Substrate processing liquid, substrate processing method, and substrate processing apparatus

Abstract

The present application provides a substrate processing liquid, a substrate processing method, and a substrate processing apparatus, which have excellent drying properties and can remove liquid attached to the surface of a substrate well. In the present application, the substrate processing liquid includes a sublimable substance, a solvent that dissolves the sublimable substance, and an additive that disperses particles of the sublimable substance exceeding the solubility in the solution obtained by dissolving the sublimable substance in the solvent. Therefore, the particles of the sublimable substance exceeding the solubility are uniformly dispersed and dissolved in the solvent in the substrate processing liquid. As a result, the sublimable substance supplied to the pattern formation surface of the substrate is more than in the prior art, and there are a large amount of sublimable substances (solid phase) in the inside of the pattern. As a result, the residual solvent between patterns can be effectively suppressed, and sublimation drying can be performed in a state in which the pattern is firmly held by the sublimable substance (solid phase).

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing liquid used when removing a liquid adhering to a substrate using a sublimation phenomenon of a sublimation substance, a substrate processing method for removing the liquid from the substrate using the substrate processing liquid, and a substrate processing apparatus. The substrate includes a semiconductor wafer, a substrate for a liquid crystal display device, a substrate for an FPD (Flat Panel Display) such as an organic EL (electroluminescence) display device, a substrate for an optical disc, a substrate for a magnetic disc, a substrate for an optical magnetic disc, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and the like.

[0002] The disclosures of the specification, drawings, and claims of the Japanese application shown below are hereby incorporated by reference in their entirety into the present specification:

[0003] Japanese Patent Application No. 2022-27520 (filed on February 25, 2022). BACKGROUND

[0004] In a manufacturing process of electronic components such as semiconductor devices and liquid crystal display devices, a process of repeatedly performing a treatment such as film formation and etching on a surface of a substrate to form a pattern is included. In addition, after the pattern formation, a cleaning treatment using a chemical liquid, a rinsing treatment using a rinsing liquid, and a drying treatment, and the like are sequentially performed, but as the pattern is miniaturized, the importance of the drying treatment becomes particularly high. That is, a technology of suppressing or preventing pattern collapse from occurring in the drying treatment becomes important. Therefore, a substrate processing technology of sublimation drying a substrate using a substrate processing liquid in which a sublimation substance such as camphor, cyclohexanone oxime, or the like is dissolved in a solvent such as IPA (isopropyl alcohol) or the like has been proposed (Japanese Patent Application Publication No. 2021-9988, and the like). SUMMARY

[0005] PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] In the above-described related art, in order to remove DIW (deionized water) adhering to a surface of a substrate after a rinsing treatment, the following process is performed. DIW is replaced with IPA by supplying IPA to the surface of the substrate. Then, after spin coating the above-described substrate processing liquid on the surface of the substrate, the solvent (IPA) of the substrate processing liquid is evaporated. Thereby, a solidification film of the sublimation substance is formed on the surface of the substrate. Finally, the solidification film is sublimated to be removed from the surface of the substrate.

[0007] Thus, in the conventional substrate treatment liquid, since a solution in which a sublimation substance is dissolved with a solvent is used, the concentration of the sublimation substance in the solution is small, and sometimes the sublimation substance does not sufficiently enter the gaps of the pattern. In this case, the solidification film is not formed in the gaps of the pattern, and a problem that the pattern is not held can occur. Also, sometimes the solidification film is formed on the top layer of the substrate surface, and the solvent remains in the solidification film. For these reasons, sometimes the collapse of the pattern cannot be suppressed.

[0008] The present application has been achieved in view of the above-described problems, and an object thereof is to provide a substrate treatment liquid, a substrate treatment method, and a substrate treatment apparatus, which have excellent drying performance and can well remove a liquid adhering to a substrate surface.

[0009] Method for solving the problems

[0010] A first aspect of the present application is a substrate treatment liquid for removing a liquid on a substrate having a pattern formation surface, characterized by comprising a sublimation substance, a solvent for dissolving the sublimation substance, and an additive, the additive being added to a solution in which the sublimation substance is dissolved with the solvent, so that particles of the sublimation substance exceeding the solubility are dispersed in the solution.

[0011] Also, a second aspect of the present application is a substrate treatment method characterized by comprising: a treatment liquid preparation step of preparing the substrate treatment liquid; a liquid film formation step of supplying the substrate treatment liquid prepared in the treatment liquid preparation step to a substrate surface on which a pattern is formed, to form a liquid film of the substrate treatment liquid on the substrate surface; a solidification film formation step of solidifying the liquid film of the substrate treatment liquid to form a solidification film of the sublimation substance; and a sublimation step of sublimating the solidification film to remove it from the substrate surface.

[0012] Also, a third aspect of the present application is a substrate treatment apparatus characterized by comprising: a storage section for storing the substrate treatment liquid; and a treatment liquid supply section for supplying the substrate treatment liquid stored in the storage section to a substrate surface on which a pattern is formed.

[0013] In the present application thus configured, the particles of the sublimation substance exceeding the solubility are uniformly dispersed and dissolved in the solvent in the substrate treatment liquid. Therefore, the sublimation substance supplied to the pattern formation surface of the substrate is more than in the prior art. Also, since the particles of the sublimation substance become a metastable state, if the substrate treatment liquid is supplied to the pattern formation surface of the substrate, enters the gaps between the patterns, and makes the flow diffusion small, the sublimation substance particles are recrystallized in the gaps between the patterns. Therefore, a large amount of the sublimation substance (solid phase) exists in the inside of the pattern. Thus, the solvent remaining in the gaps between the patterns can be effectively suppressed, and sublimation drying can be performed in a state in which the pattern is firmly held by the sublimation substance (solid phase).

[0014] Effects of the Invention

[0015] As described above, sublimation drying can be performed in a state where the solvent remaining between the patterns is inhibited, and liquid adhering to the surface of the substrate can be removed with excellent drying performance.

[0016] The plurality of components possessed by each aspect of the present application are not all necessary, and in order to solve part or all of the above problems or to achieve part or all of the effects described in this specification, part of the plurality of components can be changed, deleted, exchanged with new other components, or part of the limited content can be deleted. In addition, in order to solve part or all of the above problems or to achieve part or all of the effects described in this specification, part or all of the technical features included in one aspect of the present application can be combined with part or all of the technical features included in other aspects of the present application, as an independent aspect of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is a graph showing an increase in the concentration of a sublimation substance in a substrate processing liquid caused by the addition of an aid.

[0018] Figure 2 is a plan view showing the schematic configuration of a substrate processing system of the first embodiment of the substrate processing apparatus according to the present application.

[0019] Figure 3 is a side view of the substrate processing system shown in Figure 2 .

[0020] Figure 4 is a partial cross-sectional view showing the configuration of the first embodiment of the substrate processing apparatus according to the present application.

[0021] Figure 5 is a block diagram showing the electrical configuration of a control section that controls the substrate processing apparatus.

[0022] Figure 6 is a view showing the configuration of a processing liquid supply section.

[0023] Figure 7 is a view showing the contents of substrate processing performed by the substrate processing apparatus of Figure 2 .

[0024] Figure 8 is a flowchart showing the operation of the refining apparatus shown in Figure 6 .

[0025] Figure 9A is a view schematically showing a first operation example of the refining apparatus shown in Figure 6 .

[0026] Figure 9B is a view schematically showing Figure 6 a second operation example of the refining device shown in FIG. 2.

[0027] Figure 9C is a view schematically showing Figure 6 a third operation example of the refining device shown in FIG. 2.

[0028] Figure 9D is a view schematically showing Figure 6 a fourth operation example of the refining device shown in FIG. 2.

[0029] Figure 9E is a view schematically showing Figure 6 a fifth operation example of the refining device shown in FIG. 2.

[0030] Figure 10 is a view showing a configuration of a substrate processing system equipped with the substrate processing device of the second embodiment of the present application.

[0031] Symbol explanation

[0032] 1... substrate processing device, 4... control section, 53... nozzle, 64... processing liquid supply unit, 230... sublimation agent storage tank, 400... processing liquid supply section, 401... storage tank (storage section), 402, 512, 522, 523... ultrasonic wave application section, 500... refining device, 510, 520... ultrasonic wave tank, L... substrate processing liquid, LF... liquid film, PT... pattern, SF... solidified film, W... substrate, Wf... (front surface of) substrate. DETAILED DESCRIPTION

[0033] <Substrate processing liquid>

[0034] The substrate processing liquid of the embodiment of the present application will be described below.

[0035] In the present specification, "substrate" refers to various substrates such as a semiconductor substrate, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for a FED (Field Emission Display), a substrate for an optical disc, a substrate for a magnetic disc, a substrate for an optical magnetic disc, and the like. In addition, in the present specification, "pattern formation surface" refers to a surface on which a concavo-convex pattern is formed in an arbitrary region in a substrate, regardless of whether it is a planar surface, a curved surface, or a concavo-convex surface. Furthermore, in the present specification, "sublimation property" refers to the property of a monomer, a compound, or a mixture to change phase from a solid to a gas or from a gas to a solid without passing through a liquid, and "sublimation substance" refers to a substance having such a sublimation property.

[0036] The substrate treatment liquid of the present application contains a sublimation substance such as camphor or cyclohexanone oxime, a solvent such as IPA that dissolves the sublimation substance, and an additive that is added to a solution of the sublimation substance dissolved in the solvent to disperse the sublimation substance exceeding the solubility in the solution. Thus, in the present embodiment, by adding the additive to a substrate treatment liquid used in the related art (hereinafter referred to as "conventional substrate treatment liquid"), the concentration of the sublimation substance particles uniformly dispersed in the substrate treatment liquid is higher than the saturation concentration of the sublimation substance with respect to the conventional substrate treatment liquid, and the sublimation substance particles are uniformly dispersed in a so-called metastable state. That is, the substrate treatment liquid of the present embodiment is a supersaturated solution of the sublimation substance. For example, in the case where cyclohexanone oxime is used as the sublimation substance, IPA can be used as the solvent, and ammonia water can be used as the additive. Hereinafter, the substrate treatment liquid in which cyclohexanone oxime (sublimation substance), IPA (solvent), and ammonia water (additive) are mixed and refined will be described. Figure 1 A substrate treatment liquid in which cyclohexanone oxime (sublimation substance), IPA (solvent), and ammonia water (additive) are mixed and refined will be described.

