 36, second nozzle moving unit 37, third nozzle moving unit 38, relative component lifting unit 61, protective cover lifting unit 74, medicine valve 50, treatment liquid valve 51, upper stripping liquid valve 52, upper buffer solution valve 53, upper rinsing liquid valve 54, gas valve 55, organic solvent valve 56, lower rinsing liquid valve 86, lower stripping liquid valve 87, and heat medium valve 88.

[0174] Figure 4 This is a flowchart illustrating an example of substrate processing performed using substrate processing apparatus 1. Figure 4 The main illustration shows the processing achieved by having controller 3 execute a program. Figures 5A to 5H This is a schematic diagram illustrating the various steps involved in the aforementioned substrate processing.

[0175] In substrate processing performed using substrate processing apparatus 1, for example, Figure 4 As shown, the following processes are performed sequentially: substrate loading process (step S1), chemical solution supply process (step S2), first rinsing process (step S3), first organic solvent supply process (step S4), treatment solution supply process (step S5), rotary detachment process (step S6), heating process (step S7), buffering process (step S8), removal process (step S9), second rinsing process (step S10), second organic solvent supply process (step S11), rotary drying process (step S12), and substrate unloading process (step S13).

[0176] First, the untreated substrate W is transported by a robotic arm performing IR and CR (see...). Figure 1 The substrate W is transported from the carrier C to the processing unit 2 and then transferred to the rotary chuck 5 (step S1). Thereby, the substrate W is held horizontally by the rotary chuck 5 (substrate holding process). The holding of the substrate W based on the rotary chuck 5 continues until the rotary drying process (step S12) ends. During the loading of the substrate W, the relative member 6 retracts upwards.

[0177] Next, the handling robot CR retracts outside the processing unit 2, and then the liquid supply process begins (step S2). Specifically, the rotary motor 23 rotates the rotating base 21. This causes the substrate W, which is held horizontally, to rotate (substrate rotation process). Then, the protective cover lifting unit 74 moves the first protective cover 71A and the second protective cover 71B to the upper position.

[0178] 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 liquid valve 50 is opened. As a result, liquid can be supplied (ejected) from the first moving nozzle 8 to the central region of the upper surface of the rotating substrate W. In the liquid supply process, the substrate W rotates at a predetermined liquid rotation speed, for example, 800 rpm.

[0179] The liquid medicine supplied to the upper surface of the substrate W is radially distributed by centrifugal force, covering the entire upper surface of the substrate W. Thus, the upper surface of the substrate W can be treated with the liquid medicine. The liquid medicine ejected from the first moving nozzle 8 can be sustained for a predetermined time, for example, 30 seconds.

[0180] Next, the first rinsing process (step S3) begins. In the first rinsing process, the chemical solution on the substrate W is rinsed away by the rinsing solution.

[0181] Specifically, the chemical solution valve 50 is closed. This stops the supply of chemical solution to the substrate W. Then, the first nozzle moving unit 36 ​​moves the first moving nozzle 8 to its initial position. Next, the relative component lifting unit 61 moves the relative component 6 to a processing position between the upper and lower positions. When the relative component 6 is in the processing position, the distance between the upper surface of the substrate W and the relative surface 6a is, for example, 30 mm. During the first rinsing process, the positions of the first protective cover 71A and the second protective cover 71B are maintained in the upper position.

[0182] Then, the upper rinse fluid valve 54 is opened. This supplies (ejects) rinse fluid from the central nozzle 11 to the central region of the upper surface of the rotating substrate W. Simultaneously, the lower rinse fluid valve 86 is opened. This supplies (ejects) rinse fluid from the lower surface nozzle 12 to the central region of the lower surface of the rotating substrate W. In the first rinse step, the substrate W can rotate at a predetermined first rinse rotation speed, for example, 800 rpm.

[0183] The rinsing solution supplied from the central nozzle 11 to the upper surface of the substrate W is distributed radially by centrifugal force, covering the entire upper surface of the substrate W. As a result, the rinsing solution on the upper surface of the substrate W is rinsed away from the substrate W.

[0184] The rinsing solution supplied from the lower surface nozzle 12 to the lower surface of the substrate W is radially distributed by centrifugal force, covering the entire lower surface of the substrate W. Even if the medicine sprayed from the substrate W during the medicine supply process adheres to the lower surface, the rinsing solution supplied from the lower surface nozzle 12 can wash away the adhered medicine. The spraying of rinsing solution from the central nozzle 11 and the lower surface nozzle 12 can be sustained for a predetermined time, for example, 30 seconds.

[0185] Next, the first organic solvent supply process (step S4) begins. In the first organic solvent supply process, the rinsing solution on the substrate W is replaced with an organic solvent.

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

[0187] In the first organic solvent supply step, the substrate W can rotate 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 fixed speed in the first organic solvent supply step. For example, at the start of organic solvent supply, the rotary motor 23 rotates the substrate W at 300 rpm, and the rotation of the substrate W can be accelerated while supplying organic solvent to the substrate W until the rotation speed of the substrate W reaches 1500 rpm.

[0188] Then, the organic solvent valve 56 is opened. As a result, organic solvent is supplied (ejected) from the central nozzle 11 to the central region of the upper surface of the rotating substrate W.

[0189] The organic solvent supplied from the central nozzle 11 to the upper surface of the substrate W is distributed radially by centrifugal force, covering the entire upper surface of the substrate W. As a result, the rinsing solution on the substrate W is replaced with the organic solvent. The ejection of the organic solvent from the central nozzle 11 can continue for a specified time, for example, 10 seconds.

[0190] Next, the processing liquid supply process begins (step S5). Specifically, the organic solvent valve 56 is closed. This stops the supply of organic solvent to the substrate W. Then, the relative component lifting unit 61 moves the relative component 6 to the upper position. Then, the protective cover lifting unit 74 moves the first protective cover 71A to the upper position. During the processing liquid supply process, the substrate W can rotate at a predetermined first rotation speed, for example, several tens of rpm to 200 rpm (first rotation process).

[0191] Then, as Figure 5AAs shown, 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, processing liquid can be supplied (ejected) from the second moving nozzle 9 to the central region of the upper surface of the rotating substrate W (processing liquid supply process, processing liquid ejection process). As a result, the organic solvent on the substrate W is replaced by processing liquid, and a liquid film of processing liquid (processing liquid film 101) can be formed on the substrate W (processing liquid film formation process). The supply of processing liquid from the second moving nozzle 9 can be sustained for a predetermined time, for example, between 2 seconds and 4 seconds.

[0192] Next, the processing film formation process (steps S6 and S7) is performed. In the processing film formation process, the processing liquid on the substrate W is cured or hardened to form a processing film 100 on the upper surface of the substrate W (see...). Figure 5C ).

[0193] In the membrane formation process, until the treated membrane 100 is formed (see...) Figure 5C During this period, a rotary slinging process (thinning process) is performed (step S6). In the rotary slinging process, firstly, the processing liquid valve 51 is closed. Thus, as... Figure 5B As shown, the supply of the processing liquid to the substrate W is stopped. Then, the second moving nozzle 9 is moved to the initial position by the second nozzle moving unit 37.

[0194] During the spin-and-ejection process, with the supply of the processing liquid to the upper surface of the substrate W stopped, a portion of the processing liquid is expelled 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. During the spin-and-ejection process, the relative member 6, the first protective cover 71A, and the second protective cover 71B are maintained in the upper position.

[0195] In the rotational detachment process, the rotary motor 23 accelerates the rotation of the substrate W, changing its rotational speed to a predetermined second rotational speed (second rotational process). The second rotational speed is, for example, 1000 rpm to 1500 rpm. During the rotational detachment process, the rotational speed of the substrate W can be kept constant within the range of 1000 rpm to 1500 rpm, or it can be appropriately varied within the range of 1000 rpm to 1500 rpm midway through the process. The rotational detachment process can be carried out for a predetermined time, for example, 30 seconds.

[0196] In the film formation process, after the spin-spinning step, a heating step (step S7) is performed to heat the substrate W. During the heating step, in order to evaporate (evaporate) a portion of the solvent in the processing liquid on the substrate W, the processing liquid film 101 on the substrate W (see...) is heated. Figure 5B (Heating)

[0197] See Figure 5C Specifically, the relative component lifting unit 61 moves the relative component 6 to a near position between the upper position and the lower position. The near position can also be the lower position. The near position is a position with a distance of, for example, 1 mm from the upper surface of the substrate W to the opposite surface 6a. During the heating process, the first protective cover 71A and the second protective cover 71B are maintained in the upper position.

[0198] Then, the gas valve 55 is opened. This supplies gas from the central nozzle 11 into 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 process). This promotes the evaporation of the solvent in the processing liquid film 101 (solvent evaporation process, solvent evaporation promotion process). Therefore, the time required to form the processing film 100 can be shortened. The central nozzle 11 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0199] Then, the heat medium valve 88 is opened. As a result, heat medium is supplied (ejected) from the lower surface nozzle 12 to the central region of the lower surface of the rotating substrate W (heat medium supply process, heat medium ejection process). The heat medium supplied from the lower surface nozzle 12 to the lower surface of the substrate W is radially distributed by centrifugal force, covering the entire lower surface of the substrate W. The supply of heat medium to the substrate W can continue for a predetermined time, for example, 60 seconds. During the heating process, the substrate W can rotate at a predetermined heating rotation speed, for example, 1000 rpm.

[0200] By supplying a heat medium to the lower surface of the substrate W, the processing liquid film 101 on the substrate W can be heated through the substrate W. This promotes the evaporation of the solvent in the processing liquid film 101 (solvent evaporation process, solvent evaporation promotion process). Therefore, the time required to form the processing film 100 can be shortened. The lower surface nozzle 12 functions as an evaporation unit (evaporation promotion unit) for evaporating the solvent in the processing liquid.

