Substrate processing method, substrate processing apparatus, and processing liquid

Abstract

To provide a substrate processing method, a substrate processing apparatus, and a process liquid with which a substrate can be appropriately dried.SOLUTION: The present invention relates to a substrate processing method, a substrate processing apparatus, and a process liquid. The substrate processing method includes a process liquid supply step, a solidified film forming step, and a sublimation step. In the process liquid supply step, the process liquid g is supplied to a substrate W. The process liquid g includes a primary sublimable material, a secondary sublimable material, and a solvent. In the solidified film forming step, the solvent evaporates from the process liquid g on the substrate W. In the solidified film forming step, a solidified film is formed on the substrate W. The solidified film includes the primary sublimable material and the secondary sublimable material. In the sublimation step, the solidified film sublimes. The sublimation of the solidified film dries the substrate W. Here, the primary sublimable material is cyclohexanone oxime. The secondary sublimable material is at least one of camphor and acetoxime.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method, a substrate processing apparatus, and a processing solution for substrates such as semiconductor wafers, liquid crystal display substrates, organic electroluminescence (EL) substrates, FPD (Flat Panel Display) substrates, optical display substrates, magnetic disk substrates, optical disk substrates, magneto-optical disk substrates, photomask substrates, and solar cell substrates. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to the substrate. The processing liquid contains a first sublimable substance, a second sublimable substance, and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid on the substrate, and a solidified film is formed on the substrate. The solidified film contains the first sublimable substance and the second sublimable substance. In the sublimation step, the solidified film sublimes. In the sublimation step, the solidified film changes into a gas without passing through a liquid state. As the solidified film sublimes, it leaves the substrate. As the solidified film sublimes, the substrate is dried. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2020-10015 Summary of the Invention [Problem to be solved by the invention]

[0004] Even with conventional substrate processing methods, there are cases where the substrate cannot be dried properly. For example, even with conventional substrate processing methods, there are cases where patterns formed on the substrate collapse. For example, when the patterns are fine, conventional substrate processing methods may not be able to sufficiently prevent the collapse of the patterns.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid that can properly dry a substrate. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention has the following configuration: That is, the present invention is a substrate processing method for processing a substrate on which a pattern has been formed, comprising: a processing liquid supplying step of supplying a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate, a solidified film forming step of evaporating the solvent from the processing liquid on the substrate to form a solidified film containing the main sublimable substance and the sub-sublimable substance on the substrate, and a sublimation step of sublimating the solidified film, wherein the main sublimable substance is cyclohexanone oxime and the sub-sublimable substance is at least one of camphor and acetoxime.

[0007] The substrate processing method is for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to the substrate. The processing liquid includes a main sublimable substance, a sub-sublimable substance, and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film includes a main sublimable substance and a sub-sublimable substance. In the sublimation step, the solidified film sublimes. The substrate is dried by the sublimation of the solidified film. Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetoxime. Therefore, the substrate is appropriately dried. Specifically, the substrate is dried in a state in which the pattern formed on the substrate is appropriately protected.

[0008] As described above, according to the present substrate processing method, the substrate is properly dried.

[0009] In the above-described substrate processing method, the volume of the sub-sublimable substance contained in the processing liquid is preferably 0.5% or more and 20% or less of the volume of the main sublimable substance contained in the processing liquid. The amount of the sub-sublimable substance contained in the processing liquid is relatively small. Therefore, the influence of the sub-sublimable substance on the thickness of the processing liquid on the substrate is small. Therefore, it is easy to control the thickness of the processing liquid on the substrate in the processing liquid supply step. Therefore, it is easy to control the thickness of the solidified film. As a result, the substrate is dried more appropriately.

[0010] The present invention also provides a substrate processing method for processing a substrate on which a pattern has been formed, the method comprising: a processing liquid supplying step of supplying a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to a substrate; a solidified film forming step of evaporating the solvent from the processing liquid on the substrate to form a solidified film containing the main sublimable substance and the sub-sublimable substance on the substrate; and a sublimation step of sublimating the solidified film, wherein in the solidified film forming step, the processing liquid on the substrate generates a plurality of main crystal nuclei of the main sublimable substance and a plurality of sub-crystal nuclei of the sub-sublimable substance, and the main crystal nuclei grow on the substrate into main crystals of the main sublimable substance, and the sub-crystal nuclei grow on the substrate into sub-crystals of the sub-sublimable substance.

[0011] The substrate processing method is for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to the substrate. The processing liquid contains a main sublimable substance, a sub-sublimable substance, and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film contains a main sublimable substance and a sub-sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by the sublimation of the solidified film.

[0012] In the solidified film formation process, the processing liquid on the substrate generates a plurality of main crystal nuclei of the main sublimable substance and a plurality of sub-crystal nuclei of the sub-sublimable substance. In the solidified film formation process, the main crystal nuclei grow into main crystals of the main sublimable substance on the substrate. In the solidified film formation process, the sub-crystal nuclei grow into sub-crystals of the sub-sublimable substance on the substrate. At least one of the main crystals and the sub-crystals is relatively small. In other words, at least one of the main crystals and the sub-crystals is not excessively large. Therefore, even if a minute space is formed between the main crystals and the sub-crystals, the minute space is relatively small. In other words, the minute space is not excessively large. Therefore, the solidified film can favorably support the pattern formed on the substrate. Therefore, the substrate is dried in a state in which the pattern formed on the substrate is favorably protected.

[0013] As described above, according to the present substrate processing method, the substrate is properly dried.

[0014] In the above-described substrate processing method, in the solidified film forming step, the sub-crystals preferably grow at positions between the plurality of main crystals. The sub-crystals effectively reduce the size of the micro-space, thereby more effectively protecting the pattern formed on the substrate.

[0015] In the above-described substrate processing method, it is preferable that the sub-crystal nuclei are generated at positions between the plurality of main crystal nuclei in the solidified film forming step. The sub-crystals grow favorably at positions between the plurality of main crystal nuclei.

[0016] In the above-described substrate processing method, it is preferable that the main crystal grows before the sub-crystal in the solidified film forming step. The sub-crystal is smaller than the main crystal. Therefore, the sub-crystal more effectively reduces the size of the microspace.

[0017] In the above-described substrate processing method, it is preferable that the main crystal nuclei are generated before the sub-crystal nuclei in the solidified film forming step. It is easy for the main crystals to grow before the sub-crystals.

[0018] In the above-described substrate processing method, it is preferable that the sub-crystals grow before the main crystals in the solidified film forming step. The main crystals are smaller than the sub-crystals. Therefore, the main crystals more effectively reduce the size of the microspace.

[0019] In the above-described substrate processing method, it is preferable that the sub-crystal nuclei are generated before the main crystal nuclei in the solidified film forming step. It is easy for the sub-crystals to grow before the main crystals.