[0037] Here, before the substrate treatment liquid is described, the solubility of cyclohexanone oxime in IPA will be described. A substrate treatment liquid obtained by dissolving cyclohexanone oxime in IPA is described in Patent Document 2. More specifically, sublimation drying using a substrate treatment liquid containing cyclohexanone oxime at a content of 0.1 vol% (0.13 wt%) to 10 vol% (12.97 wt%) is exemplified. These conventional substrate treatment liquids have good solubility. The "solubility" means that, as described in Patent Document 2, 10 g or more of cyclohexanone oxime is dissolved with respect to 100 g of the solvent at 23°C, for example. In addition, "room temperature" means a temperature range of 5°C to 35°C.

[0038] However, the solubility of cyclohexanone oxime, that is, the limit amount of cyclohexanone oxime dissolved in a certain amount of IPA, is not explicitly described. Therefore, the present inventors put 4 g of cyclohexanone oxime into transparent glass containers each storing a different amount of IPA, stirred until mixed well, and then left each of the transparent glass containers to confirm the precipitation. As a result, it was confirmed that 8.3 ml of IPA is required to dissolve 4 g of cyclohexanone oxime in a saturated state. That is, it was confirmed from the above experiment that the saturation concentration of cyclohexanone oxime in the substrate treatment liquid is about 38 wt%.

[0039] In a solution in which cyclohexanone oxime is dissolved only up to the limit concentration, i.e., a saturated solution, the dissolution equilibrium is established. That is, the dissolution reaction of cyclohexanone oxime (solid phase) and the crystallization reaction of the cyclohexanone oxime particles dispersed in the solution are apparently stopped, but actually the dissolution and recrystallization proceed at the same speed. Therefore, if an aid (crystallization inhibitor) that inhibits crystallization is added to the solution, the speed of recrystallization becomes small. Therefore, the present inventors investigated a solution in which the dissolution equilibrium is destroyed, i.e., a supersaturated solution of cyclohexanone oxime in which the concentration of cyclohexanone oxime particles is higher than the above-mentioned saturated concentration, in a quasi-stable state.

[0040] In addition, by adjusting the pH of the above-mentioned solution, the cyclohexanone oxime particles are given a negative Zeta potential, so that the repulsive force between the cyclohexanone oxime particles becomes large. As a result, crystallization is inhibited. Based on such investigations, the present inventors selected aqueous ammonia as a pH adjuster that gives the cyclohexanone oxime particles a negative Zeta potential, i.e., an example of the "aid" of the present application. Also, as shown in FIG. 1, it was confirmed that by using aqueous ammonia as the aid, the concentration of cyclohexanone oxime particles in the substrate treatment liquid becomes higher than the saturated concentration, and becomes in a quasi-stable state. Note that, as the aid, aqueous ammonia is not limited, and all pH adjusters that give the cyclohexanone oxime particles a negative Zeta potential can be used. Figure 1

[0041] Figure 1 This figure shows the increase in the concentration of the sublimation substance in the substrate treatment liquid caused by the addition of the aid. In this figure, "oxime" indicates the weight of cyclohexanone oxime, which is an example of the "sublimation substance" of the present application, "IPA" indicates the amount of IPA, which is an example of the "solvent" of the present application, and "NH4OH" indicates the amount of addition of aqueous ammonia, which is an example of the "aid" of the present application. These cyclohexanone oxime, IPA (and aqueous ammonia) are mixed by stirring in a transparent glass container GC, and a substrate treatment liquid L is produced. Then, the transparent glass container GC is left to stand, and the dissolution state of the cyclohexanone oxime is schematically shown. Note that, in this figure, "wt%" indicates the weight % of cyclohexanone oxime in the substrate treatment liquid. In addition, the hatched solid OX in the "dissolution state" indicates cyclohexanone oxime (solid phase).

[0042] ​In this case, 2 g of the solid OX of cyclohexanone oxime was dissolved in 2 ml of IPA to prepare a solution. In this solution, as shown in the column (a) of the figure, the cyclohexanone oxime was 55.9 wt%, which exceeded the saturated concentration (38 wt%). Therefore, a large amount of the solid OX of cyclohexanone oxime was present in the transparent glass container GC. When ammonia water was added to the solution of the same composition as the solution, as shown in the columns (b) to (d) of the figure, the residual amount of the solid OX of cyclohexanone oxime became smaller as the added amount of ammonia water increased, and when the added amount was 0.3 ml, the 2 g of the solid OX of cyclohexanone oxime was completely dissolved. The substrate processing liquid L of 52.06 wt% of cyclohexanone oxime was generated. This means that the cyclohexanone oxime particles were uniformly dispersed in the substrate processing liquid L at a concentration of about 4 to 400 times the concentration of the substrate processing liquid (0.13 wt% of cyclohexanone oxime to 12.97 wt% of cyclohexanone oxime) described in Patent Document 2. Thus, the substrate processing liquid L containing a high concentration of cyclohexanone oxime particles was obtained. Therefore, as described later, after the substrate processing liquid L was spin-coated on the pattern formation surface of the substrate, the solvent (IPA) of the substrate processing liquid was evaporated. Moreover, the substrate processing liquid of the present application is a supersaturated solution of cyclohexanone oxime, and is in a so-called metastable state, and therefore the recrystallization of the cyclohexanone oxime particles starts immediately after the spin coating. By these recrystallization and solvent evaporation, more cyclohexanone oxime (solid phase) enters the gaps of the pattern than in the case of using the conventional substrate processing liquid. As a result, the drying performance is excellent, and the liquid adhering to the surface of the substrate can be removed well.

[0043] Note that, in the present embodiment, cyclohexanone oxime is used as the sublimation substance, but the same applies to the case where another sublimation substance for sublimation drying, such as camphor or the like, is used. In addition, although IPA is used as the solvent, as long as it has a function of dissolving the above-mentioned sublimation substance, it can be, for example, at least one selected from the group consisting of an alcohol, a ketone, an ether, a cycloalkane, and water, as described in Japanese Patent Application Publication No. 2021-9988. In addition, although ammonia water is used as the auxiliary agent, in addition to this, a crystallization inhibitor having a function of suppressing the recrystallization of the particles of the sublimation substance dissolved in the solvent by adjusting the pH of the solution in which the sublimation substance is dissolved with the solvent can be used.

[0044]

[0045] Next, a substrate processing system of a substrate processing apparatus equipped with the above-mentioned substrate processing liquid (= sublimation substance + solvent + auxiliary agent) for processing a substrate having a pattern formation surface will be described.

[0046] Figure 2 is a plan view showing the schematic configuration of the substrate processing system equipped with the substrate processing apparatus of the first embodiment of the present application. In addition, Figure 3 is​Figure 2 The accompanying drawings are side views of the substrate processing system shown. These drawings do not represent the appearance of the device, but are schematic diagrams illustrating its internal structure in a way that is easily understood by excluding the outer wall panels and other components of the substrate processing system 100. This substrate processing system 100, for example, is installed in a cleanroom and is a monolithic device that processes substrates W one by one, where a circuit pattern (or the equivalent of the aforementioned "pattern") is formed on only one main surface. The first embodiment of the substrate processing method of the present invention is then performed in the substrate processing system 100. In this specification, the pattern-forming surface (one main surface) on which the pattern is formed is referred to as the "front side Wf," and the other main surface on its opposite side without a pattern is referred to as the "back side Wb." Furthermore, the surface facing downwards is referred to as the "lower surface," and the surface facing upwards is referred to as the "upper surface." Hereinafter, a substrate processing system used in the processing of semiconductor wafers will be used as an example, and the description will be based on the accompanying drawings, but the same principle applies to the processing of various substrates illustrated above.

[0047] like Figure 2 As shown, the substrate processing system 100 includes a substrate processing unit 110 for processing substrates W and a sorting unit 120 coupled to the substrate processing unit 110. The sorting unit 120 includes a container holding unit 121 and a sorting robot 122. The container holding unit 121 can hold multiple containers C (such as FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), OC (Open Cassette), etc.) for accommodating substrates W in a sealed state. The sorting robot 122 is used to access the containers C held in the container holding unit 121, remove unprocessed substrates W from the containers C, or store processed substrates W in the containers C. Multiple substrates W are accommodated in each container C in a generally horizontal position.

[0048] The indexing robot 122 includes: a base portion 122a fixed to the device housing; a multi-joint arm 122b configured to rotate about a vertical axis relative to the base portion 122a; and a manipulator 122c mounted on the front end of the multi-joint arm 122b. The manipulator 122c is structured to place and hold the substrate W on its upper surface. Indexing robots having such a multi-joint arm and substrate holding manipulator are known, therefore detailed description is omitted.

[0049] The substrate processing section 110 has a substrate transfer robot 111 disposed at substantially the center in plan view and a plurality of substrate processing apparatuses 1 disposed so as to surround the substrate transfer robot 111. Specifically, a plurality of (eight in this example) substrate processing apparatuses 1 are disposed facing a space in which the substrate transfer robot 111 is disposed. The substrate transfer robot 111 accesses these substrate processing apparatuses 1 at random to exchange substrates W. On the other hand, each substrate processing apparatus 1 performs a prescribed process on a substrate W. In this embodiment, these substrate processing apparatuses 1 have the same function. Therefore, parallel processing of a plurality of substrates W can be performed.