[0201] By performing a rotational slinging process and a heating process, the processing liquid is solidified or hardened, forming a processing film 100 on the substrate W. As described above, the solidification unit that solidifies or hardens the processing liquid to form a solid (processing film 100) includes a substrate rotation unit (rotary motor 23) and a lower surface nozzle 12. It should be noted that the thickness of the processing film 100 is much thinner than the thickness of the substrate W, but... Figure 5C For ease of illustration, the diagram is presented in an exaggerated manner (so that it appears to be the same thickness as the substrate W). Figure 5D and Figure 5E The same applies to Naka.

[0202] In the heating process, it is preferable to heat the substrate W such that the temperature of the processing liquid on the substrate W is lower than the boiling point of the solvent. By heating the processing liquid to a temperature lower than the boiling point of the solvent, a moderate amount of solvent remains in the processing film 100. Therefore, compared to the case where no solvent remains in the processing film 100, in the subsequent removal process (step S9), the release liquid is easily wetted onto the processing film 100 by the interaction between the solvent remaining in the processing film 100 and the release liquid. Thus, it becomes easier to peel off the processing film 100 with the release liquid.

[0203] The hot medium that is dispersed outward from the substrate W by centrifugal force is received by the first protective shield 71A. The hot medium received by the first protective shield 71A may sometimes rebound from it. 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 hot medium rebounding from the first protective shield 71A. Therefore, the adhesion of the hot medium to the upper surface of the processed film 100 can be suppressed, and thus, the generation of particles caused by the rebound of the hot medium from the first protective shield 71A can be suppressed.

[0204] Furthermore, by supplying gas from the central nozzle 11, an airflow F can be formed within the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W, moving from the central region of the upper surface of the substrate W to the periphery of the upper surface of the substrate W. By forming the airflow F moving from the central region of the upper surface of the substrate W to the periphery of the upper surface of the substrate W, the hot medium rebounding from the first protective cover 71A can be pushed back towards the first protective cover 71A. Therefore, the adhesion of the hot medium to the upper surface of the processing film 100 can be further suppressed.

[0205] Next, a buffering process (step S8) is performed. Specifically, the thermal medium valve 88 is closed. This stops the supply of thermal medium to the lower surface of the substrate W. Then, the gas valve 55 is closed. This stops the supply of gas to the space between the opposing surface 6a of the opposing member 6 and the upper surface of the substrate W.

[0206] Then, the relative component lifting unit 61 moves the relative component 6 to the upper position. Then, as... Figure 5D As shown, the third nozzle moving unit 38 moves the third moving nozzle 10 to the processing position. The processing position of the third moving nozzle 10 is, for example, the central position. In the buffering process, the substrate W can rotate at a specified buffer rotation speed, for example, 800 rpm.

[0207] Then, the upper buffer valve 53 is opened. This allows buffer solution to be supplied (ejected) from the third movable nozzle 10 to the central region of the upper surface of the rotating substrate W (buffer solution supply process, buffer solution ejection process). The buffer solution supplied to the upper surface of the substrate W is spread across the entire upper surface of the substrate W by centrifugal force. The supply of buffer solution to the upper surface of the substrate W can be sustained for a predetermined time, for example, 60 seconds.

[0208] When the stripping solution supplied to the substrate W in the subsequent removal process (step S9) has a high concentration, especially at the beginning of the supply, it may sometimes act locally on the upper surface of the substrate W. Therefore, by supplying a buffer solution to the upper surface of the substrate W before supplying the stripping solution, the effect of the stripping solution on the treated film 100 can be buffered. This prevents the stripping solution from acting locally on the upper surface of the substrate W, and thus allows the stripping solution to act on the entire upper surface of the substrate W without any omissions.

[0209] Next, the removal process (step S9) is performed. In the removal process, the substrate W can be rotated at a specified removal rotation speed, for example, 800 rpm.

[0210] Then, close the upper buffer valve 53. This stops the supply of buffer solution to the upper surface of the substrate W. Then, as... Figure 5E As shown, the upper stripping fluid valve 52 is opened. This supplies (ejects) stripping fluid from the third moving nozzle 10 to the central region of the upper surface of the rotating substrate W (upper stripping fluid supply process, upper stripping fluid ejection process). The stripping fluid supplied to the upper surface of the substrate W spreads across the entire upper surface of the substrate W by centrifugal force. The supply of stripping fluid to the upper surface of the substrate W can be sustained for a predetermined time, for example, 60 seconds.

[0211] By supplying a stripping fluid to the upper surface of the substrate W, the treatment film 100 can be peeled off from the upper surface of the substrate W. When the treatment film 100 is peeled off from the upper surface of the substrate W, it splits to form a film sheet. Furthermore, the split film sheets of the treatment film 100 are subjected to centrifugal force generated by the rotation of the substrate W and are expelled from the substrate W along with the stripping fluid. Thus, the object to be removed, along with the treatment film 100, can be removed from the upper surface of the substrate W.

[0212] Here, in Figure 5A In the processing liquid supply process (step S5) shown, the processing liquid supplied to the upper surface of the substrate W sometimes meanders along the periphery of the substrate W to the lower surface of the substrate W. Additionally, processing liquid that splashes from the substrate W sometimes bounces off the first protective shield 71A and adheres to the lower surface of the substrate W. Even in this case, as... Figure 5C As shown, a heat medium is supplied to the lower surface of the substrate W in the heating process (step S7), so that the processing liquid can also be discharged from the lower surface of the substrate W through the flow of the heat medium.

[0213] Furthermore, the processing liquid adhering to the lower surface of the substrate W due to the processing liquid supply process (step S5) sometimes solidifies or hardens, forming a solid. Even in this case, such as Figure 5E As shown, during the removal process (step S9) when the stripping liquid is supplied to the upper surface of the substrate W, the lower stripping liquid valve 87 is opened, and the stripping liquid is supplied (ejected) from the lower surface nozzle 12 to the lower surface of the substrate W. Thus, the solid can also be peeled off from the lower surface of the substrate W (lower stripping liquid supply process, lower stripping liquid ejection process).

[0214] In addition, such as Figure 5D As shown, in the buffering process (step S8), if the lower rinsing fluid valve 86 is opened during the supply of buffer solution to the upper surface of the substrate W, and rinsing fluid as buffer solution is supplied (ejected) from the lower surface nozzle 12 to the lower surface of the substrate W, the effect of the stripping fluid supplied to the lower surface of the substrate W can be buffered (lower buffer solution supply process, lower buffer solution ejection process).

[0215] Next, the second rinsing process (step S10) 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 its initial position. Then, as... Figure 5F As shown, the relative component lifting unit 61 moves the relative component 6 to the processing position. In the second rinsing process, the substrate W can rotate at a specified second rinsing rotation speed, for example, 800 rpm. The first protective cover 71A and the second protective cover 71B are maintained in the upper position.

[0216] Then, the upper rinse fluid valve 54 is opened. This supplies (ejects) rinse fluid from the central nozzle 11 to the central region of the upper surface of the rotating substrate W (second upper rinse fluid supply step, second upper rinse fluid ejection step). The rinse fluid supplied to the upper surface of the substrate W is radially distributed by centrifugal force, covering the entire upper surface of the substrate W. As a result, the stripping fluid adhering to the upper surface of the substrate W is washed away by the rinse fluid.

[0217] Then, the lower rinse fluid valve 86 is opened. This supplies (ejects) rinse fluid from the lower surface nozzle 12 to the central region of the lower surface of the rotating substrate W (second lower rinse fluid supply step, second lower rinse fluid ejection step). As a result, the stripping fluid adhering to the lower surface of the substrate W is washed away by the rinse fluid. The supply of rinse fluid to the upper and lower surfaces of the substrate W can be sustained for a predetermined time, for example, 35 seconds.

[0218] Next, the second organic solvent supply process (step S11) is carried out. Specifically, as follows: Figure 5GAs shown, the protective cover lifting unit 74 moves the first protective cover 71A to the lower position. Furthermore, the opposing member 6 is maintained in the processing position. In the second organic solvent supply process, the substrate W can rotate at a predetermined second organic solvent rotation speed, for example, 300 rpm.

[0219] Then, close the upper rinse fluid valve 54 and the lower rinse fluid valve 86. This stops the supply of rinse fluid to the upper and lower surfaces of the substrate W. Then, as... Figure 5G As shown, the organic solvent valve 56 is opened. This supplies (ejects) organic solvent from the central nozzle 11 to the central region of the upper surface of the rotating substrate W (second organic solvent supply step, second organic solvent ejection step, residue removal liquid supply step). The supply of organic solvent to the upper surface of the substrate W can be sustained for a predetermined time, for example, 30 seconds.

[0220] The organic solvent supplied to the upper surface of substrate W is radially distributed by centrifugal force, covering the entire upper surface of substrate W. As a result, the rinsing solution on the upper surface of substrate W is replaced by the organic solvent. The organic solvent supplied to the upper surface of substrate W dissolves the residue of the treated film 100 remaining on the upper surface of substrate W, and is then discharged from the periphery of the upper surface of substrate W (residue removal process).

[0221] Next, a rotary drying process (step S12) 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... Figure 5H As shown, the relative component lifting unit 61 moves the relative component 6 to a drying position below the processing position. When the relative component 6 is in the drying position, the distance between the opposing surface 6a of the relative component 6 and the upper surface of the substrate W is, for example, 1.5 mm. Then, the gas valve 55 is opened. As a result, gas is supplied to the space between the upper surface of the substrate W and the opposing surface 6a of the relative component 6.