[0020] The present invention also provides a substrate processing method for processing a substrate having a pattern formed thereon, the method comprising: a processing liquid supplying step of supplying a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate; a solidified film forming step of evaporating the solvent from the processing liquid on the substrate to form a solidified film containing the main sublimable substance and the sub-sublimable substance on the substrate; and a sublimation step of sublimating the solidified film, wherein the processing liquid on the substrate is maintained at a first temperature from the processing liquid supplying step to the solidified film forming step.

[0021] The substrate processing method is for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to the substrate. The processing liquid contains a main sublimable substance, a sub-sublimable substance, and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film contains a main sublimable substance and a sub-sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by the sublimation of the solidified film.

[0022] The processing liquid on the substrate is maintained at a first temperature from the processing liquid supply step to the solidified film formation step. Therefore, in the solidified film formation step, the solvent smoothly evaporates from the processing liquid on the substrate. Therefore, in the solidified film formation step, an appropriate solidified film is formed on the substrate. Therefore, the solidified film suitably protects the pattern formed on the substrate from the processing liquid. The substrate is dried in a state in which the pattern formed on the substrate is suitably protected.

[0023] As described above, according to the present substrate processing method, the substrate is properly dried.

[0024] In the above-described substrate processing method, the first temperature is preferably lower than both the melting point of the main sublimable substance and the melting point of the sub-sublimable substance. The main sublimable substance contained in the solidified film easily maintains its solid state. The sub-sublimable substance contained in the solidified film also easily maintains its solid state. Therefore, the solidified film is more appropriately formed in the solidified film formation step.

[0025] In the above-described substrate processing method, the first temperature is preferably close to the lowest melting point among the melting points of the primary sublimable substance and the secondary sublimable substance. The solvent evaporates quickly from the processing liquid on the substrate. In other words, the evaporation rate of the solvent is suitably improved. Therefore, in the solidified film forming step, a more suitable solidified film is formed on the substrate. Therefore, the solidified film more suitably protects the pattern formed on the substrate from the processing liquid.

[0026] The present invention also provides a substrate processing apparatus comprising: a substrate holding unit that holds a substrate; and a processing liquid supply unit that supplies a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate held by the substrate holding unit, wherein the main sublimable substance is cyclohexanone oxime, and the sub-sublimable substance is at least one of camphor and acetoxime.

[0027] The substrate processing apparatus includes a substrate holding unit and a processing liquid supply unit. The substrate holding unit holds a substrate. The processing liquid supply unit supplies the processing liquid to the substrate held by the substrate holding unit. The processing liquid contains a main sublimable substance, a sub-sublimable substance, and a solvent. Therefore, when the processing liquid is supplied to the substrate, the solvent evaporates from the processing liquid on the substrate. A solidified film is formed on the substrate by evaporation of the solvent. The solidified film contains a main sublimable substance and a sub-sublimable substance. Therefore, the solidified film sublimes. The substrate is dried by sublimation of the solidified film.

[0028] Here, the main sublimable substance is cyclohexanone oxime, and the secondary sublimable substance is at least one of camphor and acetoxime. Therefore, the substrate is appropriately dried. Specifically, the substrate is dried in a state where the pattern formed on the substrate is appropriately protected.

[0029] As described above, according to the present substrate processing apparatus, the substrate is dried appropriately.

[0030] The above-described substrate processing apparatus preferably further comprises a temperature control unit that adjusts the processing liquid on the substrate to a first temperature. The processing liquid on the substrate is suitably maintained at the first temperature. Therefore, the solvent evaporates smoothly from the processing liquid on the substrate. Therefore, the solidified film is more suitably formed. As a result, the solidified film more suitably protects the pattern formed on the substrate from the processing liquid. The substrate is dried in a state in which the pattern formed on the substrate is suitably protected. In other words, the substrate is more suitably dried.

[0031] The present invention provides a treatment liquid used for drying a substrate on which a pattern has been formed, the treatment liquid including a main sublimable substance, a sub-sublimable substance, and a solvent, the main sublimable substance being cyclohexanone oxime, and the sub-sublimable substance being at least one of camphor and acetoxime.

[0032] The processing liquid is used to dry a substrate on which a pattern has been formed. Specifically, the processing liquid is a drying auxiliary liquid. The processing liquid contains a main sublimable substance, a sub-sublimable substance, and a solvent.

[0033] Here, the primary sublimable substance is cyclohexanone oxime, and the secondary sublimable substance is at least one of camphor and acetoxime. Therefore, the treatment liquid makes it easier to properly dry the substrate. Specifically, the treatment liquid makes it easier to dry the substrate while suitably protecting the pattern on the substrate. In this way, the treatment liquid is useful for drying the substrate.

[0034] As described above, the substrate is properly dried using the processing liquid. [Effects of the Invention]

[0035] According to the substrate processing method, substrate processing apparatus, and processing solution of the present invention, the substrate is dried appropriately. [Brief explanation of the drawings]

[0036] [Figure 1] FIG. 2 is a diagram schematically illustrating a part of a substrate. [Figure 2] FIG. 2 is a plan view showing the inside of the substrate processing apparatus according to the first embodiment. [Figure 3] FIG. 2 is a control block diagram of the substrate processing apparatus. [Figure 4] FIG. 2 is a diagram showing a configuration of a processing unit and a first supply source. [Figure 5] 3 is a flowchart showing the procedure of a substrate processing method according to the first embodiment. [Figure 6] FIG. 10 is a diagram schematically illustrating a substrate in a processing liquid supplying step. [Figure 7] 1A and 1B are diagrams schematically illustrating a substrate in a solidified film forming step. [Figure 8] 1A and 1B are diagrams schematically illustrating a substrate in a solidified film forming step. [Figure 9] FIG. 2 is a diagram schematically illustrating a substrate in a sublimation process. [Figure 10] FIG. 2 is a diagram schematically illustrating a substrate in a sublimation process. [Figure 11] 1 is a table showing the collapse rates of substrates processed in Experimental Examples 1-3 and Comparative Example. [Figure 12] 1 is a graph showing the collapse rates of substrates processed in Experimental Examples 1-3 and Comparative Example. [Figure 13] 1A and 1B are diagrams illustrating the mechanism of pattern collapse. [Figure 14] 1A and 1B are diagrams illustrating the mechanism of pattern collapse. [Figure 15] 1A and 1B are diagrams illustrating the mechanism of pattern collapse. [Figure 16] 1A and 1B are diagrams illustrating the mechanism of pattern collapse. [Figure 17]1A and 1B are diagrams illustrating the mechanism of pattern collapse. [Figure 18] 18(a) to 18(d) are diagrams illustrating a first example of a mechanism for protecting a pattern. [Figure 19] 19(a) to 19(d) are diagrams illustrating a second example of the mechanism for protecting patterns. [Figure 20] 20(a) to 20(d) are diagrams illustrating a third example of the pattern protection mechanism. [Figure 21] 21(a) to 21(c) are diagrams illustrating a fourth example of the pattern protection mechanism. [Figure 22] FIG. 10 is a diagram showing the configuration of a processing unit and a first supply source according to a second embodiment. [Figure 23] FIG. 10 is a diagram showing the configuration of a processing unit and a first supply source according to a modified embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0037] Hereinafter, a substrate processing method, a substrate processing apparatus, and a processing liquid according to the present invention will be described with reference to the drawings.