[0050] <Configuration of Substrate Processing Apparatus 1>

[0051] Figure 4 is a partial sectional view showing the configuration of the first embodiment of the substrate processing apparatus of the present application. In addition, Figure 5 is a block diagram showing the electrical configuration of a control section that controls the substrate processing apparatus. Note that in this embodiment, a control section 4 is provided for each substrate processing apparatus 1, but the configuration can be such that a plurality of substrate processing apparatuses 1 are controlled by one control section. In addition, the configuration can be such that the substrate processing apparatuses 1 are controlled by a control unit (not shown) that controls the entire substrate processing system 100.

[0052] The substrate processing apparatus 1 has a chamber 2 having an internal space 21 and a rotary chuck 3 housed in the internal space 21 of the chamber 2 and holding a substrate W. As shown in Figure 2 and Figure 3 A shutter 23 is provided on the side surface of the chamber 2. The shutter 23 is connected to a shutter opening / closing mechanism 22 Figure 5 ) and is opened / closed in accordance with an opening / closing command from the control section 4. More specifically, in the substrate processing apparatus 1, when an unprocessed substrate W is carried into the chamber 2, the shutter opening / closing mechanism 22 opens the shutter 23, and the unprocessed substrate W is carried into the rotary chuck 3 in a face-up posture by a robot of the substrate transfer robot 111. That is, the substrate W is placed on the rotary chuck 3 in a state in which the front face Wf faces upward. Then, after this substrate carrying-in, when the robot of the substrate transfer robot 111 retreats from the chamber 2, the shutter opening / closing mechanism 22 closes the shutter 23. Then, in the internal space 21 of the chamber 2, as will be described later, a liquid medicine, DIW, IPA, a substrate processing liquid for sublimation drying, and nitrogen gas are supplied to the front face Wf of the substrate W, and the required substrate processing is performed in a normal temperature environment. In addition, after the substrate processing is completed, the shutter opening / closing mechanism 22 again opens the shutter 23, and the robot of the substrate transfer robot 111 carries out the processed substrate W from the rotary chuck 3. In this way, in this embodiment, the internal space 21 of the chamber 2 functions as a processing space in which the substrate processing is performed while maintaining a normal temperature environment.

[0053] The rotary chuck 3 includes a plurality of chuck pins 31 that hold the substrate W, a rotary base 32 that supports the plurality of chuck pins 31 and is formed in a disc shape along the horizontal direction, a central shaft 33 that is provided so as to be rotatable about a rotation axis C1 parallel to a face normal line extending from the surface center of the substrate W in a state of being coupled to the rotary base 32, and a substrate rotation drive mechanism 34 that rotates the central shaft 33 about the rotation axis C1 by a motor. The plurality of chuck pins 31 are provided to the peripheral portion of the upper surface of the rotary base 32. In the present embodiment, the chuck pins 31 are arranged at equal intervals in the circumferential direction. Then, in a state where the substrate W placed on the rotary chuck 3 is held by the chuck pins 31, when the motor of the substrate rotation drive mechanism 34 operates according to a rotation instruction from the control section 4, the substrate W rotates about the rotation axis C1. In addition, in a state where the substrate W is thus rotated, according to a supply instruction from the control section 4, the liquid medicine, the IPA, the DIW, the substrate processing liquid, and the nitrogen gas are sequentially supplied to the front surface Wf of the substrate W from the nozzles provided to the atmosphere blocking mechanism 5.

[0054] The atmosphere blocking mechanism 5 has a blocking plate 51, an upper rotary shaft 52 provided to the blocking plate 51 in a manner that can be integrally rotated, and a nozzle 53 that penetrates the central portion of the blocking plate 51 in the vertical direction. The blocking plate 51 is processed into a circular plate shape having a diameter substantially the same as or more than that of the substrate W. The blocking plate 51 is arranged in opposition to the upper surface of the substrate W held by the rotary chuck 3 at intervals. Therefore, the lower surface of the blocking plate 51 functions as a circular substrate opposing surface 51a that opposes the entire front surface Wf of the substrate W. In addition, a through-hole 51b that is a cylindrical shape that penetrates the blocking plate 51 in the vertical direction is formed in the central portion of the substrate opposing surface 51a.

[0055] The upper rotary shaft 52 is provided so as to be rotatable about a rotation axis (an axis coinciding with the rotation axis C1 of the substrate W) that passes through the center of the blocking plate 51 and extends vertically. The upper rotary shaft 52 has a cylindrical shape. The inner peripheral surface of the upper rotary shaft 52 is formed into a cylindrical surface with the above-described rotation axis as the center. The internal space of the upper rotary shaft 52 communicates with the through-hole 51b of the blocking plate 51. The upper rotary shaft 52 is supported by a support arm 54 that extends horizontally above the blocking plate 51 in a manner that can be relatively rotated.

[0056] The nozzle 53 is arranged above the rotary chuck 3. The nozzle 53 is supported by the support arm 54 in a state that cannot be rotated with respect to the support arm 54. In addition, the nozzle 53 can be lifted and lowered integrally with the blocking plate 51, the upper rotary shaft 52, and the support arm 54. A discharge port 53a is provided to the lower end portion of the nozzle 53 so as to oppose the central portion of the front surface Wf of the substrate W held by the rotary chuck 3.

[0057] The blocking plate 51 and a blocking plate rotation drive mechanism 55 that is configured to include an electric motor or the like areFigure 5 ) combined. The blocking plate rotation drive mechanism 55 rotates the blocking plate 51 and the upper rotation shaft 52 relative to the support arm 54 about the rotation axis line Cl in accordance with a rotation instruction from the control section 4. In addition, the support arm 54 is combined with a blocking plate lifting drive mechanism 56. The blocking plate lifting drive mechanism 56 lifts the blocking plate 51, the upper rotation shaft 52, and the nozzle 53 together with the support arm 54 in the vertical direction Z in accordance with a lifting instruction from the control section 4. More specifically, the blocking plate lifting drive mechanism 56 lifts the substrate relative surface 51a between a blocking position (position shown in the drawing) at which the upper space of the front surface Wf of the substrate W is substantially blocked from the ambient environment and a retracted position which is more retracted upward than the blocking position. Figure 4 The position shown in the drawing) and a retracted position which is more retracted upward than the blocking position.

[0058] The upper end portion of the nozzle 53 is connected to a chemical liquid supply unit 61, a rinsing liquid supply unit 62, an organic solvent supply unit 63, a processing liquid supply unit 64, and a gas supply unit 65.

[0059] The chemical liquid supply unit 61 has a chemical liquid pipe 611 connected to the nozzle 53 and a valve 612 installed to the chemical liquid pipe 611. The chemical liquid pipe 611 is connected to a supply source of a chemical liquid. In the present embodiment, the chemical liquid only needs to have a function of cleaning the front surface Wf of the substrate W, and for example, as an acidic chemical liquid, a chemical liquid containing at least one of hydrofluoric acid (HF), hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid can be used. In addition, as an alkaline chemical liquid, for example, a chemical liquid containing at least one of ammonia and hydroxyl can be used. Note that in the present embodiment, hydrofluoric acid is used as the chemical liquid. Therefore, when the valve 612 is opened in accordance with an opening / closing instruction from the control section 4, the hydrofluoric acid chemical liquid is supplied to the nozzle 53 and discharged from the discharge port 53a toward the surface central portion of the substrate W.

[0060] The rinsing liquid supply unit 62 has a rinsing liquid pipe 621 connected to the nozzle 53 and a valve 622 installed to the rinsing liquid pipe 621. The rinsing liquid pipe 621 is connected to a supply source of a rinsing liquid. In the present embodiment, DIW is used as the rinsing liquid, and when the valve 622 is opened in accordance with an opening / closing instruction from the control section 4, the DIW is supplied to the nozzle 53 and discharged from the discharge port 53a toward the surface central portion of the substrate W. Note that as the rinsing liquid, in addition to DIW, for example, any one of carbonated water, electrolytic ion water, hydrogen water, ozone water, and dilute concentration (for example, around 10 ppm to 100 ppm) hydrochloric acid water can be used.

[0061] The organic solvent supply unit 63 is a unit for supplying an organic solvent that is a low surface tension liquid having a specific gravity larger than air and a surface tension lower than water. The organic solvent supply unit 63 has an organic solvent pipe 631 connected to the nozzle 53 and a valve 632 installed to the organic solvent pipe 631. The organic solvent pipe 631 is connected to a supply source of the organic solvent. In the present embodiment, IPA is used as the organic solvent, and when the valve 632 is opened according to an opening / closing instruction from the control section 4, the IPA is supplied to the nozzle 53 and discharged from the discharge port 53a toward the surface central portion of the substrate W. Note that, as the organic solvent, in addition to IPA, for example, methanol, ethanol, acetone, EG (ethylene glycol), and HFE (hydrofluoroether) can be used. Further, as the organic solvent, not only a case where only a single component is used, but also a liquid mixed with other components can be used. For example, a mixed liquid of IPA and acetone or a mixed liquid of IPA and methanol can be used.

[0062] The treatment liquid supply unit 64 is a unit for supplying a substrate treatment liquid for sublimation drying to the front surface Wf of the substrate W, the substrate treatment liquid for sublimation drying functioning as a drying assisting liquid when the substrate W held to the spin chuck 3 is dried. The treatment liquid supply unit 64 has a treatment liquid pipe 641 connected to the nozzle 53 and a valve 642 installed to the treatment liquid pipe 641. The treatment liquid pipe 641 is connected to a treatment liquid supply section functioning as a supply source of the substrate treatment liquid for sublimation drying described above.

[0063] Figure 6 Fig. 17 is a view showing the configuration of the treatment liquid supply section. The treatment liquid supply section 400 is provided with a refining device 500 for refining the substrate treatment liquid described above and a storage tank 401 for storing the substrate treatment liquid refined by the refining device 500. Note that, on the storage tank 401, an ultrasonic wave application section 402 having a vibrator for generating ultrasonic waves is installed, and when the ultrasonic wave application section 402 is activated according to a vibration instruction from the control section 4, ultrasonic wave vibration is applied to the substrate treatment liquid stored in the storage tank 401.