[0222] Then, the rotary motor 23 accelerates the rotation of the substrate W, causing it to rotate at high speed. During the rotary drying process, the substrate W can rotate at a drying speed, for example, 1500 rpm. The rotary drying process can be carried out for a specified time, for example, 30 seconds. As a result, a large centrifugal force acts on the organic solvent on the substrate W, causing it to be thrown off the substrate W and dispersed around it. During the rotary drying process, by supplying gas to the space between the upper surface of the substrate W and the opposing surface 6a of the opposing member 6, the evaporation of the organic solvent can be promoted.

[0223] Then, the rotary motor 23 stops the rotation of the substrate W. The protective cover lifting unit 74 moves the first protective cover 71A and the second protective cover 71B to the lower position. The gas valve 55 is closed. The relative component lifting unit 61 moves the relative component 6 to the upper position.

[0224] The transport robot CR enters the processing unit 2, picks up the processed substrate W from the chuck pin 20 of the rotary chuck 5, and moves it out of the processing unit 2 (step S13). The substrate W is transferred from the transport robot CR to the transport robot IR, and is stored in the carrier C by the transport robot IR.

[0225] like Figure 6 As shown, a fine convex-concave pattern 160 is formed on the upper surface of the substrate W on which the substrate treatment is performed. The convex-concave 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.

[0226] The surfaces of the raised and recessed pattern 160, namely the surface 161a of the structure 161 (convex portion) and the surface of the recess 162, form a patterned surface 165 with raised and recessed features. The surface 161a of the structure 161 is composed of a top surface 161b (top) and a side surface 161c, and the surface of the recess 162 is composed of a bottom surface 162a (bottom). When the structure 161 is cylindrical, a recess will be formed on its inner side.

[0227] Structure 161 may include an insulating film or a conductive film. Alternatively, structure 161 may be a laminated film composed of multiple layers of films.

[0228] The raised pattern 160 is a fine pattern with an aspect ratio of 3 or higher. The aspect ratio of the raised pattern 160 is, for example, 10 to 50. The width L1 of the structure 161 can be approximately 10 nm to 45 nm, and the spacing L2 between the structures 161 can be approximately 10 nm to several μm. The height of the structure 161 (pattern height T1) can be, for example, approximately 50 nm to 5 μm. The pattern height T1 is the distance between the top surface 161b of the structure 161 and the bottom surface 162a (bottom) of the recess 162.

[0229] Next, refer to Figures 7A to 7C The process of forming a treatment film 100 on the patterned surface 165 and peeling the treatment film 100 off the patterned surface 165 will be explained. Figure 7A The patterned surface 165 of the substrate W is shown after the processing liquid supply process (step S5). Figure 7B The patterned surface 165 of the substrate W is shown after the spin-spinning process (step S6). Figure 7C The situation near the patterned surface 165 of the substrate W is shown during the removal process (step S9).

[0230] In the processing liquid supply step (step S5) performed before the spin-off step, the substrate W is rotated at a low first rotation speed (first rotation step). Therefore, as Figure 7A As shown, before the processing liquid is thrown off the pattern surface 165, the processing liquid enters the recess 162 of the embossed pattern 160 due to its own weight, and the processing liquid is filled into the recess 162 (processing liquid filling process).

[0231] In the spin-off process, the substrate W is rotated at a second rotation speed, which is faster than the first rotation speed (second spin-off process). Therefore, with the processing liquid reaching the bottom of the recess 162 of the embossed pattern 160, the processing liquid film 101 on the substrate W is thinned. During thinning, the solvent evaporates from the processing liquid film 101, thus... Figure 7B As shown, a thin semi-solid film 106 extends following (along) the raised and recessed pattern 160. Then, in the heating process (step S7), the semi-solid film 106 (processing liquid film 101) is heated, thereby further evaporating (evaporating) the solvent in the semi-solid film 106 (processing liquid film 101), and the formation of the processing film 100 is completed (processing film formation process).

[0232] The processing film 100 covers the object to be removed 103 existing on the surface (i.e., pattern surface 165) of the raised pattern 160. The adhesion force between the processing film 100 and the object to be removed 103 is greater than the adhesion force between the object to be removed 103 and the raised pattern 160. Therefore, the processing film 100 can firmly hold the object to be removed 103.

[0233] The thickness D of the processing film 100 is thinner than the pattern height T1 in the thickness direction T of the substrate W. The thickness D of the portion of the processing film 100 following the bottom surface 162a of the recess 162 and the top surface 161b of the structure 161 is equal to the width of the processing film 100 in the thickness direction T of the substrate W. The thickness D of the portion of the processing film 100 following the side surface 161c of the structure 161 is equal to the width of the processing film 100 in a direction orthogonal to the thickness direction T of the substrate W. The surface of the processing film 100 is located in the recess 162 further from the bottom surface 162a than the top surface 161b (top) of the structure 161 (protrusion) adjacent to the recess 162.

[0234] Then, refer to Figure 7C In the removal process, when a stripping liquid is supplied to the patterned surface 165 of the substrate W, the stripping liquid penetrates the treatment film 100 and acts on the interface between the treatment film 100 and the patterned surface 165. The treatment film 100 splits due to the energy received from the stripping liquid flowing on the substrate W, becoming a film sheet 105. The film sheet 105 of the treatment film 100 is peeled off from the patterned surface 165 while still holding the object to be removed 103 (treatment film splitting process, stripping process). Then, the object to be removed 103, while held by the treatment film 100, is discharged together with the treatment film 100 to the outside of the substrate W and removed from the substrate W.

[0235] Next, refer to Figures 8A to 8C The internal condition of the treatment film 100 when it is peeled off from the substrate W will be described. Figure 8A The interior of the treatment membrane 100 is shown after the heating process (step S7) and before the buffering process (step S8) begins. Figure 8B and Figure 8C The interior of the treatment membrane 100 is shown during the removal process (step S9).

[0236] like Figure 8A As shown, the processing film 100 formed by heating the substrate W has a first solid 110 formed by a first component contained in the solute of the processing liquid, and a second solid 111 formed by a second component contained in the solute of the processing liquid.

[0237] Reference Figure 8B In the removal process, when a stripping solution is supplied to the upper surface of the substrate W, the first solid 110, which is formed by the first component and has a higher solubility in the stripping solution than the second component, is mainly dissolved. As a result, through-holes 102 are formed in the processed film 100 at the portions where the first solid 110 is concentrated (through-hole formation process). Through-holes 102 are particularly easily formed in the portions of the first solid 110 that extend along the thickness direction of the processed film 100. When viewed from above, the through-holes 102 are, for example, several nm in diameter.

[0238] The stripping fluid dissolves not only the first solid 110 but also the second solid 111. However, since the second component is less soluble in the stripping fluid than the first component, the second solid 111 is only slightly dissolved by the stripping fluid near its surface.

[0239] Therefore, the stripping fluid reaching the vicinity of the patterned surface 165 via the through-hole 102 will slightly dissolve the portion of the second solid 111 near the patterned surface 165. Thus, as... Figure 8B As shown in the enlarged view, the stripping liquid slowly dissolves the second solid 111 near the patterned surface 165 while entering the gap G1 between the treatment film 100 and the patterned surface 165 (the stripping liquid enters the process).

[0240] Then, for example, starting from the periphery of the through-hole 102, the processed membrane 100 splits to form a membrane sheet 105. For example... Figure 8C As shown, the membrane 105 of the processing membrane 100 is peeled off from the patterned surface 165 while the object to be removed 103 is still in the process.

[0241] It should be noted that the stripping solution may sometimes hardly dissolve the second solid 111. Even in this case, the treatment film 100 can be peeled off from the substrate W by entering the tiny gap G between the treatment film 100 and the upper surface of the substrate W.

[0242] In this embodiment, during the film formation process (steps S6 and S7), the processing film 100 is formed by following the raised and recessed patterns 160 (the raised and recessed areas of the patterned surface 165) of the patterned surface 165. Therefore, the film thickness D of the processing film 100 can be reduced over the entire area of ​​the patterned surface 165. Consequently, the stripping liquid can easily pass through the processing film 100 over the entire area of ​​the patterned surface 165, and can easily reach the interface between the processing film 100 and the patterned surface 165.

[0243] Furthermore, by reducing the thickness D of the treatment membrane 100, the strength of the treatment membrane 100 can be reduced. Therefore, the energy received by the stripping liquid flowing on the patterned surface 165 can easily be used to cause the treatment membrane 100 to split into membrane sheets 105. Thus, the stripping liquid can quickly reach the interface between the treatment membrane 100 and the patterned surface 165 from between the split membrane sheets 105.

[0244] By rapidly extending the stripping fluid across the entire area of ​​the patterned surface 165 to the interface between the treatment film 100 and the patterned surface 165, the object to be removed 103 can be efficiently peeled off from the patterned surface 165 along with the treatment film 100. As a result, the object to be removed 103 can be efficiently removed from the substrate W.

[0245] Furthermore, according to this embodiment, the thickness D of the processed film 100 formed in the processed film formation process is thinner than the height (pattern height T1) of the unevenness of the patterned surface 165 in the thickness direction T of the substrate W. Therefore, the distance between the surface of the processed film 100 and the patterned surface 165 in the thickness direction T can be reduced. Consequently, the stripping liquid can quickly reach the interface between the patterned surface 165 and the processed film 100. As a result, the object to be removed 103 and the processed film 100 can be more efficiently peeled off from the patterned surface 165 together.