[0038] 1. First Embodiment <1-1. Circuit board> The substrate W is, for example, a semiconductor wafer, a liquid crystal display substrate, an organic EL (Electroluminescence) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, or a solar cell substrate. The substrate W has a thin, flat plate shape. The substrate W has a substantially circular shape in a plan view.

[0039] 1 is a diagram schematically illustrating a part of a substrate W. The substrate W has a pattern WP. The pattern WP is formed on the surface of the substrate W.

[0040] The pattern WP has, for example, an uneven shape. The pattern WP has, for example, a plurality of protrusions T. The protrusions T are parts of the substrate W. The protrusions T are structures. The protrusions T are made of, for example, at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN), and a polysilicon film. The protrusions T protrude upward from the surface of the substrate W. The plurality of protrusions T are spaced apart from one another. The plurality of protrusions T are arranged, for example, horizontally. The protrusions T define recesses A. The recesses A are spaces. The recesses A are located between two adjacent protrusions T. The recesses A are adjacent to the sides of the protrusions T. Each protrusion T has a first side and a second side. The second side is opposite the first side. The recesses A contact, for example, the first side of the protrusions T and the second side of the protrusions T. The recesses A are, for example, open upward.

[0041] The protrusion T has a height HP. Specifically, the protrusion T has a base end Tp and a tip end Td. The base end Tp corresponds to the proximal end of the protrusion T. The tip end Td corresponds to the distal end of the protrusion T. The height HP corresponds to the distance between the base end Tp and the tip end Td. In this specification, the height HP will be referred to as the height HP of the pattern WP as appropriate.

[0042] <1-2. Processing liquid (drying aid)> In this specification, the processing liquid used to dry the substrate W is simply referred to as the "processing liquid." The processing liquid has a function of assisting in drying the substrate W. The processing liquid can also be called a drying auxiliary liquid.

[0043] The processing liquid includes a main sublimable substance and a sub-sublimable substance. The main sublimable substance is, for example, made up of one type of compound. The sub-sublimable substance is, for example, made up of one type of compound. Alternatively, the sub-sublimable substance includes, for example, two types of compounds. In other words, the sub-sublimable substance includes, for example, a first sub-sublimable substance and a second sub-sublimable substance.

[0044] The compounds contained in the sub-sublimable substance do not overlap with the compounds contained in the main sublimable substance. Specifically, the main sublimable substance does not contain any compounds contained in the sub-sublimable substance. The sub-sublimable substance does not contain any compounds contained in the main sublimable substance. The sub-sublimable substance contains only compounds different from the main sublimable substance.

[0045] The primary and secondary sublimable substances each have sublimability. "Sublimability" refers to the property of a single substance, compound, or mixture to undergo a phase transition from solid to gas or from gas to solid without passing through a liquid state.

[0046] The main sublimable substance and the sub-sublimable substance each preferably have a vapor pressure of 0.1 Pa or more at normal temperature. Here, normal temperature includes room temperature. Normal temperature is, for example, a temperature in the range of 5°C or more and 35°C or less. Normal temperature is, for example, a temperature in the range of 10°C or more and 30°C or less. In this specification, the vapor pressure value is indicated as absolute pressure based on absolute vacuum.

[0047] The vapor pressure of the main sublimable substance at room temperature is not lower than 0.1 Pa. The main sublimable substance does not include compounds having a vapor pressure lower than 0.1 Pa at room temperature. The vapor pressure of the auxiliary sublimable substance at room temperature is not lower than 0.1 Pa. The auxiliary sublimable substance does not include compounds having a vapor pressure lower than 0.1 Pa at room temperature.

[0048] In this specification, the melting point (°C) of the primary sublimable substance is referred to as melting point PA. The melting point of the secondary sublimable substance is referred to as melting point PB. The melting point of the first secondary sublimable substance is referred to as melting point PB1. The melting point of the second secondary sublimable substance is referred to as melting point PB2. The melting point PB includes, for example, melting point PB1 and melting point PB2. The melting point PA is, for example, higher than room temperature. The melting point PB is, for example, higher than room temperature. The melting point PB1 is, for example, higher than room temperature. The melting point PB2 is, for example, higher than room temperature.

[0049] The main sublimable substance is, for example, cyclohexanone oxime. The main sublimable substance is, for example, cyclohexanone oxime alone.

[0050] The vapor pressure of cyclohexanone oxime at room temperature is 0.1 Pa or more. The melting point of cyclohexanone oxime is higher than room temperature.

[0051] The sub-sublimable substance is, for example, at least one of camphor and acetoxime. The sub-sublimable substance is, for example, camphor. The sub-sublimable substance is, for example, acetoxime. The sub-sublimable substance includes, for example, camphor and acetoxime. The first sub-sublimable substance is, for example, camphor. The second sub-sublimable substance is, for example, acetoxime.

[0052] The vapor pressure of camphor at room temperature is 0.1 Pa or more. The vapor pressure of acetoxime at room temperature is 0.1 Pa or more. The melting point of camphor is higher than room temperature. The melting point of acetoxime is higher than room temperature.

[0053] The treatment liquid includes a solvent. The solvent dissolves a main sublimable substance and a sub sublimable substance. The main sublimable substance and the sub sublimable substance in the treatment liquid are dissolved in the solvent. That is, the treatment liquid includes a solvent, a main sublimable substance dissolved in the solvent, and a sub sublimable substance dissolved in the solvent. The main sublimable substance and the sub sublimable substance each correspond to a solute of the treatment liquid.

[0054] The solvent has a relatively high vapor pressure at room temperature, and the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the main sublimable substance at room temperature, and the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the sub-sublimable substance at room temperature.

[0055] In this specification, the melting point of the solvent is referred to as the melting point PC. The melting point PC is preferably lower than the melting points PA and PB. The melting point PC is preferably lower than the melting points PB1 and PB2. The melting point PC is, for example, lower than room temperature.

[0056] The solvent is, for example, an organic solvent. The solvent is, for example, an alcohol.

[0057] The solvent is, for example, isopropyl alcohol (IPA). The solvent is, for example, isopropyl alcohol alone.

[0058] Isopropyl alcohol dissolves cyclohexanone oxime, camphor and acetoxime well.

[0059] The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of cyclohexanone oxime at room temperature. The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of camphor at room temperature. The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of acetoxime at room temperature.