[0064] The refining device 500 is a device for refining a supersaturated solution of cyclohexanone oxime having high purity as the substrate treatment liquid by removing particles in the liquid from a used substrate treatment liquid and a raw liquid of the substrate treatment liquid provided by a chemical liquid manufacturer. Here, the "used substrate treatment liquid" refers to the substrate treatment liquid recovered from the substrate W by a cup at the time of spin coating as described later. The "raw liquid of the substrate treatment liquid provided by the chemical liquid manufacturer" refers to a cyclohexanone oxime solution (for example, cyclohexanone oxime solution 3 wt%) in which cyclohexanone oxime is dissolved with IPA by the chemical liquid manufacturer.

[0065] In order to deliver the substrate treatment liquid (= sublimation substance + solvent + additive) refined by the refining device 500 to the storage tank 401, the refining device 500 is connected to the storage tank 401 through a pipe 403 in which a filter 404 is installed. Therefore, during the operation of the substrate treatment device 1, the refining device 500 is also operated in parallel, and the substrate treatment liquid for sublimation drying is refined in batches and delivered to the storage tank 401 through the pipe 403. Then, the storage tank 401 stores the refined substrate treatment liquid. Note that the configuration and refining operation of the refining device 500 and the like will be described in detail later after the substrate treatment method is explained.

[0066] The bottom of the storage tank 401 is connected to a treatment liquid pipe 641 through a pipe 405. A pump 406, a valve 407, and a filter 408 are installed on the pipe 405. Therefore, when the pump 406 is operated based on a control instruction from the control section 4 and the valve 407 is opened, the above-described substrate treatment liquid is delivered from the treatment liquid supply section 400 to the nozzle 53. As a result, during the opening of the valve 642, the substrate treatment liquid (a supersaturated solution of cyclohexanone oxime) is supplied from the nozzle 53 to the front surface Wf of the substrate W.

[0067] In addition, in the present embodiment, although the illustration of Figure 6 is omitted, an ultrasonic wave application section is provided along the supply path of the substrate treatment liquid from the storage tank 401 (the pipe 405, the treatment liquid pipe 641, and the nozzle 53). Therefore, the ultrasonic wave vibration can be continuously applied to the substrate treatment liquid until it is supplied to the substrate W, and the metastable state can be maintained, that is, the crystallization of the cyclohexanone oxime particles contained in the substrate treatment liquid can be effectively suppressed. As a result, the substrate treatment liquid in the metastable state can be reliably supplied to the front surface Wf of the substrate W. Note that the manner in which the ultrasonic wave vibration is applied to the substrate treatment liquid is arbitrary, and for example, a vibrator can be built in the nozzle 53. In addition, the vibrator can be provided to the nozzle 53 in an adjacent state.

[0068] Returning to Figure 4 The description will be continued. When the substrate treatment liquid is delivered toward the nozzle 53 as described above, the substrate treatment liquid is discharged from the discharge port 53a of the nozzle 53 toward the surface central portion of the substrate W.

[0069] The gas supply unit 65 has a gas supply pipe 651 connected to the nozzle 53 and a valve 652 that opens and closes the gas supply pipe 651. The gas supply pipe 651 is connected to a supply source of a gas. In the present embodiment, dehumidified nitrogen gas is used as the gas, and when the valve 652 is opened according to an opening and closing instruction from the control section 4, the nitrogen gas is supplied to the nozzle 53 and blown from the discharge port 53a toward the surface central portion of the substrate W. Note that, as the gas, in addition to the nitrogen gas, a non-active gas such as dehumidified argon gas can be used.

[0070] In the substrate processing apparatus 1, an exhaust tank 80 is provided to surround the rotating chuck 3. Additionally, multiple cups 81 and 82 (first cup 81 and second cup 82) are disposed between the rotating chuck 3 and the exhaust tank 80, and multiple protective covers 84 to 86 (first protective cover 84 to third protective cover 86) are provided to catch processing liquid that splashes onto the substrate W. Furthermore, protective cover lifting drive mechanisms 87 to 89 (first to third protective cover lifting drive mechanisms 87 to 89) are connected to the protective covers 84 to 86 respectively. The protective cover lifting drive mechanisms 87 to 89 independently raise and lower the protective covers 84 to 86 according to lifting commands from the control unit 4. It should be noted that... Figure 4 The illustration of the first protective cover lifting drive mechanism 87 is omitted. Furthermore, the second protective cover 85 of the three protective covers faces the peripheral end face of the substrate W during spin coating of the substrate processing liquid (liquid film formation process S6-1 described later). Therefore, the substrate processing liquid ejected from the substrate W is captured by the second protective cover 85 and recovered by the second cup 82. The recovered substrate processing liquid is then sent to the refining apparatus 500 via the recovery pipe 821 for reuse after refining.

[0071] The control unit 4 includes an arithmetic unit such as a CPU, a storage unit such as a fixed storage device and a hard disk drive, and an input / output unit. The storage unit stores the program executed by the arithmetic unit. Then, the control unit 4 controls each part of the device according to the above program, thereby using a quasi-stable substrate processing solution that dissolves cyclohexanone oxime in a supersaturated state to perform the operation. Figure 7 The substrate processing shown.

[0072] <Substrate Processing Method>

[0073] Next, refer to Figure 7 For use Figure 2 The substrate processing method of the substrate processing system 100 shown will be described. Figure 7 It means by Figure 2 This diagram illustrates the substrate processing performed by a substrate processing apparatus 1. The left side of the diagram shows a flowchart of the substrate processing performed by the substrate processing apparatus 1. The upper right, middle right, and lower right sections schematically illustrate the liquid film formation process, the curing film formation process, and the sublimation process, respectively, with a portion of the front side Wf ​​of the substrate W shown enlarged. For ease of understanding, the dimensions and quantity of each part are exaggerated or simplified as needed.

[0074] The processing target in the substrate processing system 100 is, for example, a silicon wafer on which a concave-convex pattern PT is formed on the front surface Wf as a pattern formation surface. In the present embodiment, the convex portion PT1 has a height in the range of 100 to 600 nm and a width in the range of 5 to 50 nm. In addition, the shortest distance (the shortest width of the concave portion) between two adjacent convex portions PT1 is in the range of 5 to 150 nm. The aspect ratio of the convex portion PT1, which is the value obtained by dividing the height by the width (height H / width WD), is in the range of 5 to 35.

[0075] In addition, the pattern PT can also be a pattern in which a linear pattern formed of a fine groove is repeatedly arranged. In addition, the pattern PT can also be formed by providing a plurality of fine holes (voids or pores) in a thin film. The pattern PT includes, for example, an insulating film. In addition, the pattern PT can also include a conductor film. More specifically, the pattern PT is formed of a laminated film in which a plurality of films are laminated, and can further include an insulating film and a conductor film. The pattern PT can also be a pattern composed of a single layer film. The insulating film can be a silicon oxide film, a silicon nitride film. In addition, the conductor film can be an amorphous silicon film into which an impurity for low resistance is introduced, or a metal film (for example, a TiN film). In addition, the pattern PT can be formed in the front end, or can be formed in the back end. Further, the pattern PT can be a hydrophobic film, or can be a hydrophilic film. As the hydrophilic film, for example, a TEOS film (one type of silicon oxide film) is included.

[0076] In addition, Figure 7 Each of the processes shown is performed under an atmospheric pressure environment, unless otherwise specifically indicated. Here, the atmospheric pressure environment refers to an environment of 0.7 atmospheres or more and 1.3 atmospheres or less centered on the standard atmospheric pressure (1 atmosphere, 1013 hPa). In particular, in the case where the substrate processing system 100 is disposed in a clean room that becomes a positive pressure, the environment of the front surface Wf of the substrate W is higher than 1 atmosphere.

[0077] Before the unprocessed substrate W is carried into the substrate processing apparatus 1, the control section 4 issues an instruction to each section of the apparatus, and the substrate processing apparatus 1 is set to an initial state. That is, the shutter 23 is closed by the shutter opening and closing mechanism 22 Figure 2 Figure 3 The rotary chuck 3 is positioned and stopped at a position suitable for loading of the substrate W by the substrate rotation drive mechanism 34, and the chuck pins 31 are made to be in an open state by a not-shown chuck opening and closing mechanism. The blocking plate 51 is positioned at a retracted position by the blocking plate lifting drive mechanism 56, and the blocking plate 51 is stopped from rotating by the blocking plate rotation drive mechanism 55. Each of the shields 84 to 86 is moved downward to be positioned. Also, each of the valves 612, 622, 632, 642, and 652 is closed.

[0078] ​When the unprocessed substrate W is gradually carried in by the substrate carrying robot 111, the shutter 23 is opened. In correspondence with the opening of the shutter 23, the substrate W is carried into the inner space 21 of the chamber 2 by the substrate carrying robot 111, and is handed over to the spin chuck 3 in a state where the front surface Wf is oriented upward. Then, the chuck pin 31 becomes the closed state, and the substrate W is held to the spin chuck 3 (step S1: substrate carrying-in).

[0079] After the substrate W is carried in, the substrate carrying robot 111 is retracted outside the chamber 2, and after the shutter 23 is closed again, the control section 4 controls the motor of the substrate rotation driving mechanism 34 to raise the rotation speed (number of revolutions) of the spin chuck 3 to a prescribed processing speed (in the range of about 10 to 3000 rpm, for example, 800 to 1200 rpm) and maintain it at that processing speed. In addition, the control section 4 controls the blocking plate elevation driving mechanism 56 to lower the blocking plate 51 from the retracted position to the blocking position (step S2). In addition, the control section 4 raises the first to third shields 84 to 86 to the upper position by controlling the shield elevation driving mechanisms 87 to 89, and thereby brings the first shield 84 into opposition with the peripheral end surface of the substrate W.