[0246] According to this embodiment, in the processing film formation process, the processing film 100 is formed in the recess 162 such that the surface of the processing film 100 is located closer to the bottom surface 162a (bottom) of the recess 162 than the top of the structure 161 (protrusion) adjacent to the recess 162. Therefore, compared to the case where the processing film 100 is formed by filling the entire recess 162 in the processing film formation process, the film thickness D (distance between the bottom surface 162a and the surface of the processing film 100) of the processing film 100 in the recess 162 can be reduced. Therefore, the stripping liquid can quickly reach the interface between the bottom surface 162a of the recess 162 of the patterned surface 165 and the processing film 100. As a result, the object to be removed 103 and the processing film 100 can be removed from the raised and recessed pattern 160 more efficiently.

[0247] According to this embodiment, in the processing film formation process, the processing film 100 is formed by covering the object to be removed 103. This increases the contact area between the processing film 100 and the object to be removed 103, thereby improving the holding force of the processing film 100 in retaining the object to be removed 103. Consequently, the amount of object to be removed 103 that detaches from the processing film 100 is reduced. Therefore, most of the object to be removed 103 can be removed from the substrate W along with the processing film 100, thus efficiently removing the object to be removed 103 from the substrate W while preventing it from re-attaching to the substrate W.

[0248] According to this embodiment, in the processing film formation process, the processing film 100 can be formed such that the adhesion force between the processing film 100 and the object to be removed 103 is greater than the adhesion force between the object to be removed 103 and the substrate W. Therefore, when the processing film 100 is peeled off from the patterned surface 165 using a stripping solution, the number of objects to be removed 103 remaining on the patterned surface 165 that have not been removed can be reduced. Therefore, most of the objects to be removed 103 can be removed from the substrate W together with the processing film 100, thus efficiently removing the objects to be removed from the substrate W.

[0249] According to this embodiment, in the removal process (step S9), the first solid 110 is dissolved by using a stripping liquid, that is, by partially dissolving the treatment membrane 100, a through hole 102 is formed on the treatment membrane 100 (through hole forming process).

[0250] Therefore, the stripping fluid can quickly reach the interface between the treatment film 100 and the patterned surface 165 through the through hole 102. Thus, the stripping fluid can act on the interface between the treatment film 100 and the patterned surface 165, and can efficiently peel the object to be removed 103 and the treatment film 100 together from the patterned surface 165.

[0251] On the other hand, although the processing film 100 is partially dissolved by the stripping liquid in order to form the through-hole 102, the remaining portion (the second solid 111) is maintained in a solid state. Therefore, the processing film 100, which holds the object to be removed 103, can be peeled off from the patterned surface 165 while forming the through-hole 102. As a result, the object to be removed 103 and the processing film 100 can be efficiently removed from the patterned surface 165 together.

[0252] According to this embodiment, during the removal process, the stripping liquid enters between the treatment film 100 and the patterned surface 165 through the through hole 102 (the stripping liquid entry process). Therefore, the stripping liquid can act on the interface between the treatment film 100 and the patterned surface 165, and the treatment film 100 can be peeled off from the patterned surface 165 more efficiently.

[0253] According to this embodiment, the processed membrane 100 formed in the processed membrane forming process has a first solid 110 formed of a first component and a second solid 111 formed of a second component. Since the first component has higher solubility in the stripping solution than the second component, the first solid 110 is more easily dissolved in the stripping solution than the second solid 111.

[0254] Therefore, while reliably forming the through hole 102 by dissolving the first solid 110 with the stripping liquid, the second solid 111 is hardly dissolved in the stripping liquid, maintaining the solid state of the second solid 111. Therefore, while holding the object to be removed 103 with the second solid 111, the stripping liquid can act on the interface between the second solid 111 and the patterned surface 165.

[0255] As a result, the object to be removed 103 and the processing film 100 can be quickly peeled off from the patterned surface 165 together, while the object to be removed 103 and the processing film 100 can be efficiently removed from the patterned surface 165 together.

[0256] According to this embodiment, during a predetermined period from the start of supplying the processing liquid to the patterned surface 165 to the formation of the processing film 100, the substrate W is rotated at a first speed (first rotation step). That is, during the period from the start of supplying the processing liquid to the patterned surface 165 to the formation of the processing film 100, the substrate W is rotated at a lower first speed. Therefore, the processing liquid is thrown off by centrifugal force, and before the amount of processing liquid on the patterned surface 165 is extremely reduced, the processing liquid enters the recesses 162 of the raised and recessed pattern 160 due to its own weight.

[0257] Furthermore, after the first rotation step until the formation of the processing film 100, the rotation of the substrate W is accelerated, and the substrate W rotates at a second speed that is faster than the first speed (second rotation step). As a result, the processing liquid is removed from the patterned surface 165 of the substrate W. Therefore, a sufficiently thin processing film 100 can be formed even when the processing liquid has entered the recesses 162 of the embossed pattern 160 due to its own weight.

[0258] This invention is not limited to the embodiments described above, and can also be implemented in other ways.

[0259] For example, in substrate processing apparatus 1, substrate processing can be performed without the chemical solution supply step (step S2), the first rinsing step (step S3), and the first organic solvent supply step (step S4).

[0260] Furthermore, in the substrate processing of the above embodiments, during the film formation process (steps S6 and S7), the solvent of the processing liquid is evaporated by heating the substrate W using a heat medium. However, the substrate W is not limited to being heated by supplying a heat medium; for example, it can also be heated by a heater (not shown) built into the rotating base 21 and the opposing member 6. In this case, the heater functions as both a substrate heating unit and an evaporation unit (evaporation promotion unit).

[0261] Furthermore, heating the substrate W is not always necessary during the formation of the processed film 100. That is, if the solvent is sufficiently evaporated (evaporated) during the spin-spinning process (step S6) to complete the formation of the processed film 100, the subsequent heating process (step S7) may not be required. In particular, if solvent can remain inside the processed film 100, the solvent can be easily evaporated to the desired extent even without heating the substrate W.

[0262] In addition, the buffer process (step S8) can be omitted in each of the above substrate processing steps.

[0263] Furthermore, in the embodiments described above, the content of the second component in the processing solution is greater than the content of the first component in the processing solution. Therefore, compared to a configuration where the content of the second component in the processing solution is less than the content of the first component in the processing solution, the portion of the processing film 100 that can be dissolved by the stripping liquid can be reduced. Therefore, the amount of removable material 103 that detaches from the processing film 100 along with the partial dissolution of the processing film 100 can be reduced. Therefore, most of the removable material 103 can be removed from the upper surface of the substrate W along with the processing film 100, thus efficiently removing the removable material 103 from the substrate W while preventing it from re-adhering to the substrate W.

[0264] However, unlike the embodiments described above, the content of the second component in the processing solution can be less than the content of the first component in the processing solution. In this case, compared to a configuration where the content of the second component in the processing solution is greater than the content of the first component, the portion of the processing film 100 that can be dissolved by the stripping liquid can be increased. Therefore, the processing film 100 can be split into smaller film sheets 105. Since the processing film 100 is split into smaller film sheets 105, the film sheets 105 are more likely to float due to the force exerted by the flow of the stripping liquid and are more likely to be discharged outside the substrate W along with the flow of the stripping liquid. Therefore, the processing film 100 can be removed from the substrate W efficiently.

[0265] Furthermore, in the embodiments described above, the components of the solute (the first component and the second component) contained in the treatment solution are synthetic resins. However, the components of the solute do not necessarily have to be synthetic resins; they can be any substances that can be dissolved by the solvent contained in the treatment solution, and the solubility of the first component in the stripping solution is higher than that of the second component in the stripping solution. In this case, the components of the solute may also be, for example, metals or salts.

[0266] Alternatively, organic solvents such as IPA can be used as the stripping fluid. In this case, the first and second components contained in the solute of the treatment fluid can also be the same resins used when using an aqueous stripping fluid.

[0267] Furthermore, in the above embodiments, the solute contained in the treatment solution includes the first component and the second component. However, the solute may be composed of a single component, or it may contain three or more components with different solubilities in the stripping solution.

[0268] Furthermore, when the processing liquid and stripping liquid described in the above embodiments are the processing liquid and stripping liquid described below, they can also achieve the same effect as the above embodiments.

[0269] Below, "C" x～y “C” x ~C y "and "C x The number of carbon atoms in a molecule or substituent is specified. For example, C... 1～6 Alkyl refers to an alkyl chain having one or more but no more than six carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0270] The following describes copolymerization of polymers having multiple repeating units. Unless otherwise specified, the copolymerization described above can be any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When polymers or resins are represented by structural formulas, n, m, etc., as indicated in parentheses represent the number of repeating units.

[0271] <Treatment Fluid>

[0272] The processing solution comprises (A) a second component as an insoluble or sparingly soluble solute, (B) a first component as a soluble solute, and (C) a solvent. The processing solution is dropwise added to a substrate, and the solvent (C) is removed by drying, causing the second component (A) to form a film, which, together with the first component (B), remains on the substrate as a film. Then, the aforementioned film is removed from the substrate using a stripping solution. Preferably, the second component (A) is insoluble or sparingly soluble with respect to the stripping solution. Additionally, it is preferable that the first component (B) is soluble with respect to the stripping solution. The term "solute" as used above is not limited to a state of dissolution in the solvent (C), but also allows for a suspended state. As a preferred embodiment, the solute, components, and additives contained in the processing solution are dissolved in the solvent (C). It is believed that the processing solution using this method exhibits good embedding performance or film uniformity.

[0273] Here, preferably, "together as a film" means coexisting in a single film, rather than being formed into separate layers. One way to "form a film" is through "curing." It should be noted that the film obtained from the treatment liquid only needs to have a degree of hardness sufficient to retain the particles; it is not necessary to completely remove the solvent (C) (e.g., by vaporization). The aforementioned treatment liquid forms a film while slowly shrinking as the solvent (C) evaporates. The aforementioned "residue on the substrate as a film" is allowed to be removed in very small amounts relative to the whole (e.g., by evaporation, volatilization). For example, it is permissible to remove 0 to 10% by mass (preferably 0 to 5% by mass, more preferably 0 to 3% by mass, further preferably 0 to 1% by mass, and even more preferably 0 to 0.5% by mass) relative to the initial amount.