[0060] The melting point of isopropyl alcohol is lower than that of cyclohexanone oxime. The melting point of isopropyl alcohol is lower than that of camphor. The melting point of isopropyl alcohol is lower than that of acetoxime. The melting point of isopropyl alcohol is lower than room temperature.

[0061] The processing liquid is, for example, composed of only a main sublimable substance, a sub-sublimable substance, and a solvent. The processing liquid is, for example, composed of only cyclohexanone oxime, camphor, and isopropyl alcohol. The processing liquid is, for example, composed of only cyclohexanone oxime, acetoxime, and isopropyl alcohol. The processing liquid is, for example, composed of only cyclohexanone oxime, camphor, acetoxime, and isopropyl alcohol.

[0062] Here, the composition of the main sublimable substance, sub-sublimable substance, and solvent in the treatment liquid will be explained. Let volume QA be the volume of the main sublimable substance contained in the treatment liquid. Let volume QB be the volume of the sub-sublimable substance contained in the treatment liquid. Volume QB is smaller than volume QA. For example, volume QB is 0.5% or more and 20% or less of volume QA.

[0063] The volume QB1 is the volume of the first sub-sublimable material contained in the treatment liquid. The volume QB2 is the volume of the second sub-sublimable material contained in the treatment liquid. The volume QB is, for example, the sum of the volumes QB1 and QB2.

[0064] The volume QC is the volume of the solvent contained in the treatment liquid. The volume QC is larger than the volume QA. For example, the volume QC is sufficiently larger than the volume QA.

[0065] <1-3. Overview of substrate processing equipment> 2 is a plan view showing the inside of the substrate processing apparatus 1 of the first embodiment. The substrate processing apparatus 1 performs processing on the substrate W. The processing in the substrate processing apparatus 1 includes a drying process.

[0066] The substrate processing apparatus 1 includes an indexer unit 3 and a processing block 7. The processing block 7 is connected to the indexer unit 3. The indexer unit 3 supplies substrates W to the processing block 7. The processing block 7 processes the substrates W. The indexer unit 3 retrieves the substrates W from the processing block 7.

[0067] For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is referred to as the "front-rear direction X." The front-rear direction X is horizontal. Within the front-rear direction X, the direction from the processing block 7 toward the indexer unit 3 is referred to as the "front." The direction opposite to the front is referred to as the "rear." The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y." One direction in the "width direction Y" is referred to as the "right" as appropriate. The direction opposite to the right is referred to as the "left." The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z." For reference, in each figure, front, rear, right, left, top, and bottom are indicated as appropriate.

[0068] The indexer unit 3 includes a plurality of (for example, four) carrier placement units 4. Each carrier placement unit 4 places one carrier C thereon. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, a FOUP (Front Opening Unified Pod), a SMIF (Standard Mechanical Interface), or an OC (Open Cassette).

[0069] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is disposed behind the carrier platform 4. The transport mechanism 5 transports a substrate W. The transport mechanism 5 is accessible to a carrier C placed on the carrier platform 4. The transport mechanism 5 includes a hand 5a and a hand driver 5b. The hand 5a supports the substrate W. The hand driver 5b is connected to the hand 5a. The hand driver 5b moves the hand 5a. The hand driver 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 5b rotates the hand 5a, for example, in a horizontal plane.

[0070] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 and the transport mechanism 5 can exchange substrates W with each other. The transport mechanism 8 includes a hand 8a and a hand driver 8b. The hand 8a supports the substrate W. The hand driver 8b is connected to the hand 8a. The hand driver 8b moves the hand 8a. The hand driver 8b moves the hand 8a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 8b rotates the hand 8a, for example, in a horizontal plane.

[0071] The processing block 7 includes a plurality of processing units 11. The processing units 11 are arranged on the sides of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

[0072] The processing unit 11 includes a substrate holder 13. The substrate holder 13 holds a substrate W.

[0073] The transport mechanism 8 is accessible to each processing unit 11. The transport mechanism 8 can deliver a substrate W to the substrate holder 13. The transport mechanism 8 can take a substrate W from the substrate holder 13.

[0074] 3 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 is capable of communicating with the transport mechanisms 5 and 8 and the processing units 11. The control unit 10 controls the transport mechanisms 5 and 8 and the processing units 11.

[0075] The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a random-access memory (RAM) that serves as a work area for the processes, a storage medium such as a fixed disk, etc. The control unit 10 has various types of information pre-stored in the storage medium. The information held by the control unit 10 is, for example, transport condition information for controlling the transport mechanisms 5 and 8. The information held by the control unit 10 is, for example, processing condition information for controlling the processing unit 11. The processing condition information is also called a processing recipe.

[0076] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0077] The indexer unit 3 supplies the substrate W to the processing block 7. Specifically, the transport mechanism 5 transfers the substrate W from the carrier C to the transport mechanism 8 of the processing block 7.

[0078] The transport mechanism 8 distributes the substrates W to the processing units 11. Specifically, the transport mechanism 8 transports the substrates W from the transport mechanism 5 to the substrate holders 13 of the processing units 11.

[0079] The processing unit 11 processes the substrate W held by the substrate holder 13. The processing unit 11 performs drying processing on the substrate W, for example.

[0080] After the processing units 11 have processed the substrates W, the transport mechanism 8 collects the substrates W from each processing unit 11. Specifically, the transport mechanism 8 receives the substrates W from each substrate holder 13. Then, the transport mechanism 8 hands over the substrates W to the transport mechanism 5.

[0081] The indexer unit 3 retrieves the substrate W from the processing block 7. Specifically, the transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C.

[0082] <1-4. Configuration of processing unit 11> 4 is a diagram showing the configuration of the processing units 11. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer processing units. That is, each processing unit 11 processes only one substrate W at a time.

[0083] The processing unit 11 includes a housing 12. The housing 12 has a substantially box shape. The substrate W is processed inside the housing 12.

[0084] The inside of the housing 12 is kept at room temperature, so the substrate W is processed in a room temperature environment.

[0085] The inside of the housing 12 is kept at atmospheric pressure, so that the substrate W is processed in an atmospheric pressure environment.

[0086] Here, atmospheric pressure includes standard atmospheric pressure (1 atmosphere, 101,325 Pa). Normal pressure is, for example, an atmospheric pressure in the range of 0.7 atmospheres or more and 1.3 atmospheres or less. In this specification, pressure values ​​are indicated as absolute pressures based on absolute vacuum.

[0087] The above-described substrate holding unit 13 is installed inside the housing 12. The substrate holding unit 13 holds one substrate W. The substrate holding unit 13 holds the substrate W in a substantially horizontal position.

[0088] The substrate holding part 13 is positioned below the substrate W held by the substrate holding part 13. The substrate holding part 13 comes into contact with at least one of the lower surface of the substrate W and the peripheral edge of the substrate W. The substrate holding part 13 does not come into contact with the upper surface of the substrate W.