[0080] When the rotation of the substrate W reaches the processing speed, then the control section 4 opens the valve 612. By this, the liquid medicine (HF in this embodiment) is discharged from the discharge port 53a of the nozzle 53 and supplied to the front surface Wf of the substrate W. On the front surface Wf of the substrate W, the HF is moved toward the peripheral edge portion of the substrate W by the centrifugal force generated by the rotation of the substrate W. By this, the entire front surface Wf of the substrate W is subjected to the liquid medicine cleaning using the HF (step S3). At this time, the HF that has reached the peripheral edge portion of the substrate W is discharged from the peripheral edge portion of the substrate W toward the lateral direction of the substrate W, is blocked by the inner wall of the first shield 84, and is sent to the waste liquid treatment equipment outside the machine along the not-illustrated liquid discharge path. This liquid medicine cleaning based on the HF supply is continued for a prescribed cleaning time, and when the cleaning time elapses, the control section 4 closes the valve 612 to stop the discharge of the HF from the nozzle 53.

[0081] After the chemical liquid cleaning, a rinsing process using a rinsing liquid (DIW) is performed (step S4). In this DIW rinsing, the control section 4 opens the valve 622 while maintaining the positions of the first to third shields 84 to 86. Thus, DIW is supplied as a rinsing liquid from the discharge port 53a of the nozzle 53 to the central portion of the front face Wf of the substrate W that has undergone the chemical liquid cleaning. Then, the DIW is moved toward the peripheral edge portion of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, the HF adhering to the substrate W is washed away by the DIW. At this time, the DIW discharged from the peripheral edge portion of the substrate W is discharged from the peripheral edge portion of the substrate W to the side of the substrate W, and is sent to the waste liquid processing device outside the machine, like the HF. This DIW rinsing is continued for a predetermined rinsing time, and when the rinsing time elapses, the control section 4 closes the valve 622 to stop the discharge of the DIW from the nozzle 53.

[0082] After the DIW rinsing, a displacement process using an organic solvent (IPA in this embodiment) having a lower surface tension than the DIW is performed (step S5). In the IPA displacement, the control section 4 lowers the first and second shields 84 and 85 to the lower positions by controlling the shield lift drive mechanisms 87 and 88, thereby bringing the third shield 86 into opposition with the peripheral end face of the substrate W. Then, the control section 4 opens the valve 632. Thus, IPA as a low surface tension liquid is discharged from the discharge port 53a of the nozzle 53 to the central portion of the front face Wf of the substrate W on which the DIW is adhered. The IPA supplied to the front face Wf of the substrate W is diffused to the entire region of the front face Wf of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, the DIW (rinsing liquid) adhering to the entire front face Wf of the substrate W is displaced by the IPA. Note that the IPA moving on the front face Wf of the substrate W is discharged from the peripheral edge portion of the substrate W to the side of the substrate W, and is blocked by the inner wall of the third shield 86, and is sent to the recovery device along the recovery path not shown. This IPA displacement is continued for a predetermined displacement time, and when the displacement time elapses, the control section 4 closes the valve 632 to stop the discharge of the IPA from the nozzle 53.

[0083] After the IPA displacement, a sublimation drying process equivalent to the first embodiment of the substrate processing method of the present application is performed (step S6). This sublimation drying process includes a liquid film forming process (step S6-1) of forming a liquid film of a substrate processing liquid, a solidified film forming process (step S6-2) of solidifying the liquid film of the substrate processing liquid to form a solidified film of cyclohexanone oxime, and a sublimation process (step S6-3) of sublimating the solidified film to be removed from the front face Wf of the substrate W.

[0084] In step S6-1, the control section 4 controls the second shield lifting drive mechanism 88 to raise the second shield 85 to the upper position, thereby bringing the second shield 85 into opposition with the peripheral end surface of the substrate W. Then, the control section 4 opens the valve 642. Thus, as shown in the upper right section of Fig. 6, the substrate processing liquid (a supersaturated solution of cyclohexanone oxime) is discharged from the discharge port 53a of the nozzle 53 toward the central portion of the front surface Wf of the substrate W to which IPA is attached, and is supplied to the front surface Wf of the substrate W. The substrate processing liquid on the front surface Wf of the substrate W is diffused to the entire area of the front surface Wf of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, on the entire front surface Wf of the substrate W, the IPA attached to the front surface Wf is replaced by the substrate processing liquid, and the IPA is removed from the front surface Wf of the substrate W. Figure 7 As shown in the upper right section of Fig. 6, the substrate processing liquid (a supersaturated solution of cyclohexanone oxime) is discharged from the discharge port 53a of the nozzle 53 toward the central portion of the front surface Wf of the substrate W to which IPA is attached, and is supplied to the front surface Wf of the substrate W. The substrate processing liquid on the front surface Wf of the substrate W is diffused to the entire area of the front surface Wf of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, on the entire front surface Wf of the substrate W, the IPA attached to the front surface Wf is replaced by the substrate processing liquid, and the IPA is removed from the front surface Wf of the substrate W. Figure 7 As shown in the upper right section of Fig. 6, the substrate processing liquid (a supersaturated solution of cyclohexanone oxime) is discharged from the discharge port 53a of the nozzle 53 toward the central portion of the front surface Wf of the substrate W to which IPA is attached, and is supplied to the front surface Wf of the substrate W. The substrate processing liquid on the front surface Wf of the substrate W is diffused to the entire area of the front surface Wf of the substrate W by the centrifugal force generated by the rotation of the substrate W. Thus, on the entire front surface Wf of the substrate W, the IPA attached to the front surface Wf is replaced by the substrate processing liquid, and the IPA is removed from the front surface Wf of the substrate W.

[0085] A portion of the substrate processing liquid diffused to the entire front surface Wf of the substrate W enters the inside of the pattern PT, but is greatly different from the invention described in Patent Document 2 in the following point. That is, the concentration of the cyclohexanone oxime particles uniformly dispersed in the substrate processing liquid that has entered the inside of the pattern PT is high. More specifically, the concentration is as high as 4 to 400 times that of the invention described in Patent Document 2. Moreover, in the substrate processing liquid, the cyclohexanone oxime particles are uniformly dispersed in a state of exceeding the solubility, that is, the substrate processing liquid is in a metastable state, and thus when the flow diffusion in the inside of the pattern PT is reduced, the cyclohexanone oxime particles start to recrystallize. Moreover, in the present embodiment, the above recrystallization is further promoted by the rotation of the substrate W and the evaporation of the solvent component (that is, IPA) in the substrate processing liquid caused by the next nitrogen gas supply (step S6-2).

[0086] In addition, after the metastable state is released, the rotation of the substrate W and the supply of nitrogen gas are continued. That is, in step S6-2, the control section 4 opens the valve 652, and as shown in the middle right section of Fig. 6, the dehumidified nitrogen gas is discharged toward the front surface Wf of the substrate W that is rotating in a state covered with the liquid film LF of the substrate processing liquid. As a result, a solidification film SF of cyclohexanone oxime at a high concentration is formed in the inside of the pattern PT. Here, the timing of opening the valve 652, that is, the timing of starting the discharge of nitrogen gas, can be before the recrystallization of the cyclohexanone oxime particles starts, or after the recrystallization starts. In addition, the discharge of nitrogen gas is not essential for forming the solidification film of cyclohexanone oxime, but in order to achieve an increase in production volume, it is preferable to use the discharge of nitrogen gas in combination. Figure 7 As shown in the middle right section of Fig. 6, the dehumidified nitrogen gas is discharged toward the front surface Wf of the substrate W that is rotating in a state covered with the liquid film LF of the substrate processing liquid. As a result, a solidification film SF of cyclohexanone oxime at a high concentration is formed in the inside of the pattern PT. Here, the timing of opening the valve 652, that is, the timing of starting the discharge of nitrogen gas, can be before the recrystallization of the cyclohexanone oxime particles starts, or after the recrystallization starts. In addition, the discharge of nitrogen gas is not essential for forming the solidification film of cyclohexanone oxime, but in order to achieve an increase in production volume, it is preferable to use the discharge of nitrogen gas in combination.

[0087] Next, the control section 4 executes the sublimation process (step S6-3). The control section 4 lowers the second shield 85 to the lower position by controlling the second shield lift drive mechanism 88, thereby bringing the third shield 86 into opposition with the peripheral edge surface of the substrate W. Note that in this embodiment, the control section 4 continues the rotation speed of the substrate W from the solidification film SF forming process (step S6-2), but can accelerate to a high speed. In addition, the control section 4 controls the blocking plate rotation drive mechanism 55 to rotate the blocking plate 51 at the same speed in the same direction as the rotation of the substrate W. As the substrate W rotates, the contact speed of the solidification film SF with the atmosphere around it increases. Thus, sublimation of the solidification film SF can be promoted, and the solidification film SF can be sublimated in a short period of time. However, the rotation of the blocking plate 51 is not a necessary component of the sublimation process, but is an optional component.

[0088] In addition, in the sublimation process S6-3, the control section 4 continues to maintain the state of opening the valve 652 from the solidification film SF forming process, as shown in the lower right section of FIG. 6, and discharges the dehumidified nitrogen gas from the discharge port 53a of the nozzle 53 toward the central portion of the front surface Wf of the substrate W in the rotating state. Thus, the sublimation process can be performed while maintaining the blocking space sandwiched by the front surface Wf of the substrate W and the substrate-opposing surface 51a of the blocking plate 51 in a low-humidity state. In this sublimation process S6-3, the sublimation heat is taken away along with the sublimation of the solidification film SF, and the solidification film SF is maintained below the freezing point (melting point) of cyclohexanone oxime. Therefore, the cyclohexanone oxime, which is the sublimation substance constituting the solidification film SF, can be effectively prevented from melting. Thus, there is no liquid phase between the patterns PT on the front surface Wf of the substrate W, so the collapse problem of the patterns PT can be mitigated, and the substrate W can be dried. Figure 7 If a predetermined sublimation time elapses from the start of the sublimation drying process S6, in step S7, the control section 4 controls the motor of the substrate rotation drive mechanism 34 to stop the rotation of the spin chuck 3. In addition, the control section 4 controls the blocking plate rotation drive mechanism 55 to stop the rotation of the blocking plate 51, and controls the blocking plate lift drive mechanism 56 to raise the blocking plate 51 from the blocking position and position it in the retracted position. Furthermore, the control section 4 controls the third shield lift drive mechanism 89 to lower the third shield 86, and retracts all of the shields 86 to 88 downward from the peripheral edge surface of the substrate W.