[0274] Not intended to limit the scope of rights, nor theoretically restricted, but it is believed that the aforementioned membrane holds particles on the substrate, which are then stripped away by the stripping liquid and thus removed. Furthermore, since component (B)1 remains in the aforementioned membrane, it is considered that this creates a portion that becomes the starting point for the stripping of the aforementioned membrane.

[0275] <Second ingredient>

[0276] (A) The second component comprises at least one copolymer of Novolac, polyhydroxystyrene, polystyrene, polyacrylic acid derivatives, polymaleic acid derivatives, polycarbonate, polyvinyl alcohol derivatives, polymethacrylic acid derivatives, and combinations thereof. Preferably, (A) the second component may comprise at least one copolymer of Novolac, polyhydroxystyrene, polyacrylic acid derivatives, polycarbonate, polymethacrylic acid derivatives, and combinations thereof. More preferably, (A) the second component may comprise at least one copolymer of Novolac, polyhydroxystyrene, polycarbonate, and combinations thereof. Novolac may be phenol Novolac.

[0277] It goes without saying that the treatment solution may contain one or more of the preferred embodiments described above as the second component (A). For example, the second component (A) may contain both Novolac and polyhydroxystyrene.

[0278] (A) The second component forms a film by drying. For the aforementioned film, a preferred method is that most of it is not dissolved by the stripping solution described later, so as to be stripped while still containing particles. It should be noted that it is permissible for a very small portion of the second component in (A) to be dissolved by the stripping solution.

[0279] Preferably, component (A) does not contain fluorine and / or silicon, and more preferably, it does not contain either of these two substances.

[0280] The aforementioned copolymers are preferably random copolymers or block copolymers.

[0281] Not intended to limit the scope of the rights, but as specific examples of component (A), the compounds shown in chemical formulas 7 to 13 below can be cited.

[0282] [Chemical Formula 7]

[0283]

[0284] [Chemical Formula 8]

[0285]

[0286] [Chemical Formula 9]

[0287]

[0288] [Chemical Formula 10]

[0289]

[0290] (R refers to C) 1～4 Alkyl and other substituents)

[0291] [Chemical Formula 11]

[0292]

[0293] [Chemical Formula 12]

[0294]

[0295] [Chemical Formula 13]

[0296]

[0297] (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.

[0298] (A) Component 2 can be obtained through synthesis. Alternatively, it can be purchased. In the case of purchase, the following supplier can be cited as an example. The supplier can also synthesize polymer (A).

[0299] Novolac: Showa Kasei Corporation, Asahi Organic Materials Co., Ltd., Gunei Chemical Industry Co., Ltd., Sumitomo Bakelite Co., Ltd.

[0300] Polyhydroxystyrene: Nippon Soda Co., Ltd., Maruzen Petrochemical Co., Ltd., Toho Chemical Co., Ltd.

[0301] Polyacrylic acid derivatives: Nippon Shokubai Co., Ltd.

[0302] Polycarbonate: Sigma-Aldrich Co. LLC.

[0303] Polymethacrylic acid derivatives: Sigma-Aldrich Co. LLC.

[0304] Compared to the total mass of the treatment liquid, 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. That is, based on a total mass of 100% by mass, the second component (A) is 0.1 to 50% by mass. In other words, "compared to..." can be paraphrased as "based on...". The same applies below unless otherwise specified.

[0305] Solubility can be evaluated using known methods. For example, under conditions of 20°C to 35°C (more preferably 25±2°C), 100 ppm of the aforementioned (A) or the following (B) is added to 5.0% by mass ammonia solution in a flask, the flask is capped, and the mixture is shaken for 3 hours. The solubility can then be determined by whether (A) or (B) dissolves. Shaking can also be done by stirring. Solubility can also be judged visually. If it does not dissolve, the solubility is less than 100 ppm; if it dissolves, the solubility is greater than 100 ppm. Solubility less than 100 ppm is considered insoluble or sparingly soluble, while solubility greater than 100 ppm is considered soluble. Broadly speaking, soluble includes slightly soluble. Solubility decreases in the order of insoluble, sparingly soluble, and soluble. Narrowly defined, slightly soluble has lower solubility than soluble but higher solubility than sparingly soluble.

[0306] Alternatively, the aforementioned 5.0% by mass ammonia solution can be replaced with a stripping solution used in subsequent processes. The liquid used for solubility evaluation does not need to be the same as the stripping solution; components with different solubilities can coexist. Component (B) 1, present in the treated film (particle retention layer) formed by the treatment solution, is dissolved by the stripping solution, thereby providing a starting point for the treated film to be stripped from the substrate. Therefore, if a portion of component (B) 1 can be dissolved using the stripping solution, a starting point for stripping can be provided to the treated film. Therefore, for example, the alkalinity of the stripping solution can be weaker than that of the liquid used in the solubility evaluation.

[0307] <First ingredient>

[0308] (B) The first component is (B') a crack-promoting component. (B') The crack-promoting component contains a hydrocarbon, and also contains a hydroxyl group (-OH) and / or a carbonyl group (-C(=O)-). When (B') is a polymer, one of the structural units contains a hydrocarbon within each unit, and also has a hydroxyl group and / or a carbonyl group. Examples of carbonyl groups include carboxylic acids (-COOH), aldehydes, ketones, esters, amides, and ketenes, with carboxylic acids being preferred.

[0309] Not intended to limit the scope of the rights, and not theoretically restricted, it is believed that when the processing solution is dried to form a processing film on the substrate, and the processing film is peeled off by a stripping solution, component (B)1 is generated as the starting point for the peeling of the processing film. Therefore, the solubility of component (B)1 in the stripping solution is preferably higher than that of component (A)2. As a way to include a ketone as a carbonyl group in the crack-inducing component (B'), cyclic hydrocarbons can be cited. Specific examples include 1,2-cyclohexanedione and 1,3-cyclohexanedione.

[0310] In a more specific manner, (B) the first component is represented by at least one of the following formulas (B-1), (B-2) and (B-3).

[0311] (B-1) is a compound comprising 1 to 6 (preferably 1 to 4) of the following chemical formula 14 as structural units, wherein each structural unit is connected by a linking group L1.

[0312] [Chemical Formula 14]

[0313]

[0314] Here, L1 is selected from single bonds and C. 1～6 At least one of the alkylene groups. The aforementioned C 1～6 Alkyl groups act as linkers to connect structural units, and are not limited to divalent groups. Preferably, they are divalent to tetravalent. The aforementioned C 1～6 The alkylene group can be either straight-chain or branched. L1 is preferably a single bond, methylene, ethylene, or propylene.

[0315] Cy1 is C 5～30 The hydrocarbon ring is preferably phenyl, cyclohexane, or naphthyl, more preferably phenyl. Preferably, connector L1 connects multiple Cy1 rings.

[0316] R1 is independently C 1～5 Alkyl groups, preferably methyl, ethyl, propyl, or butyl. The aforementioned C 1～5 Alkyl groups can be either straight-chain or branched.

[0317] n b1 It can be 1, 2, or 3, preferably 1 or 2, and more preferably 1. b1’ The value can be 0, 1, 2, 3 or 4, preferably 0, 1 or 2.

[0318] Not intended to limit the scope of the claims, but as preferred examples of (B-1), 2,2-bis(4-hydroxyphenyl)propane, 2,2'-methylenebis(4-methylphenol), 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, 1,3-cyclohexanediol, 4,4'-dihydroxybiphenyl, 2,6-naphthalenediol, 2,5-di-tert-butylhydroquinone, and 1,1,2,2-tetra(4-hydroxyphenyl)ethane can be obtained by polymerization and condensation.

[0319] As an example, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, represented by formula 15, is used for illustration. In this compound, (B-1) contains three structural units of formula 14, linked by L1 (methylene). b1 =n b1’ =1, R1 is a methyl group.

[0320] [Chemical Formula 15]

[0321]

[0322] (B-2) is represented by the following chemical formula 16.

[0323] [Chemical Formula 16]

[0324]

[0325] R 21 R 22 R 23 and R 24 Each is independently hydrogen or C 1～5 The alkyl group is preferably hydrogen, methyl, ethyl, tert-butyl, or isopropyl, more preferably hydrogen, methyl, or ethyl, and even more preferably methyl or ethyl.

[0326] L 21 and L22 Each independently is C 1～20 alkylene, C 1～20 Cycloalkylene, C 2～4 imidene group, C 2～4 The ethynyl group, or C 6～20 arylene groups. These groups can be converted by C... 1～5 Alkyl or hydroxyl substitution. Here, "alkenyl" refers to a divalent hydrocarbon with one or more double bonds, and "ynyneyl" refers to a divalent hydrocarbon with one or more triple bonds. L 21 and L 22 C is preferred 2～4 Alkylene, ethynylene (C2 ethynylene), or phenylene, more preferably C2 2～4 The alkylene or ethynylene group, more preferably ethynylene group.

[0327] n b2 It can be 0, 1, or 2, preferably 0 or 1, and more preferably 0.

[0328] Not intended to limit the scope of the claims, but as preferred examples of (B-2), 3,6-dimethyl-4-octyne-3,6-diol and 2,5-dimethyl-3-hexyn-2,5-diol may be cited. Other preferred examples of (B-2) may be 3-hexyn-2,5-diol, 1,4-butynediol, 2,4-hexadiyn-1,6-diol, 1,4-butanediol, cis-1,4-dihydroxy-2-butene, and 1,4-benzylenedimethanol.