[0089] The processing unit 11 includes a rotational drive unit 14. At least a portion of the rotational drive unit 14 is installed inside the housing 12. The rotational drive unit 14 is connected to the substrate holding unit 13. The rotational drive unit 14 rotates the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates integrally with the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates around a rotational axis B. The rotational axis B, for example, passes through the center of the substrate W and extends in the vertical direction Z.

[0090] The processing unit 11 includes a supply unit 15. The supply unit 15 supplies a liquid or a gas to the substrate W held by the substrate holding unit 13. Specifically, the supply unit 15 supplies a liquid or a gas to the upper surface of the substrate W held by the substrate holding unit 13.

[0091] The supply unit 15 includes a first supply unit 15a, a second supply unit 15b, a third supply unit 15c, a fourth supply unit 15d, and a fifth supply unit 15e. The first supply unit 15a supplies a processing liquid. The second supply unit 15b supplies a chemical liquid. The third supply unit 15c supplies a rinse liquid. The fourth supply unit 15d supplies a replacement liquid. The fifth supply unit 15e supplies a drying gas.

[0092] The first supply unit 15a is an example of the processing liquid supply unit defined in the present invention.

[0093] As described above, the inside of the housing 12 is at room temperature and pressure. Therefore, the processing liquid is used in an environment at room temperature. The processing liquid is used in an environment at normal pressure.

[0094] The chemical liquid supplied by the second supply unit 15b is, for example, an etching liquid, which includes, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0095] The rinse liquid supplied by the third supply unit 15c is, for example, deionized water (DIW).

[0096] The substitute liquid supplied by the fourth supply unit 15d is, for example, an organic solvent, or isopropyl alcohol (IPA).

[0097] The dry gas supplied by the fifth supply unit 15e preferably has a dew point lower than room temperature. The dry gas is, for example, at least one of air and an inert gas. The air is, for example, compressed air. The inert gas is, for example, nitrogen gas.

[0098] The first supply unit 15a includes a nozzle 16a. Similarly, the second to fifth supply units 15b-15e include nozzles 16b-16e, respectively. The nozzles 16a-16e are installed inside the housing 12. The nozzle 16a discharges a processing liquid. The nozzle 16b discharges a chemical liquid. The nozzle 16c discharges a rinse liquid. The nozzle 16d discharges a substitute liquid. The nozzle 16e discharges a drying gas.

[0099] The first supply unit 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to a nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is open, the nozzle 16a discharges the processing liquid. When the valve 18a is closed, the nozzle 16a does not discharge the processing liquid. Similarly, the second to fifth supply units 15b-15e include pipes 17b-17e and valves 18b-18e, respectively. The pipes 17b-17e are connected to the nozzles 16b-16e, respectively. The valves 18b-18e are provided on the pipes 17b-17e, respectively. The valves 18b-18e control the discharge of the chemical liquid, the rinse liquid, the replacement liquid, and the drying gas, respectively.

[0100] At least a portion of pipe 17a may be provided outside of housing 12. Pipes 17b-17e may be arranged in the same manner as pipe 17a. Valve 18a may be provided outside of housing 12. Valves 18b-18e may be arranged in the same manner as valve 18a.

[0101] The substrate processing apparatus 1 includes a first supply source 19a. The first supply source 19a is connected to a first supply unit 15a. The first supply source 19a is connected to, for example, a pipe 17a. The first supply source 19a supplies the processing liquid to the first supply unit 15a.

[0102] The second supply unit 15b is connected to the second supply source 19b. The second supply source 19b is connected to, for example, the pipe 17b. The second supply source 19b supplies the chemical solution to the second supply unit 15b. Similarly, the third to fifth supply units 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. The third to fifth supply sources 19c-19e are connected to, for example, the pipes 17c-17e, respectively. The third supply source 19c supplies the rinse liquid to the third supply unit 15c. The fourth supply source 19d supplies the replacement liquid to the fourth supply unit 15d. The fifth supply source 19e supplies the drying gas to the fifth supply unit 15e.

[0103] The first supply source 19a is provided outside the housing 12. Similarly, the second to fifth supply sources 19b to 19e are each provided outside the housing 12.

[0104] The first supply source 19a may supply the processing liquid to multiple processing units 11. Alternatively, the first supply source 19a may supply the processing liquid to only one processing unit 11. The same applies to the second to fifth supply sources 19b to 19e.

[0105] The second supply source 19b may be a component of the substrate processing apparatus 1. For example, the second supply source 19b may be a chemical tank provided in the substrate processing apparatus 1. Alternatively, the second supply source 19b may not be a component of the substrate processing apparatus 1. For example, the second supply source 19b may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the third to fifth supply sources 19c-19e may each be a component of the substrate processing apparatus 1. Alternatively, the third to fifth supply sources 19c-19e may each be a component of the substrate processing apparatus 1.

[0106] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12. The cup is arranged around the substrate holder 13. The cup catches liquid splashed from the substrate W held by the substrate holder 13.

[0107] See Fig. 3. The control unit 10 controls the rotary drive unit 14. The control unit 10 controls the supply unit 15. The control unit 10 controls the valves 18a-18e.

[0108] <1-5. Configuration of first supply source 19a> See Figure 4. The first supply source 19a also produces a processing liquid.

[0109] An example of the configuration of the first supply source 19a is shown below. The first supply source 19a is divided into a generation unit 21 and a pumping unit 31. The generation unit 21 generates a treatment liquid. The pumping unit 31 sends the treatment liquid to the first supply part 15a.

[0110] The generation unit 21 includes a tank 22 and supply parts 23a, 23b, 23c, and 23d. The supply part 23a supplies a main sublimable substance to the tank 22. The supply parts 23b and 23c each supply a sub-sublimable substance to the tank 22. Specifically, the supply part 23b supplies a first sub-sublimable substance to the tank 22. The supply part 23c supplies a second sub-sublimable substance to the tank 22. The supply part 23d supplies a solvent to the tank 22. The main sublimable substance, the sub-sublimable substance, and the solvent are mixed in the tank 22. The main sublimable substance, the sub-sublimable substance, and the solvent become a treatment liquid g in the tank 22.

[0111] The tank 22 is installed in an environment at room temperature. The tank 22 is installed in an environment at normal pressure. Therefore, the processing solution g is produced in an environment at room temperature. The processing solution g is produced in an environment at normal pressure.

[0112] Furthermore, the generation unit 21 stores the processing liquid g. Specifically, the processing liquid g is stored in a tank 22. The processing liquid g is stored in an environment at room temperature. The processing liquid g is stored in an environment at normal pressure.