[0089] After that, the control section 4 controls the shutter opening / closing mechanism 22 to open the shutter 23 (step S8-1), and controls the substrate lift drive mechanism 34 to lower the substrate W to the substrate exchange position (step S8-2). Then, the control section 4 controls the substrate exchange mechanism 31 to exchange the substrate W (step S8-3).

[0090] Figure 2 , Figure 3 ​After that, the substrate handling robot 111 enters the internal space of the chamber 2 and moves the processed substrate W, which has been released from the holding of the chuck pin 31, out of the chamber 2 (step S8). It should be noted that when the removal of the substrate W is completed and the substrate handling robot 111 leaves the substrate processing device 1, the control unit 4 controls the baffle opening and closing mechanism 22 to close the baffle 23.

[0091] As described above, in this embodiment, similar to the invention disclosed in Japanese Patent Application Publication No. 2021-9988, cyclohexanone oxime, one of the sublimation substances used for sublimation drying, is used to dry the substrate W. However, the cyclohexanone oxime (solid phase) present inside the pattern PT is quite different. That is, in this embodiment, a large amount of cyclohexanone oxime (solid phase) is present inside the pattern PT, which can effectively suppress the residue of solvent component (IPA). In other words, sublimation drying is performed while the pattern PT is firmly held by the cyclohexanone oxime (solid phase). Therefore, compared with the invention disclosed in Patent Document 2, the occurrence of pattern collapse can be suppressed.

[0092] Furthermore, in this embodiment, the substrate processing liquid ejected from the substrate W is recovered using the second cup 82, and the recovered substrate processing liquid is refined and reused using the refining apparatus 500. That is, the amount of expensive cyclohexanone oxime used can be suppressed, thereby reducing operating costs.

[0093] Furthermore, as explained below, the refining apparatus 500 improves the purity of cyclohexanone oxime by recrystallizing the cyclohexanone oxime particles in a quasi-stable state. Therefore, it is possible to reduce the number of liquid particles contained in the substrate processing solution, thereby further reducing the occurrence of pattern collapse.

[0094] <Refining Device>

[0095] When a substrate processing solution containing quasi-stable cyclohexanone oxime particles is placed, the cyclohexanone oxime particles exceeding their solubility will recrystallize. For example, when storing... Figure 1 When the transparent glass container GC containing the substrate processing solution shown in column (d) is left to stand at room temperature, cyclohexanone oxime precipitates out. Analysis of the precipitate using Fourier transform infrared spectroscopy and gas chromatography (with a flame ionization detector) confirmed that the precipitate was cyclohexanone oxime (solid phase) with a purity of 99.99%. That is, even with substrate processing solutions containing liquid particles, high-purity cyclohexanone oxime (solid phase) can be obtained through recrystallization. Then, by adding an auxiliary agent (NH4OH) to a solution obtained by dissolving the precipitated cyclohexanone oxime (solid phase) in a solvent (IPA), a high-purity substrate processing solution (a supersaturated solution of cyclohexanone oxime) free of liquid particles can be purified.

[0096] Therefore, in this embodiment, Figure 6The refining apparatus 500 shown is assembled into the substrate processing apparatus 1. Hereinafter, with reference to... Figure 6 After explaining the structure of the refining apparatus 500, refer to... Figure 8 , Figures 9A to 9E The operation of the refining device 500 will be explained.

[0097] like Figure 6 As shown, the refining apparatus 500 has two ultrasonic tanks 510 and 520. The ultrasonic tank 510 has a tank 511 capable of storing a substrate processing solution and an ultrasonic application unit 512 mounted on the tank 511. The ultrasonic application unit 512 is operated according to instructions from the control unit 4. If the substrate processing solution containing quasi-stable cyclohexanone oxime particles is stored in the ultrasonic tank 510, and the ultrasonic application unit 512 operates according to the operation instructions from the control unit 4, ultrasonic vibration can be applied to the substrate processing solution stored in the tank 511 to maintain a quasi-stable state. On the other hand, when the ultrasonic application unit 512 stops according to the operation stop instruction from the control unit 4, recrystallization of the cyclohexanone oxime particles occurs in the ultrasonic tank 510, and high-purity cyclohexanone oxime (solid phase) precipitates in the tank 511. It should be noted that the ultrasonic tank 520, like the ultrasonic tank 510, has a tank 521 capable of storing substrate processing liquid and an ultrasonic application part 522 installed in the tank 521, and performs the same function.

[0098] Ultrasonic tanks 510 and 520 are interconnected via connecting pipe 530. One end of connecting pipe 530 is connected to the bottom of ultrasonic tank 510, and the other end is connected to the bottom of ultrasonic tank 520. A pump 531 is installed in the center of connecting pipe 530. A three-way valve 532 is installed between one end of connecting pipe 530 and the pump 531, and a three-way valve 533 is installed between the other end of connecting pipe 530 and the aforementioned installation position. Therefore, if pump 531 operates according to a command from control unit 4, and three-way valves 532 and 533 switch to the liquid delivery position according to a command from control unit 4 (see reference...), Figure 9C Then, the substrate processing liquid is supplied between the ultrasonic tanks 510 and 520. In addition, the three-way valves 532 and 533, besides having a first port and a second port for controlling the supply of the substrate processing liquid, also have a third port for discharging liquid from the ultrasonic tank 510. Therefore, according to the command from the control unit 4, with all ports of the three-way valve 533 closed, the first port and the third port of the three-way valve 532 are opened, thereby allowing liquid to be discharged from the ultrasonic tank 510 via the piping 534 (see reference). Figure 9D Additionally, according to instructions from the control unit 4, the first and third ports of the three-way valve 533 are opened when all ports of the three-way valve 532 are closed, thereby allowing liquid to be discharged from the ultrasonic tank 520 via the piping 535.

[0099] In addition, the ultrasonic tank 510 is connected with pipes 513 to 515. The pipe 515 is connected with a supply source of cyclohexanone oxime. Therefore, cyclohexanone oxime is supplied from the supply source to the ultrasonic tank 510 according to a replenishment instruction from the control section 4. Note that, the cyclohexanone oxime supplied from the supply source can be cyclohexanone oxime (solid phase) or a cyclohexanone oxime solution with a high concentration dissolved with a solvent identical to the solvent component in the substrate treatment liquid described above.

[0100] The pipe 514 is connected with a supply source of a solvent of the substrate treatment liquid (IPA in the present embodiment). Therefore, IPA is supplied from the supply source to the ultrasonic tank 510 according to a supply instruction from the control section 4.

[0101] The pipe 513 is connected with a supply source of an auxiliary of the substrate treatment liquid (ammonia in the present embodiment). Therefore, ammonia is supplied from the supply source to the ultrasonic tank 510 according to a supply instruction from the control section 4.

[0102] In addition, in the ultrasonic tank 510, a branch pipe 822 extending from the recovery pipe 821 extending from the second cup 82 is provided, and the used substrate treatment liquid recovered by the second cup 82 is guided to the ultrasonic tank 510. A valve 516 is installed in the branch pipe 822, and is controlled to open and close according to an open / close instruction from the control section 4. That is, by opening the valve 516, the recovered substrate treatment liquid is transported to the ultrasonic tank 510 (recovery treatment). On the contrary, by closing the valve 516, the transportation of the recovered substrate treatment liquid to the ultrasonic tank 510 is stopped.

[0103] Further, in order to measure the concentration of cyclohexanone oxime in the ultrasonic tank 510, a concentration meter 541 is provided in the ultrasonic tank 510.

[0104] Thus, the cyclohexanone oxime, the IPA, the NH4OH, and the used substrate processing liquid can be supplied to the ultrasonic tank 510 independently. Therefore, when the cyclohexanone oxime concentration in the substrate processing liquid stored in the ultrasonic tank 510 is detected to be low based on the measurement result of the concentration meter 541, the control section 4 increases the concentration to be higher than the saturation concentration by supplying the cyclohexanone oxime. Further, the cyclohexanone oxime concentration can be adjusted by adding the IPA to the substrate processing liquid stored in the ultrasonic tank 510. Further, the cyclohexanone oxime particles can be adjusted to the metastable state by adding the NH4OH to the substrate processing liquid in which the cyclohexanone oxime concentration exceeds the saturation concentration. Furthermore, as described later, by supplying the IPA in the state where only the cyclohexanone oxime (solid phase) separated in the ultrasonic tank 510 remains in the ultrasonic tank 510, the surface layer of the separated product (cyclohexanone oxime (solid phase)) can be peeled off thinly, and the impurities adhering to the separated product can be removed. Thus, only the cyclohexanone oxime (solid phase) of high purity remains in the ultrasonic tank 510, and by supplying the IPA and the NH4OH in appropriate amounts, respectively, the substrate processing liquid containing the cyclohexanone oxime particles of high purity and in the metastable state can be obtained (refining processing).

[0105] In order to deliver the substrate processing liquid refined in this way to the storage tank 401, a pipe 517 is provided which connects the bottom of the ultrasonic tank 510 to the pipe 403. A pump 518 and a valve 519 are installed in the pipe 517. Therefore, in the state where the valve 519 is opened based on the opening instruction from the control section 4, the pump 518 is operated based on the operation instruction from the control section 4, whereby the substrate processing liquid refined as described above is delivered to the storage tank 401 via the pipe 517. In this way, the replenishment processing of the substrate processing liquid is performed. In this way, in the ultrasonic tank 510, the recovery / refining processing and the replenishment processing can be performed alternately.