[0329] (B-3) is a polymer containing structural units represented by the following chemical formula 17 and having a weight-average molecular weight (Mw) of 500 to 10,000. Mw is preferably 600 to 5,000, more preferably 700 to 3,000.

[0330] [Chemical Formula 17]

[0331]

[0332] Here, R 25 The form is -H, -CH3, or -COOH, preferably -H or -COOH. It is also permissible for one (B-3) polymer to contain more than two structural units, each represented by chemical formula 14.

[0333] Not intended to limit the scope of the claims, polymers of acrylic acid, maleic acid, acrylic acid, or combinations thereof are cited as preferred examples of polymers (B-3). Polyacrylic acid and maleic acid-acrylic acid copolymers are further preferred examples.

[0334] In the case of copolymerization, random copolymerization or block copolymerization is preferred, and random copolymerization is more preferred.

[0335] As an example, the maleic acid-acrylic acid copolymer represented by chemical formula 18 is given for illustration. This copolymer is contained in (B-3) and has two structural units represented by chemical formula 14, in which R 25 For -H, in another structural unit, R 25 It is -COOH.

[0336] [Chemical Formula 18]

[0337]

[0338] It goes without saying that the treatment solution may contain one or more of the preferred examples described above as component (B). For example, component (B) may contain 2,2-bis(4-hydroxyphenyl)propane and 3,6-dimethyl-4-octyne-3,6-diol.

[0339] (B) The molecular weight of the first component may be 80 to 10,000. The molecular weight of the first component is preferably 90 to 5,000, more preferably 100 to 3,000. (B) When the first component is a resin, polymer, or a polymer, the molecular weight is expressed as weight-average molecular weight (Mw).

[0340] (B) Component 1 can be obtained through synthesis or by purchase. Examples of suppliers include Sigma-Aldrich Co., LLC., Tokyo Chemical Industry Co., Ltd., and Nippon Shokubai.

[0341] In the treatment solution, the mass percentage of component (B) 1 compared to component (A) 2 is preferably 1 to 100% by mass, more preferably 1 to 50% by mass. In the treatment solution, the mass percentage of component (B) 1 compared to component (A) 2 is even more preferably 1 to 30% by mass.

[0342] <Solvent>

[0343] (C) The solvent preferably contains an organic solvent. The solvent (C) may be volatile. Volatility means that it is more volatile than water. For example, the boiling point of the solvent (C) at 1 atmosphere is preferably 50–250°C. More preferably, the boiling point of the solvent at 1 atmosphere is 50–200°C, and even more preferably 60–170°C. The boiling point of the solvent at 1 atmosphere is even more preferably 70–150°C. It is also permissible for the solvent (C) to contain a small amount of pure water. The pure water contained in the solvent (C) is preferably 30% by mass or less compared to the total volume of the solvent (C). More preferably, the pure water contained in the solvent is 20% by mass or less, and even more preferably 10% by mass or less. The pure water contained in the solvent is even more preferably 5% by mass or less. It is also preferred that the solvent does not contain pure water (0% by mass). Pure water is preferably distilled water (DIW).

[0344] Examples of organic solvents include alcohols such as isopropanol (IPA), ethylene glycol monomethyl ethers and ethylene glycol monoethyl ethers, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE), propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, lactates such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, and cyclohexanone, amides such as N,N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These organic solvents can be used alone or in mixtures of two or more.

[0345] As a preferred embodiment, the organic solvent contained in (C) is selected from IPA, PGME, PGEE, EL, PGMEA, and any combination thereof. When the organic solvent is a combination of two, the volume ratio is preferably 20:80 to 80:20, more preferably 30:70 to 70:30.

[0346] The amount of solvent (C) is 0.1 to 99.9% by mass relative to the total mass of the treatment liquid. The amount of solvent (C) is preferably 50 to 99.9% by mass relative to the total mass of the treatment liquid, more preferably 75 to 99.5% by mass. The amount of solvent (C) is further preferably 80 to 99% by mass relative to the total mass of the treatment liquid, and even more preferably 85 to 99% by mass.

[0347] <Other Additives>

[0348] The treatment solution of the present invention may further comprise (D) other additives. As one aspect of the present invention, (D) other additives include surfactants, acids, bases, antibacterial agents, bactericides, preservatives, or antifungal agents (preferably surfactants), and may comprise any combination thereof.

[0349] As one aspect of the present invention, compared to the mass of component (A) 2 in the treatment liquid, the mass of other additives (D) (if multiple additives exist, the sum of them) is 0 to 100% by mass (preferably 0 to 10% by mass, more preferably 0 to 5% by mass, further preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass). It is also one aspect of the present invention that the treatment liquid does not contain other additives (D) (0% by mass).

[0350] <Separation Fluid>

[0351] As described above, the processing liquid is dropwise added to the substrate, and the solvent (C) is removed by drying, causing the second component (A) to form a film. Thus, the second component (A) and the first component (B) remain on the substrate as a processing film. Then, the processing film (particle holding layer) is removed from the substrate using a removal liquid. The processing film retains particles present on the substrate and is removed by a stripping liquid while still retaining the particles present on the substrate.

[0352] The stripping solution can be alkaline, neutral, or acidic, preferably alkaline. The pH of the stripping solution is preferably 7-13. More specifically, the pH of the stripping solution is preferably 8-13, more preferably 10-13, and even more preferably 11-12.5. For pH measurement, to avoid the influence of dissolved carbon dioxide in the air, it is preferable to perform the measurement after degassing.

[0353] Not intended to limit the scope of the claims, but as specific examples of stripping solutions, ammonia, SC-1 washing solution, TMAH aqueous solution, choline aqueous solution, and any combination thereof (preferably ammonia) can be cited. The solvent of the stripping solution is predominantly pure water. The proportion of pure water in the solvent of the stripping solution is 50–100% by mass (preferably 70–100% by mass, more preferably 90–100% by mass, further preferably 95–100% by mass, and even more preferably 99–100% by mass). The concentration of the solute in the stripping solution is 0.1–10% by mass (preferably 0.2–8% by mass, further preferably 0.3–6% by mass). By adding the aforementioned alkaline component to the treatment solution, pure water (with a solute concentration of 0.0% by mass, preferably 0.00% by mass) can also be used as the stripping solution.

[0354] The formation of the treatment film and its peeling off from the substrate can also be described as follows.

[0355] The processing solution comprises (A) a second component, (B') a crack-promoting component (first component), and (C) a solvent. The processing solution of the present invention is dropped onto a substrate and dried, thereby forming a film of (A) the second component. By forming a film of (A) the second component, a processed film is formed. Then, by supplying a stripping solution to the processed film, the crack-promoting component dissolves into the stripping solution. By dissolving the crack-promoting component into the stripping solution, traces (pores) of the dissolution of the crack-promoting component are created on the processed film. These traces promote the peeling off of the particle layer from the substrate. Cracks propagate from these traces. The processed film, fractured due to crack propagation, is removed from the substrate while still containing particles.

[0356] When the stripping solution removes (e.g., peels off) the treated membrane, it is assumed that the residual (B) first component in the membrane becomes the starting point for the peeling of the treated membrane. Therefore, it is preferable that the solubility of (B) first component in the stripping solution is higher than that of (A) second component. Preferably, the treated membrane is not completely dissolved by the stripping solution and is removed from the substrate while still containing particles. It is assumed that the treated membrane is removed, for example, as a broken piece due to the aforementioned "starting point for peeling".

[0357] The present invention will be illustrated by various examples as described below. It should be noted that the processing liquid and stripping liquid are not limited to these examples.

[0358] Preparation of patterned substrate

[0359] A KrF resist composition (AZ DX-6270P, Merck Performance Materials Co., Ltd., hereinafter referred to as MPM) was spin-coated onto an 8-inch Si substrate at 1500 rpm. The substrate was then soft-baked at 120°C for 90 seconds. A KrF stepper exposure machine (FPA-3000EX5, Canon) was used with a flux of 20 mJ / cm². 2 Exposure was performed, followed by PEB (post-exposure baking) at 130°C for 90 seconds, and development was carried out with a developer (AZ MIF-300, MPM). This yielded a resist pattern with a line spacing of 360 nm and a duty ratio of 1:1. This resist pattern was used as an etching mask, and the substrate was etched using a dry etching apparatus (NE-5000N, ULVAC). The substrate was then washed with a stripper (AZ 400T, MPM) to remove the resist pattern and resist residue. This resulted in a patterned substrate with a 360 nm spacing, a 1:1 duty ratio, and a line height of 150 nm.

[0360] Preparation of bare substrate

[0361] Use an 8-inch Si substrate.

[0362] Evaluation of substrate preparation

[0363] Particles are attached to the above-mentioned patterned substrate and bare substrate.

[0364] Ultra-high purity colloidal silica (PL-10H, Fuso Chemical Industry, average primary particle size 90 nm) was used as the experimental particles. 50 mL of the silica particle composition was added dropwise and coated by rotating at 500 rpm for 5 seconds. Then, the solvent of the silica particle composition was dried by rotating at 1000 rpm for 30 seconds. This yielded the evaluation substrate.

[0365] Evaluation of solubility

[0366] Add 4 mg of each component to a 50 mL sample vial (e.g., 2,2-bis(4-hydroxyphenyl)propane), and add 5.0% (w / w) ammonia to a total volume of 40 g. Cap the vial and shake for 3 hours. This yields a liquid with a component concentration of 100 ppm. Repeat the above steps with each component added at 40 mg to obtain a liquid with a concentration of 1,000 ppm.

[0367] Their solubility is confirmed visually. The evaluation criteria are as follows.