[0113] Supply unit 23a includes, for example, a pipe 24a and a valve 25a. Pipe 24a is connected in communication with tank 22. Valve 25a is provided on pipe 24a. When valve 25a is open, supply unit 23a supplies the main sublimable substance to tank 22. When valve 25a is closed, supply unit 23a does not supply the main sublimable substance to tank 22. Similarly, supply units 23b-23d include pipes 24b-24d and valves 25b-25d, respectively. Pipes 24b-24d are connected to tank 22, respectively. Valves 25b-25d are provided on pipes 24b-24d, respectively. Valves 25b and 25c each control the supply of the sub-sublimable substance to tank 22. Specifically, valve 25b controls the supply of the first sub-sublimable substance to tank 22. Valve 25c controls the supply of the second secondary sublimable substance to the reservoir 22. Valve 25d controls the supply of the solvent to the reservoir 22.

[0114] Furthermore, the valve 25a adjusts the amount of the main sublimable substance supplied to the tank 22. The amount of the main sublimable substance supplied to the tank 22 corresponds to the volume of the main sublimable substance for producing the treatment solution g. More specifically, the amount of the main sublimable substance supplied to the tank 22 corresponds to the volume of the main sublimable substance used to produce the treatment solution g. The amount of the main sublimable substance supplied to the tank 22 corresponds to the above-mentioned volume QA. Therefore, the valve 25a adjusts the volume QA.

[0115] Similarly, valves 25b and 25c adjust the amount of the sub-sublimable substance supplied to tank 22. The amount of the sub-sublimable substance supplied to tank 22 corresponds to the volume of the sub-sublimable substance for producing treatment liquid g. The amount of the main sublimable substance supplied to tank 22 corresponds to the above-mentioned volume QB. Therefore, valves 25b and 25c adjust volume QB.

[0116] Valve 25b adjusts the amount of the first sub-sublimable substance supplied to tank 22. The amount of the first sub-sublimable substance supplied to tank 22 corresponds to the volume of the first sub-sublimable substance for producing treatment liquid g. The amount of the first sub-sublimable substance supplied to tank 22 corresponds to the above-mentioned volume QB1. Therefore, valve 25b adjusts volume QB1.

[0117] Valve 25c adjusts the amount of the second sub-sublimable substance supplied to tank 22. The amount of the second sub-sublimable substance supplied to tank 22 corresponds to the volume of the second sub-sublimable substance for producing treatment liquid g. The amount of the second sub-sublimable substance supplied to tank 22 corresponds to the above-mentioned volume QB2. Therefore, valve 25c adjusts volume QB2.

[0118] Valve 25d adjusts the amount of solvent supplied to tank 22. The amount of solvent supplied to tank 22 corresponds to the volume of solvent required to produce treatment liquid g. The amount of solvent supplied to tank 22 corresponds to the volume QC described above. Therefore, valve 25d adjusts the volume QC.

[0119] Each of the valves 25a-25d may include, for example, a flow control valve. Each of the valves 25a-25d may include, for example, a flow control valve and an on-off valve.

[0120] The supply unit 23a is connected in communication with the supply source 26a. For example, the supply source 26a is connected to the pipe 24a. The supply source 26a sends the main sublimable substance to the supply unit 23a. Similarly, the supply units 23b-23d are connected in communication with the supply sources 26b-26d. For example, the supply sources 26b-26d are connected to the pipes 24b-24d, respectively. The supply sources 26b and 26c send the sub-sublimable substance to the supply units 23b and 23c, respectively. Specifically, the supply source 26b sends the first sub-sublimable substance to the supply unit 23b. The supply source 26c sends the second sub-sublimable substance to the supply unit 23c. The supply source 26d sends the solvent to the supply unit 23d.

[0121] The pumping unit 31 includes a pipe 32 and a joint 33. The pipe 32 is connected to the tank 22. The joint 33 is connected to the pipe 32. The joint 33 is further connected to the pipe 17a. The pipe 32 is connected to the pipe 17a by the joint 33. Therefore, the tank 22 is connected to the first supply unit 15a via the pipe 32 and the joint 33. The tank 22 is connected to the nozzle 16a.

[0122] The pumping unit 31 further includes a pump 34 and a filter 35. The pump 34 is provided in the piping 32. When the pump 34 is operating, the pump 34 pumps the processing liquid g from the tank 22 to the first supply section 15a. When the pump 34 is stopped operating, the pump 34 does not pump the processing liquid g from the tank 22 to the first supply section 15a. The filter 35 is provided in the piping 32. The processing liquid g passes through the filter 35. The filter 35 filters the processing liquid g. The filter 35 removes foreign matter from the processing liquid g.

[0123] See Figure 3. The control unit 10 is capable of communicating with the first supply source 19a. The control unit 10 controls the first supply source 19a. The control unit 10 controls the generation unit 21. The control unit 10 controls the supply units 23a-23d. The control unit 10 controls the valves 25a-25d. The control unit 10 controls the pumping unit 31. The control unit 10 controls the pump 34.

[0124] The control unit 10 has processing liquid condition information for controlling the first supply source 19a. The processing liquid condition information includes information related to the conditions of the processing liquid. The processing liquid condition information includes, for example, a target regarding the composition of the processing liquid g. The target regarding the composition of the processing liquid g specifies, for example, the values ​​of volumes QA, QB, and QC. The target regarding the composition of the processing liquid g specifies, for example, the ratio of volumes QA, QB, and QC. The processing liquid condition information is pre-stored in a storage medium of the control unit 10.

[0125] <1-6. Operational Example of First Supply Source 19a and Processing Unit 11> 5 is a flowchart showing the steps of the substrate processing method of the first embodiment. The substrate processing method includes step S1 and steps S11-S18. Step S1 is performed by first supply source 19a. Steps S11-S18 are substantially performed by processing unit 11. Step S1 is performed in parallel with steps S11-S18. First supply source 19a and processing unit 11 operate under the control of control unit 10.

[0126] Each of steps S1, S11 to S18 will be described with reference to FIG. 4 as needed.

[0127] Step S1: Processing liquid generation process In the processing liquid generating step, processing liquid g is generated.

[0128] The control unit 10 controls the generation unit 21 based on the processing solution condition information. The generation unit 21 generates the processing solution g. Specifically, the control unit 10 controls the supply units 23a-23d based on a target for the composition of the processing solution g. The supply unit 23a supplies the main sublimable substance to the tank 22. The supply units 23b and 23c supply the sub-sublimable substance to the tank 22. The supply unit 23b supplies the first sub-sublimable substance to the tank 22. The supply unit 23c supplies the second sub-sublimable substance to the tank 22. The supply unit 23d supplies the solvent to the tank 22. The processing solution g is generated in the tank 22. The processing solution g contains a main sublimable substance, a sub-sublimable substance, and a solvent. The actual composition of the main sublimable substance, the sub-sublimable substance, and the solvent in the processing solution g conforms to the target for the composition of the processing solution g. That is, the processing liquid g conforms to the processing liquid condition information. The processing liquid g is stored in the tank 22.