[0106] As for the other ultrasonic tank 520, the pipes 523 to 525 are connected thereto as with the ultrasonic tank 510. Further, the replenishment of the cyclohexanone oxime via the pipe 525 based on the measurement result of the concentration meter 542, the supply of the IPA (solvent) via the pipe 524, and the replenishment of the ammonia water (adjuvant) via the pipe 523 can be performed independently, respectively. Further, the ultrasonic tank 520 is connected to a branch pipe 823 of the recovery pipe 821 extending from the second cup 82, and by opening the valve 526 installed in the branch pipe 823, the recovered substrate processing liquid is delivered to the ultrasonic tank 520. On the contrary, by closing the valve 526, the delivery of the recovered substrate processing liquid to the ultrasonic tank 520 is stopped. Therefore, in the ultrasonic tank 520 as well, the recovery / refining processing and the replenishment processing can be performed alternately as with the ultrasonic tank 510.

[0107] Figure 8 is a flowchart showing the operation of the refining device shown in Figure 6 Fig. 6. Figures 9A to 9Eare respectively schematic views Figure 6 Fig. 2 is a view showing an example of the operation of the refining device. In these drawings, the symbols ON, OFF indicate the operation / operation stop of the ultrasonic wave applying sections 512, 522, and in the symbols indicating the valves and the three-way valves, the portions of the triangles in black indicate the state in which the ports and the valves are open, and the portions of the triangles in white indicate the state in which the ports and the valves are closed. Also, the thick lines indicate the flow of the liquid.

[0108] The respective sections of the refining device 500 operate in parallel with the substrate processing in the substrate processing device 1 in accordance with the refining program stored in advance in the control section 4, as follows. Thereby, the replenishment processing is performed in parallel with the recovery / refining processing in the ultrasonic wave tank 510, 520. Note that in this embodiment, the refining device 500 is controlled by the control section 4 that controls the entire substrate processing device 1, but it can also be configured so that a dedicated control section for controlling the refining device 500 is provided, and the respective sections of the refining device 500 are controlled by this control section. Figure 6 The control section 4 sets the functions of the respective ultrasonic wave tanks 510, 520 in step Sll so as to alternately switch the ultrasonic wave tank that performs the recovery / refining processing and the ultrasonic wave tank that performs the replenishment processing. Here, in this step Sll, it is assumed that the control section 4 is set so that the ultrasonic wave tanks 510, 520 perform the recovery / refining processing and the replenishment processing, respectively, and the explanation will be made. At this time, the valves 516, 526 are closed, and the supply of the substrate processing liquid recovered to the second cup 82 to the refining device 500 is stopped. Also, all of the ports of the three-way valves 532, 533 are closed, whereby the passage of the substrate processing liquid before refining (hereinafter referred to as "pre-refining processing liquid") between the ultrasonic wave tanks 510, 520 is restricted. Also, the ultrasonic wave applying sections 522, 523 are both in operation, and the ultrasonic wave tank 510 stores the pre-refining processing liquid, and on the other hand, the ultrasonic wave tank 520 stores the substrate processing liquid after refining.

[0109] In the ultrasonic wave tank 520 that performs the replenishment processing, as shown in Fig. 2, the valve 529 is opened, and at the same time, the pump 528 is operated. Thereby, the substrate processing liquid after refining is transported to the storage tank 401 of the processing liquid supply section 400 via the pipe 527 (step S12). Also, in conjunction with the transport of the substrate processing liquid, the storage amount of the substrate processing liquid in the ultrasonic wave tank 520 gradually decreases, and becomes empty (YES in step S13). Then, the pump 528 is stopped, and at the same time, the valve 529 is closed (step S14). Thereby, the replenishment processing is completed.

[0110] Figure 9A In parallel with the replenishment processing, the recovery / refining processing is performed in the ultrasonic wave tank 510 (steps S15 to S19). In step S15, as shown in Fig. 2, the valve 516 is opened, and at the same time, the pump 515 is operated. Thereby, the pre-refining processing liquid is transported to the storage tank 401 of the processing liquid supply section 400 via the pipe 517 (step S16). Also, in conjunction with the transport of the pre-refining processing liquid, the storage amount of the pre-refining processing liquid in the ultrasonic wave tank 510 gradually decreases, and becomes empty (YES in step S17). Then, the pump 515 is stopped, and at the same time, the valve 516 is closed (step S18). Thereby, the recovery / refining processing is completed. Figure 6

[0111] In parallel with the replenishment processing, the recovery / refining processing is performed in the ultrasonic wave tank 510 (steps S15 to S19). In step S15, as shown in Fig. 2, the valve 516 is opened, and at the same time, the pump 515 is operated. Thereby, the pre-refining processing liquid is transported to the storage tank 401 of the processing liquid supply section 400 via the pipe 517 (step S16). Also, in conjunction with the transport of the pre-refining processing liquid, the storage amount of the pre-refining processing liquid in the ultrasonic wave tank 510 gradually decreases, and becomes empty (YES in step S17). Then, the pump 515 is stopped, and at the same time, the valve 516 is closed (step S18). Thereby, the recovery / refining processing is completed.​​Figure 9A As shown, the valve 516 is opened, and the substrate processing liquid recovered to the second cup 82 is recovered to the ultrasonic tank 510 functioning as a polishing ultrasonic tank via the pipes 821, 822, and mixed with the already stored pre-polishing liquid. When this operation is completed, the valve 516 is closed.

[0112] When the concentration of the cyclohexanone oxime particles contained in the pre-polishing liquid is below the saturation concentration according to the measurement result of the concentration meter 541, that is, when the pre-polishing liquid has not become supersaturated (NO in step S16), cyclohexanone oxime, IPA, or NH4OH is supplied to the ultrasonic tank 510, and the concentration of the cyclohexanone oxime particles in the pre-polishing liquid is adjusted (step S17), and the process returns to step S16.

[0113] On the other hand, when it is confirmed that the concentration of the cyclohexanone oxime particles exceeds the saturation concentration, and that there is a pre-polishing liquid in a supersaturated state in the ultrasonic tank 510 (YES in step S16), as shown in Figure 9B The ultrasonic application section 512 is stopped, and the application of ultrasonic vibration to the pre-polishing liquid is stopped (step S18). As a result, the recrystallization of the cyclohexanone oxime particles in the quasi-stable state is started, and cyclohexanone oxime (solid phase) OX is precipitated in the ultrasonic tank 510. When it is confirmed that the recrystallization is completed and the replenishment treatment is completed based on the measurement result of the concentration meter 541, as shown in Figure 9C The first and second ports of the three-way valve 532, 533 are opened, and the pump 531 is operated to transfer the pre-polishing liquid stored in the ultrasonic tank 510 to the empty ultrasonic tank 520 via the pipe 530. That is, the pre-polishing liquid is transferred from the polishing ultrasonic tank 510 to the empty ultrasonic tank 520 (step S19), and the ultrasonic tank 520 receives the pre-polishing liquid from the polishing ultrasonic tank 510 (step S20). As a result, only the precipitate (cyclohexanone oxime (solid phase)) remains in the ultrasonic tank 510, and on the other hand, the pre-polishing liquid containing cyclohexanone oxime particles at a concentration below the saturation concentration is stored in the ultrasonic tank 520, and becomes a state similar to that of the ultrasonic tank 510 before the start of the recovery / polishing treatment.

[0114] When the transfer of the pre-polishing liquid is completed, the pump 531 is stopped. In addition, the first and second ports of the three-way valve 532, 533 are closed. Then, as shown in Figure 9DAs shown, only IPA is supplied to the ultrasonic tank 510. Thereby, the surface layer of the precipitate is peeled off thinly, and the impurities adhering to the precipitate are removed, i.e., the cyclohexanone oxime (solid phase) OX is cleaned. After this cleaning, the first port and the third port of the three-way valve 532 are opened, and the cleaned IPA is discharged from the ultrasonic tank 510 along with the impurities through the drain path formed by the pipe 530, the three-way valve 532, and the pipe 534. By repeating such precipitate cleaning, the cyclohexanone oxime (solid phase) OX of high purity is obtained (step S21). Next, as shown in FIG. 6, IPA and NH4OH are supplied to the ultrasonic tank 510, and the operation of the ultrasonic wave application unit 512 is started again. Thereby, the supersaturated substrate processing liquid is refined, and is stored in the ultrasonic tank 510 as a substrate processing liquid suitable for sublimation drying, as with the ultrasonic tank 520 before the above replenishment treatment is performed (step S22). Figure 9E

[0115] Thus, when the replenishment treatment and the recovery / refinement treatment are completed, the process returns to step Sll, and the replenishment treatment and the recovery / refinement treatment are repeated. That is, the replenishment treatment and the recovery / refinement treatment and the replenishment treatment are performed in the ultrasonic tanks 510, 520, respectively.

[0116] As described above, in the refinement device 500, the substrate processing liquid is refined using the cyclohexanone oxime (solid phase) OX obtained by recrystallization of the cyclohexanone oxime particles in the quasi-stable state. Therefore, a substrate processing liquid free of impurities, liquid particles, and the like can be obtained. Moreover, by performing sublimation drying using this substrate processing liquid, the collapse of the pattern PT can be further suppressed.

[0117] <Batch-type substrate processing system>

[0118] The application object of the present application is not limited to the single-wafer substrate processing device, and can be applied to a substrate processing device equipped in a so-called batch-type substrate processing system.