[0368] X: Undissolved residues of the component were detected at concentrations of 100 ppm and 1,000 ppm. In this case, the component is determined to be insoluble or sparingly soluble.

[0369] Y: No undissolved residue was detected when the concentration of the component was 100 ppm, and undissolved residue was detected when the concentration of the component was 1,000 ppm. In this case, the component is judged to be slightly soluble.

[0370] Z: No undissolved residue was detected at component concentrations of 100 ppm and 1,000 ppm. In this case, the component is considered soluble.

[0371] The evaluation results are recorded in Tables 1 to 4 below.

[0372] Preparation Example 1 of Washing Solution 1

[0373] Novolac (Mw about 300) is used as component 2 in (A), and 2,2-bis(4-hydroxyphenyl)propane is used as component 1 in (B).

[0374] Weigh 2,2-bis(4-hydroxyphenyl)propane to make it 5% by mass relative to Novolac (Mw approximately 300). Weigh out 5g of these components and add them to 95g of IPA ((C) solvent). Stir the mixture with a stir bar for 1 hour to obtain a liquid with a solid content of 5% by mass.

[0375] The liquid was filtered using an Optimizer UPE (Entegris Japan Co., Ltd., UPE, pore size 10 nm). This yielded washing solution 1, as shown in Table 1.

[0376] In Tables 1 to 4 below, the numbers in parentheses in column (B) represent the concentration (mass%) of component (B) relative to component (A) 2.

[0377] [Table 1]

[0378] Table 1

[0379]

[0380] [Table 2] Table 2

[0381]

[0382] [Table 3]

[0383] Table 3

[0384]

[0385] [Table 4]

[0386] Table 4

[0387]

[0388] In the table above, abbreviations will be used as follows.

[0389] Novolac (approximately 300 Mw) will be abbreviated as A1.

[0390] Novolac (approximately 500 Mw) is abbreviated as A2.

[0391] Novolac (approximately Mw 1,000) will be abbreviated as A3.

[0392] Novolac (approximately 10,000 Mw) will be abbreviated as A4.

[0393] Novolac (approximately 100,000 Mw) will be abbreviated as A5.

[0394] Novolac (approximately 500,000 Mw) will be abbreviated as A6.

[0395] Phenol Novolac (Mw approximately 5,000) is abbreviated as A7.

[0396] Polyhydroxystyrene (Mw approximately 5,000) is abbreviated as A8.

[0397] Polybutyl acrylate (Mw approximately 60,000, Sigma-Aldrich Co. LLC.) formed from the structure shown in chemical formula 19 below will be abbreviated as A9.

[0398] [Chemical Formula 19]

[0399]

[0400] Polycarbonate (Mw approximately 5,000) is abbreviated as A10.

[0401] 4,4'-Dihydroxytetraphenylmethane (Mw352) is abbreviated as A11.

[0402] Novolac (approximately 5,000 Mw) will be abbreviated as A12.

[0403] Polyfluoroalkyl acid (TAR-015, DAIKIN INDUSTRIES, LTD.) is abbreviated as A13.

[0404] KF-351A (a Si-containing polyether modified polymer, Shin-Etsu Silicone) is abbreviated as A14.

[0405] Polyvinylimidazolium (Mw approximately 5,000) is abbreviated as A15.

[0406] Polyallylamine (Mw approximately 5,000) is abbreviated as A16.

[0407] 2,2-bis(4-hydroxyphenyl)propane is abbreviated as B1.

[0408] 1,1,2,2-Tetra(4-hydroxyphenyl)ethane is abbreviated as B2.

[0409] 1,3-Cyclohexanediol is abbreviated as B3.

[0410] 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol is abbreviated as B4.

[0411] 2,2'-Methylenebis(4-methylphenol) is abbreviated as B5.

[0412] 4,4'-dihydroxybiphenyl is abbreviated as B6.

[0413] 2,6-Naphthalenediol is abbreviated as B7.

[0414] 2,5-Dimethyl-3-hexyn-2,5-diol is abbreviated as B8.

[0415] 3,6-Dimethyl-4-octyne-3,6-diol is abbreviated as B9.

[0416] 2,5-Di-tert-butylhydroquinone is abbreviated as B10.

[0417] Polyacrylic acid (Mw approximately 1,000) is abbreviated as B11.

[0418] The maleic acid-acrylic acid copolymer (Mw approximately 3,000) formed by the structure shown in the following chemical formula 20 is abbreviated as B12.

[0419] [Chemical Formula 20]

[0420]

[0421] Novolac (approximately 15,000 Mw) is abbreviated as B13.

[0422] Comparative Preparation Example 1 of Comparative Washing Solution 1

[0423] Weigh 5g of A12 and add it to 95g of IPA ((C) solvent). Otherwise, perform the same preparation as in Preparation Example 1 to obtain Comparative Wash Solution 1. It is recorded in Table 4.

[0424] Comparative Preparation Example 2 of Washing Solution 2

[0425] Weigh 5g of B4 and add it to 95g of IPA ((C) solvent). Otherwise, perform the same preparation as in Preparation Example 1 to obtain Comparative Wash Solution 2. The results are shown in Table 4.

[0426] Preparation Examples 2-33 of Washing Solutions 2-33, and Comparative Preparation Examples 3-7 of Comparative Washing Solutions 3-7

[0427] By changing (A) the second component, (B) the first component, and (C) the solvent and concentration to those listed in Tables 1 to 4, and otherwise operating in the same manner as in Preparation Example 1, washing solutions 2 to 33 and comparative washing solutions 3 to 7 were prepared. These are listed in Tables 1 to 4.

[0428] Evaluation of particle residue in detergents 1-33 and 1-7. The evaluation substrate is prepared as described in the preparation of the evaluation substrate above.

[0429] Using a Coater·Developer RF3 (SOKUDO Co., Ltd.), 10cc of each treatment solution was dropped onto each evaluation substrate, and the substrate was rotated at 1,500 rpm for 60 seconds to coat and dry. While rotating the substrate at 100 rpm, 5.0% ammonia solution was dropped onto it for 10 seconds to cover the entire substrate with 5.0% ammonia solution, and this state was maintained for 20 seconds. The substrate was then rotated at 1,500 rpm to peel off the film and allow the substrate to dry.

[0430] The particle residue levels of these substrates were compared. Bright-field defect inspection equipment (UVision 4, AMAT) was used for the evaluation of patterned substrates, while dark-field defect inspection equipment (LS-9110, Hitachi High-Technologies) was used for the evaluation of bare substrates.

[0431] The coating condition and film removal status were verified, and the number of residual particles was counted. The evaluation was conducted according to the following criteria. The evaluation results are recorded in Tables 1 to 4.

[0432] AA: ≤10

[0433] A: >10, ≤100

[0434] B: >100, ≤1,000

[0435] C: >1000

[0436] D: The membrane was not coated evenly, or the membrane was not removed.

[0437] The comparison wash solutions 1-7 do not contain multiple components with different solubilities. It was confirmed that the substrates washed with wash solutions 1-33 had less particle residue compared to the comparison wash solutions 1-7.

[0438] In this specification, unless otherwise specified, the singular form includes the plural form, and "1 (kind)" or "the (described)" means "at least 1 (kind)". Unless otherwise specified, elements of a concept may be presented in multiple ways, and where the quantity is stated (e.g., mass % or mole %), the quantity refers to the sum of the multiple described.

[0439] "and / or" includes all combinations of elements, as well as uses made in the form of individual elements.

[0440] In this specification, when “~” or “-” is used to indicate a numerical range, unless otherwise specified, they include both endpoints and the units are shared. For example, 5–25 mol% means more than 5 mol% and less than 25 mol%.

[0441] Although embodiments of the present invention have been described in detail, they are merely specific examples used to illustrate the technical content of the present invention. The present invention should not be interpreted as limited to these specific examples, and the scope of the present invention is not limited to the appended claims.

Claims

1. A substrate processing method, comprising: In the processing liquid supply process, processing liquid is supplied to the patterned surface of a substrate having a patterned surface with uneven surfaces; The process of forming a treatment film involves solidifying or hardening the treatment liquid that has been supplied to the patterned surface to form a treatment film that retains the object to be removed on the patterned surface. In the removal process, a stripping liquid is supplied to the patterned surface to peel the treatment film and the object to be removed from the patterned surface together, and the treatment film is removed from the substrate while maintaining the object to be removed by the treatment film. and In the substrate rotation process, the substrate is held horizontally and rotated about a vertical axis passing through the center of the substrate. The processing film forming process includes the following steps: forming the processing film in a recess of the patterned surface, wherein the surface of the processing film is located closer to the bottom side of the recess than the top of the protrusion adjacent to the recess. The substrate rotation process includes: a first rotation process in which, during the period from the start of supplying the processing liquid to the patterned surface to the formation of the processing film, the substrate is rotated at a first speed, thereby causing the processing liquid to enter the recess of the patterned surface; Following the first rotation step, the rotation of the substrate is accelerated to a second speed, which is faster than the first speed, so that a semi-solid film is formed from the processing liquid on the substrate. It also includes a heating process, in which the semi-solid film is heated after it has been formed until the processed film is formed.

2. The substrate processing method as described in claim 1, wherein, In the first rotation process, the processing liquid enters the recesses of the patterned surface due to its own weight. With the processing liquid entering the bottom of the recess of the patterned surface due to its own weight, the processing liquid is removed from the patterned surface of the substrate in the second rotation step, thereby forming the thin-film processing film in the processing film forming step.

3. The substrate processing method as described in claim 1 or 2, wherein, The processing film forming process includes forming the processing film in such a way that the thickness of the processing film is thinner than the height of the unevenness of the patterned surface in the thickness direction of the substrate.