[0129] Step S11: Rotation start process The substrate holder 13 holds the substrate W. The substrate W is held in a substantially horizontal position. The rotation driver 14 rotates the substrate holder 13. As a result, the substrate W held by the substrate holder 13 starts to rotate.

[0130] In steps S12-S17 described below, the substrate W continues to rotate, for example.

[0131] Step S12: Chemical solution supply process In the chemical liquid supplying step, the chemical liquid is supplied to the substrate W.

[0132] The second supply unit 15b supplies the chemical liquid to the substrate W held by the substrate holder 13. Specifically, the valve 18b opens. The nozzle 16b ejects the chemical liquid. The chemical liquid is supplied to the upper surface of the substrate W. For example, the chemical liquid etches the substrate W. For example, the chemical liquid removes a native oxide film from the substrate W.

[0133] Thereafter, the second supply unit 15b stops supplying the chemical liquid to the substrate W. Specifically, the valve 18b closes, and the nozzle 16b stops discharging the chemical liquid.

[0134] Step S13: Rinse liquid supply process In the rinse liquid supplying step, the rinse liquid is supplied to the substrate W.

[0135] The third supply unit 15c supplies the rinse liquid to the substrate W held by the substrate holder 13. Specifically, the valve 18c opens. The nozzle 16c ejects the rinse liquid. The rinse liquid is supplied to the upper surface of the substrate W. For example, the rinse liquid cleans the substrate W. For example, the rinse liquid removes chemicals from the substrate W.

[0136] Thereafter, the third supply unit 15c stops supplying the rinsing liquid to the substrate W. Specifically, the valve 18c closes, and the nozzle 16c stops discharging the rinsing liquid.

[0137] Step S14: Substitute liquid supply process In the substitute liquid supplying step, the substitute liquid is supplied to the substrate W.

[0138] The fourth supply unit 15d supplies the substitute liquid to the substrate W held by the substrate holder 13. Specifically, the valve 18d opens. The nozzle 16d discharges the substitute liquid. The substitute liquid is supplied to the upper surface of the substrate W. The substitute liquid removes the rinse liquid from the substrate W. The rinse liquid on the substrate W is replaced with the substitute liquid.

[0139] Thereafter, the fourth supply unit 15d stops supplying the substitute liquid to the substrate W. Specifically, the valve 18d closes. The nozzle 16d stops discharging the substitute liquid.

[0140] Step S15: Processing liquid supply process In the processing liquid supplying step, the processing liquid g is supplied to the substrate W.

[0141] The pressure-feeding unit 31 supplies the processing liquid g to the first supply unit 15a. The first supply unit 15a supplies the processing liquid g to the substrate W held by the substrate holder 13. Specifically, the pump 34 pressure-feeds the processing liquid g from the tank 22 to the first supply unit 15a. The valve 18a opens. The nozzle 16a ejects the processing liquid g. The processing liquid g is supplied to the upper surface of the substrate W. The processing liquid g removes the substitute liquid from the substrate W. The substitute liquid on the substrate W is replaced with the processing liquid g.

[0142] Thereafter, the pumping unit 31 stops supplying the processing liquid g to the first supply unit 15a. The first supply unit 15a stops supplying the processing liquid g to the substrate W. Specifically, the pump 34 stops. The valve 18a closes. The nozzle 16a stops discharging the processing liquid g.

[0143] 6 is a diagram schematically illustrating the substrate W in the processing liquid supply step. When the substrate W is held by the substrate holder 13, the pattern WP is located on the upper surface of the substrate W. When the substrate W is held by the substrate holder 13, the pattern WP faces upward.

[0144] The processing liquid g on the substrate W forms a liquid film G. The liquid film G is located on the substrate W. The liquid film G contacts the substrate W. The liquid film G covers the substrate W. The liquid film G covers the upper surface of the substrate W.

[0145] The entire pattern WP is immersed in the liquid film G. The entire protrusions T are immersed in the liquid film G. The recesses A are filled with the liquid film G. The entire recesses A are filled with only the liquid film G.

[0146] The liquid film G has an upper surface G1. The upper surface G1 is located at a position higher than the entire pattern WP. The upper surface G1 does not intersect with the pattern WP. The upper surface G1 is located at a position higher than the entire protrusions T. The upper surface G1 does not intersect with the protrusions T.

[0147] The substitute liquid has already been removed from the substrate W by the processing liquid g. Therefore, the substitute liquid does not exist on the substrate W. The substitute liquid does not remain in the recess A.

[0148] Gas J exists above the liquid film G. The pattern WP does not come into contact with gas J. The pattern WP is not exposed to gas J. The protrusions T do not come into contact with gas J. The protrusions T are not exposed to gas J.

[0149] The gas J contacts the liquid film G. The gas J contacts the upper surface G1. The upper surface G1 corresponds to the gas-liquid interface between the liquid film G and the gas J. Therefore, the pattern WP does not intersect with the gas-liquid interface between the liquid film G and the gas J. The convex portion T does not intersect with the gas-liquid interface between the liquid film G and the gas J.

[0150] In the processing liquid supplying step, the height position of the upper surface G1 may further be adjusted. For example, the height position of the upper surface G1 may be adjusted while the nozzle 16a is supplying the processing liquid g to the substrate W. For example, the height position of the upper surface G1 may be adjusted after the nozzle 16a stops supplying the processing liquid g. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation time of the substrate W.

[0151] Here, adjusting the height position of the upper surface G1 corresponds to adjusting the thickness HG of the liquid film G. The thickness HG of the liquid film G corresponds to the thickness of the processing liquid g on the substrate W. The thickness HG of the liquid film G is, for example, the distance in the vertical direction Z between the base end Tp of the convex portion T and the upper surface G1.

[0152] Step S16: Solidified film formation process In the solidified film forming step, the solvent evaporates from the processing solution g on the substrate W. In the solidified film forming step, a solidified film is formed on the substrate W. The solidified film includes a primary sublimable substance and a secondary sublimable substance.

[0153] FIG. 7 is a diagram schematically illustrating the substrate W in the solidified film forming process. As described above, the solvent has a relatively high vapor pressure. At room temperature, the solvent has a higher vapor pressure than the primary and secondary sublimable substances. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W. The solvent changes smoothly from a liquid to a gas.

[0154] When the solvent evaporates from the processing solution g on the substrate W, the solvent leaves the processing solution g on the substrate W. As the solvent evaporates from the processing solution g on the substrate W, the amount of solvent contained in the liquid film G decreases. As the amount of solvent contained in the liquid film G decreases, the concentration of the primary sublimable substance in the liquid film G increases. As the amount of solvent contained in the liquid film G decreases, the concentration of the secondary sublimable substance in the liquid film G also increases.