[0119] Figure 10 ​is a view showing the configuration of a substrate processing system equipped with the substrate processing apparatus of the second embodiment of the present application. The substrate processing system 200 is a batch type substrate processing system that processes a plurality of substrates W at once. The substrate processing system 200 includes a chemical liquid storage tank 210 that stores a chemical liquid, a rinse liquid storage tank 220 that stores a rinse liquid (e.g., water), a sublimation agent storage tank 230 that stores a substrate processing liquid used for sublimation drying in the first embodiment, and a supply liquid storage tank 240 that stores a supply liquid (e.g., an aqueous liquid). Note that the sublimation agent storage tank 230 is connected to a pipe 405 that extends from the processing liquid supply section 400 described above. In addition, the substrate processing liquid recovered by the overflow tank provided to the sublimation agent storage tank 230 is recovered to the refining apparatus 500 via a pipe 821. In this refining apparatus 500, recovery / refining processing is performed. Then, the refined substrate processing liquid is returned to the sublimation agent storage tank 230 via the processing liquid supply section 400. Also, although not shown in the drawing, an ultrasonic wave generator described in, for example, Japanese Patent Application Publication No. 2021-034442 is provided to the lower side of the sublimation agent storage tank 230, and can switch between giving and stopping giving of ultrasonic waves to the substrate processing liquid in the sublimation agent storage tank 230. Figure 10

[0120] The substrate processing system 200 further includes a lifter 250 that immerses the substrates W in the supply liquid stored in the supply liquid storage tank 240, and a lifter lifting section 260 that lifts the lifter 250. The lifter 250 supports a plurality of substrates W in a vertical posture, respectively. The lifter lifting section 260 lifts the lifter 250 between a processing position (position shown by a solid line in the drawing) in which the substrates W held to the lifter 250 are located in the supply liquid storage tank 240, and a retreat position (position shown by a double-dot chain line in the drawing) in which the substrates W held to the lifter 250 are retreated upward from the supply liquid storage tank 240. Figure 10 Figure 10

[0121] ​​​In a series of processes in the substrate processing system 200, a plurality of substrates W carried into the processing units of the substrate processing system 200 are dipped in the chemical liquid stored in the chemical liquid storage tank 210. Thus, the chemical liquid process (cleaning process, etching process) is performed on each substrate W (chemical liquid process). If a predetermined period elapses from the start of dipping in the chemical liquid, the plurality of substrates W are lifted from the chemical liquid storage tank 210 and moved to the rinse liquid storage tank 220. Next, the plurality of substrates W are dipped in the rinse liquid stored in the rinse liquid storage tank 220. Thus, the rinse process is performed on the substrates W (rinse process). If a predetermined period elapses from the start of dipping in the rinse liquid, the plurality of substrates W are lifted from the rinse liquid storage tank 220 and moved to the sublimation agent storage tank 230. Next, the plurality of substrates W are dipped in the substrate processing liquid stored in the sublimation agent storage tank 230. If a predetermined period elapses from the start of dipping in the substrate processing liquid, the plurality of substrates W are lifted from the sublimation agent storage tank 230. At this time, the cyclohexanone oxime particles in the substrate processing liquid are precipitated, and the solidification film starts to be formed on the surface of each substrate W. Then, the substrates W with the solidification film are moved to the supply liquid storage tank 240.

[0122] On the surface of each substrate W moved to the supply liquid storage tank 240, the solidification film of the substrate processing liquid is formed on the entire area thereof. Then, the lifter lifting section 260 is controlled so that the lifter 250 is moved from the retreat position to the processing position, and thus the plurality of substrates W held by the lifter 250 are dipped in the supply liquid.

[0123] If a predetermined period elapses from the start of dipping of the substrates W in the supply liquid, the lifter lifting section 260 is controlled so that the lifter 250 is moved from the processing position to the retreat position. Thus, the plurality of substrates W dipped in the supply liquid are lifted from the supply liquid.

[0124] At the time of lifting of the substrates W from the supply liquid, the lifting drying (supply liquid removal process) is performed. The lifting drying is performed by lifting the substrates W at a slow speed (for example, several mm / sec) while blowing a gas (for example, non-active gas such as nitrogen gas) against the surface of the substrates W lifted from the supply liquid storage tank 240. Thus, the supply liquid is removed from the entire area of the surface of the substrates W.

[0125] After that, the solidification film, that is, the cyclohexanone oxime (solid phase) is sublimated into a gas. Thus, the solidification film can be removed from the surface of the substrates W without passing through a liquid state, and thus the collapse of the pattern can be effectively suppressed or prevented, and the surface of the substrates W can be dried.

[0126] In the above-described embodiment, the purification of the substrate processing liquid performed by the purification device 500 corresponds to an example of the "processing liquid preparation process" of the present application, Figure 8The steps S15 to S17 in FIG. 15 correspond to an example of the "first process" of the present application, the step S18 corresponds to an example of the "second process" of the present application, the steps S21 and S22 correspond to an example of the "third process" of the present application, and the step S12 corresponds to an example of the "fourth process" of the present application. In addition, the storage tank 401 corresponds to an example of the "storage section" of the present application.

[0127] Note that the present application is not limited to the above-described embodiments, and various modifications can be made to the above-described embodiments without departing from the gist thereof. For example, in the above-described embodiments, the substrate processing liquid recovered is mixed and then purified using the purification device 500, but the mixing is not essential and is optional. However, the mixing is advantageous in terms of achieving a reduction in operating costs and the like.

[0128] In addition, in the above-described embodiments, the separated cyclohexanone oxime OX is subjected to the cleaning treatment, but the cleaning treatment can be omitted.

[0129] In addition, in the above-described embodiments, the substrate processing liquid before purification is moved back and forth between the ultrasonic tanks 510 and 520, and as the number of times of back and forth movement increases, impurities, liquid particles, and the like in the substrate processing liquid before purification increase. Therefore, the substrate processing liquid before purification can be discharged via the pipes 534 and 535 when the number of times of back and forth movement reaches a certain value.

[0130] In addition, in the above-described embodiments, the substrate processing liquid after purification by the purification device 500 is used, but the purification treatment is not essential. For example, a supersaturated solution of a sublimable substance obtained by uniformly dispersing particles of a sublimable substance (solid phase) exceeding the solubility in a solution by adding an aid when dissolving the sublimable substance in a solvent can be used as the substrate processing liquid.

[0131] The present application has been described above with reference to specific embodiments, but the description is not intended to be construed in a limiting sense. Various modifications to the disclosed embodiments can be apparent to those skilled in the art upon reference to the description of the present application. Therefore, it is understood that such modifications or variations are intended to be included within the scope of the appended claims, which are to be interpreted in the broadest sense possible. The present application is not limited to the embodiments described above, but can be applied to all substrate processing liquids used when removing a liquid adhering to a substrate using the sublimation phenomenon of a sublimable substance and all substrate processing techniques for removing the liquid from the substrate using the substrate processing liquid.

[0132] The present application can be applied to all substrate processing liquids used when removing a liquid adhering to a substrate using the sublimation phenomenon of a sublimable substance and all substrate processing techniques for removing the liquid from the substrate using the substrate processing liquid.

Claims

1. A substrate processing liquid, which is a substrate processing liquid for removing a liquid on a substrate having a patterned surface, characterized by, Comprising: a sublimation substance; a solvent that dissolves the sublimation substance; and an auxiliary agent that disperses particles of the sublimation substance in excess of solubility in the solution by adding to a solution obtained by dissolving the sublimation substance with the solvent, the sublimation substance is cyclohexanone oxime, the auxiliary agent adjusts the pH of the solution in a manner that the Zeta potential of the sublimation substance in the solution is negative, the particles of the sublimation substance in excess of solubility are dispersed in the solution.

2. The substrate processing liquid according to claim 1, wherein the auxiliary agent is a crystallization inhibitor that inhibits crystallization of the sublimation substance in the solution.

3. The substrate processing liquid according to claim 1, wherein the auxiliary agent is aqueous ammonia.

4. A substrate processing method characterized by, Including: a treatment liquid preparation step of preparing a substrate treatment liquid described in any one of claims 1 to 3; a liquid film formation step of supplying the substrate treatment liquid prepared by the treatment liquid preparation step to a pattern-formed substrate surface to form a liquid film of the substrate treatment liquid on the substrate surface; a solidified film formation step of solidifying the liquid film of the substrate treatment liquid to form a solidified film of the sublimation substance; and a sublimation step of subliming the solidified film to remove from the substrate surface. The treatment liquid preparation step includes a step of storing the substrate treatment liquid in a storage tank to which ultrasonic vibration is applied.

5. The substrate processing method according to claim 4, wherein The treatment liquid preparation step has:

6. The substrate processing method according to claim 5, wherein a first step of adjusting a supersaturated solution of the sublimation substance; a second step of precipitating the sublimation substance from the supersaturated solution; a third step of refining the substrate treatment liquid by adding the auxiliary agent to a solution obtained by dissolving the precipitated sublimation substance with the solvent; and a fourth step of replenishing the substrate treatment liquid refined by the third step to the storage tank. The third step includes a step of cleaning the precipitated sublimation substance before dissolving the precipitated sublimation substance with the solvent.

8. The substrate treatment method according to claim 6, wherein 7. The substrate processing method according to claim 6, wherein the first step is performed in an ultrasonic tank to which ultrasonic vibration is applied, the second step is performed by stopping application of ultrasonic waves to the ultrasonic tank in which the supersaturated solution is stored, the third step is performed by again starting application of ultrasonic vibration to the ultrasonic tank. The liquid film formation step includes a step of supplying the substrate treatment liquid to the substrate surface by discharging the substrate treatment liquid from a nozzle to the substrate surface while applying ultrasonic vibration to the substrate treatment liquid in the nozzle. The liquid film formation step includes a step of transporting the substrate treatment liquid from the storage tank to the nozzle while applying ultrasonic vibration to the substrate treatment liquid.

9. The substrate processing method according to claim 5, wherein Possessing:

10. The substrate processing method according to claim 9, wherein a storage section that stores a substrate treatment liquid described in any one of claims 1 to 3; and 11. A substrate processing apparatus, characterized by comprising: a treatment liquid supply section that supplies the substrate treatment liquid stored in the storage section to a pattern-formed substrate surface. ​ ​

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