4. The substrate processing method as described in claim 1 or 2, wherein, The process of forming the treatment membrane includes the process of forming the treatment membrane by covering the object to be removed with the treatment membrane.

5. The substrate processing method as described in claim 1 or 2, wherein, The process of forming the treatment film includes a process of forming the treatment film in such a way that the adhesion force between the treatment film and the object to be removed is greater than the adhesion force between the object to be removed and the patterned surface.

6. The substrate processing method as described in claim 1 or 2, wherein, The removal process includes a through-hole forming process, in which the stripping solution is used to partially dissolve the treatment membrane to form through-holes on the treatment membrane.

7. The substrate processing method as described in claim 6, wherein, The removal process includes a stripping liquid entry process, in which the stripping liquid enters between the treatment film and the patterned surface through the through hole.

8. The substrate processing method as described in claim 1 or 2, wherein, The heating process includes a heat medium supply process that supplies heat medium to the lower surface of the substrate while rotating the substrate. The rotational speed of the substrate in the heat medium supply process is lower than the rotational speed of the substrate in the second rotation process.

9. The substrate processing method as described in claim 1 or 2, wherein, The treatment solution has a solute and a solvent for dissolving the solute, the solute having a first component and a second component whose solubility in the stripping solution is lower than that of the first component. The process of forming the treatment membrane includes the process of forming the treatment membrane having a first solid formed from the first component and a second solid formed from the second component.

10. The substrate processing method as described in claim 9, wherein, 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 thereof.

11. The substrate processing method as described in claim 9, wherein, The first component is a crack-promoting component. The crack-promoting component comprises hydrocarbons, and hydroxyl and / or carbonyl groups.

12. The substrate processing method as described in claim 9, wherein, The first component is represented by at least one of the following formulas (B-1), (B-2) and (B-3); (B-1) is a compound comprising 1 to 6 chemical formulas 1 as structural units, wherein each of the structural units is connected by a linking group L1. [Chemical Formula 1] Here, L1 is selected from single bonds and C. 1～6 At least one of the alkylene groups, Cy1 being C 5～30 The hydrocarbon rings, where R1 is independently C1. 1～5 alkyl, n b1 n is 1, 2, or 3. b1’ It can be 0, 1, 2, 3, or 4; (B-2) is a compound represented by chemical formula 2. [Chemical Formula 2] Here, R 21 R 22 R 23 and R 24 Each is independently hydrogen or C 1～5 alkyl, L 21 and L 22 Each independently is C 1～20 alkylene, C 1～20 Cycloalkylene, C 2～4 imidene group, C 2～4 The ethynyl group, or C 6～20 arylene groups, these groups can be C 1～5 Alkyl or hydroxyl substitution, n b2 It can be 0, 1, or 2; (B-3) is a polymer containing structural units represented by chemical formula 3 and having a weight-average molecular weight (Mw) of 500 to 10,000. [Chemical Formula 3] R 25 It can be -H, -CH3, or -COOH.

13. The substrate processing method as described in claim 9, wherein, The solubility of the second component in 5.0% by mass ammonia water is less than 100 ppm, while the solubility of the first component in 5.0% by mass ammonia water is greater than 100 ppm.

14. The substrate processing method as described in claim 9, wherein, The mass of the second component is 0.1 to 50% of the total mass of the treatment liquid.

15. The substrate processing method as described in claim 9, wherein, The weight-average molecular weight (Mw) of the second component is 150 to 500,000.

16. A substrate processing apparatus, comprising: A processing liquid supply unit supplies processing liquid to the patterned surface of a substrate having a patterned surface with uneven surfaces; A solid forming unit that solidifies or hardens the treatment liquid; A stripping fluid supply unit supplies stripping fluid to the patterned surface; A substrate holding unit that holds the substrate horizontally; A substrate rotation unit that rotates the substrate about a vertical axis passing through the center of the substrate; A substrate heating unit, wherein the substrate heating unit heats the substrate; and The controller controls the processing liquid supply unit, the solid formation unit, the stripping liquid supply unit, the substrate holding unit, the substrate rotation unit, and the substrate heating unit. The controller is programmed in the following manner: The following steps are performed: a processing liquid supply step, in which the processing liquid is supplied from the processing liquid supply unit to the patterned surface of the substrate held by the substrate holding unit; a processing film formation step, in which the processing liquid supplied to the patterned surface is solidified or hardened in the solid forming unit to form a processing film that retains the object to be removed on the patterned surface; and a removal step, in which a stripping liquid is supplied from the stripping liquid supply unit to the patterned surface, thereby stripping the processing film and the object to be removed together from the patterned surface, and removing the processing film from the substrate while maintaining the object to be removed in the state held by the processing film. The controller is programmed in the following manner: during the processing film formation process, the processing film is formed in a position where the surface of the processing film is located closer to the bottom side of the recess than the top of the protrusion adjacent to the recess. The controller is programmed in the following manner: The following steps are performed: a first rotation step, in which, during the period from the start of supplying the processing liquid to the patterned surface to the formation of the processing film, the substrate is rotated at a first speed by the substrate rotation unit, thereby causing the processing liquid to enter the recesses of the patterned surface; and a second rotation step, after the first rotation step, in which the rotation of the substrate is accelerated by the substrate rotation unit, causing the substrate to rotate at a second speed faster than the first speed, so that a semi-solid film is formed from the processing liquid on the substrate. The controller is programmed in the following manner: The heating process is performed after the semi-solid film is formed. The semi-solid film is then heated through the substrate by the substrate heating unit until the processed film is formed.

17. The substrate processing apparatus of claim 16, wherein, In the first rotation process, the processing liquid enters the recesses of the patterned surface due to its own weight. With the processing liquid entering the bottom of the recess of the patterned surface due to its own weight, the processing liquid is removed from the patterned surface of the substrate in the second rotation step, thereby forming the thin-film processing film in the processing film forming step.

18. The substrate processing apparatus of claim 16 or 17, wherein, The controller is programmed to form the processing film in a manner in which the thickness of the processing film is thinner than the height of the unevenness of the patterned surface in the thickness direction of the substrate.

19. The substrate processing apparatus of claim 16 or 17, wherein, The controller is programmed to form the treatment membrane in such a way that the treatment membrane covers the object to be removed during the treatment membrane formation process.

20. The substrate processing apparatus of claim 16 or 17, wherein, The controller is programmed in such a way that, during the processing film formation process, the processing film is formed such that the adhesion force between the processing film and the object to be removed is greater than the adhesion force between the object to be removed and the patterned surface.

21. The substrate processing apparatus of claim 16 or 17, wherein, The controller is programmed in the following manner: In the removal process, a through-hole forming process is performed, in which the stripping liquid is used to partially dissolve the treatment membrane to form through-holes on the treatment membrane.

22. The substrate processing apparatus of claim 21, wherein, The controller is programmed in the following manner: In the removal process, a stripping liquid entry process is performed, in which the stripping liquid enters between the treatment film and the patterned surface through the through hole.

23. The substrate processing apparatus as claimed in claim 16 or 17, wherein, The substrate heating unit includes a heat medium supply unit that supplies heat medium to the lower surface of the substrate to heat the substrate. The controller is programmed to perform a heat medium supply process, wherein, during the heating process, the substrate is rotated by the substrate rotation unit while a heat medium is supplied from the heat medium supply unit to the lower surface of the substrate. The rotational speed of the substrate in the heat medium supply process is lower than the rotational speed of the substrate in the second rotation process.

24. The substrate processing apparatus of claim 16 or 17, wherein, The treatment liquid has a first component, a second component whose solubility in the stripping liquid is lower than that of the first component, and a solvent for dissolving the first component and the second component. The controller is programmed to perform the process of forming the processed membrane having a first solid formed from the first component and a second solid formed from the second component in the membrane forming process.

25. The substrate processing apparatus of claim 24, wherein, 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 thereof.

26. The substrate processing apparatus of claim 24, wherein, The first component is a crack-promoting component. The crack-promoting component comprises hydrocarbons, and hydroxyl and / or carbonyl groups.

27. The substrate processing apparatus of claim 24, wherein, The first component is represented by at least one of the following formulas (B-1), (B-2) and (B-3); (B-1) is a compound comprising 1 to 6 chemical formulas 4 as structural units, wherein each of the structural units is linked by a linking group L1. [Chemical Formula 4] Here, L1 is selected from single bonds and C. 1～6 At least one of the alkylene groups, Cy1 being C 5～30 The hydrocarbon rings, where R1 is independently C1. 1～5 alkyl, n b1 n is 1, 2, or 3. b1’ It can be 0, 1, 2, 3, or 4; (B-2) is a compound represented by chemical formula 5. [Chemical Formula 5] Here, R 21 R 22 R 23 and R 24 Each is independently hydrogen or C 1～5 alkyl, L 21 and L 22 Each independently is C 1～20 alkylene, C 1～20 Cycloalkylene, C 2～4 imidene group, C 2～4 The ethynyl group, or C 6～20 arylene groups, these groups can be C 1～5 Alkyl or hydroxyl substitution, n b2 It can be 0, 1, or 2; (B-3) is a polymer containing structural units represented by chemical formula 6 and having a weight-average molecular weight (Mw) of 500 to 10,000. [Chemical Formula 6] R 25 It can be -H, -CH3, or -COOH.

28. The substrate processing apparatus of claim 24, wherein, The solubility of the second component in 5.0% by mass ammonia water is less than 100 ppm, while the solubility of the first component in 5.0% by mass ammonia water is greater than 100 ppm.

29. The substrate processing apparatus of claim 24, wherein, The mass of the second component is 0.1 to 50% of the total mass of the treatment liquid.

30. The substrate processing apparatus of claim 24, wherein, The weight-average molecular weight (Mw) of the second component is 150 to 500,000.

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