[0155] Eventually, the main sublimable substance and the sub-sublimable substance in the liquid film G begin to precipitate on the substrate W. That is, the main sublimable substance changes from a solute in the processing liquid g to a solid-phase main sublimable substance. The sub-sublimable substance changes from a solute in the processing liquid g to a solid-phase sub-sublimable substance. The solid-phase main sublimable substance and the solid-phase sub-sublimable substance produce a solidified film K. The solid-phase main sublimable substance and the solid-phase sub-sublimable substance form the solidified film K. The solidified film K does not contain solvent. The solidified film K is solid. The solidified film K is formed on the substrate W.

[0156] Due to evaporation of the solvent and precipitation of the main sublimable substance and the sub-sublimable substance, the liquid film G gradually decreases. Due to the precipitation of the main sublimable substance and the sub-sublimable substance, the liquid film G gradually changes into a solidified film K. Due to the precipitation of the main sublimable substance and the sub-sublimable substance, the solidified film K gradually increases. The solidified film K gradually grows.

[0157] First, the upper part of the liquid film G turns into a solidified film K. The solidified film K is located above the liquid film G. The solidified film K covers the upper surface G1 of the liquid film G.

[0158] When the solidified film K covers the entire upper surface G1, the solidified film K separates the liquid film G from the gas J. The liquid film G is in contact with the solidified film K. The upper surface G1 of the liquid film G is in contact with the solidified film K. The liquid film G is not in contact with the gas J. The upper surface G1 is not in contact with the gas J. The gas-liquid interface between the liquid film G and the gas J disappears. The gas J is in contact with the solidified film K.

[0159] Therefore, the pattern WP does not intersect with the gas-liquid interface. The liquid film G does not exert a significant force on the pattern WP. The protrusion T does not intersect with the gas-liquid interface. The liquid film G does not exert a significant force on the protrusion T.

[0160] The solidified film K has an upper surface K1. The upper surface K1 is in contact with the gas J. The height position of the upper surface K1 when the liquid film G begins to change into the solidified film K is called the initial height position of the upper surface K1. The initial height position of the upper surface K1 is substantially equal to the height position of the upper surface G1 immediately before the liquid film G begins to change into the solidified film K.

[0161] The solidified film K has a thickness HK. The thickness HK of the solidified film K is, for example, the distance in the vertical direction Z between the upper surface G1 of the liquid film G and the upper surface K1 of the solidified film K.

[0162] As the solidified film K increases, the liquid film G decreases. As the thickness HK of the solidified film K increases, the thickness HG of the liquid film G decreases. As the thickness HK of the solidified film K increases, the height position of the upper surface G1 decreases. The liquid film G gradually decreases without exerting a significant force on the protrusions T. The solvent gradually leaves the substrate W without exerting a significant force on the protrusions T.

[0163] The solidified film K may be formed before the processing liquid supply process is completed. A part of the period during which the solidified film forming process is performed may overlap a part of the period during which the processing liquid supply process is performed.

[0164] 8 is a diagram showing a substrate W in the solidified film forming process. FIG. 8 shows a schematic diagram of the substrate W at the end of the solidified film forming process, for example. Only the solidified film K remains on the substrate W. At the end of the solidified film forming process, all of the liquid film G has disappeared from the substrate W. No liquid film G remains in the recess A. All of the solvent has disappeared from the substrate W. No solvent remains in the recess A either.

[0165] The solidified film K extends to the base end Tp of the substrate W. The recess A is filled with the solidified film K. The entire recess A is filled only with the solidified film K. After the entire liquid film G has disappeared from the substrate W, the thickness HK of the solidified film K is, for example, the distance in the vertical direction Z between the base end Tp of the protrusion T and the upper surface K1 of the solidified film K.

[0166] The solidified film K is in contact with the pattern WP. The solidified film K supports the pattern WP. The solidified film K protects the pattern WP. For example, the solidified film K prevents the pattern WP from collapsing.

[0167] The solidified film K contacts the protrusion T. The solidified film K contacts both the first side and the second side of the protrusion T. The solidified film K supports the protrusion T. The solidified film K supports the protrusion T from both the first side and the second side of the protrusion T. The solidified film K protects the protrusion T. For example, the solidified film K prevents the protrusion T from collapsing. For example, the solidified film K prevents the protrusion T from tilting toward the first side. For example, the solidified film K prevents the protrusion T from tilting toward the second side.

[0168] Step S17: Sublimation process In the sublimation step, the solidified film K is sublimated.

[0169] The fifth supply unit 15e supplies dry gas to the substrate W held by the substrate holder 13. Specifically, the valve 18e opens. The nozzle 16e ejects dry gas. The nozzle 16e blows the dry gas onto the substrate W. The dry gas is supplied to the upper surface of the substrate W. The dry gas is supplied to the solidified film K. The solidified film K is exposed to the dry gas. This causes the solidified film K to sublimate. The solidified film K changes into gas without passing through a liquid state. The solidified film K is removed from the substrate W by sublimation.

[0170] Thereafter, the fifth supply unit 15e stops supplying the dry gas to the solidified film K. Specifically, the valve 18e closes, and the nozzle 16e stops blowing out the dry gas.

[0171] 9 is a diagram schematically showing the substrate W in the sublimation process. As the solidified film K sublimes, the solidified film K gradually decreases in thickness. As the solidified film K sublimes, the height position of the upper surface K1 of the solidified film K decreases. As the solidified film K sublimes, the thickness HK of the solidified film K gradually decreases. As the solidified film K sublimes, the solidified film K gradually becomes thinner.

[0172] Note that the sublimable substance has sublimation properties. Therefore, sublimation of the solidified film K may start before the liquid film G disappears from the substrate W. A part of the period during which the sublimation process is performed may overlap a part of the period during which the solidified film forming process is performed.

[0173] The pattern WP begins to be exposed to the gas J. The protrusion T begins to be exposed to the gas J.

[0174] When the solidified film K sublimes, the solidified film K does not change into a liquid. Therefore, in the sublimation process, no liquid exists on the substrate W. In the sublimation process, no liquid exists in the recess A. In the sublimation process, no gas-liquid interface occurs near the pattern WP.

[0175] Therefore, the pattern WP does not intersect with the gas-liquid interface. The solidified film K does not exert a significant force on the pattern WP. The solidified film K leaves the substrate W without exerting a significant force on the pattern WP. The protrusions T do not intersect with the gas-liquid interface. The solidified film K does not exert a significant force on the protrusions T. The solidified film K leaves the substrate W without exerting a significant force on the protrusions T.

[0176] FIG. 10 is a diagram showing a substrate W during the sublimation process. FIG. 10 shows a schematic diagram of the substrate W at the end of the sublimation process, for example. At the end of the sublimation process, the entire solidified film K disappears from the substrate W. No liquid exists on the substrate W. The entire pattern WP is exposed to gas. The entire protrusions T are exposed to gas. The entire recesses A are filled only with gas J. The substrate W is dried.

[0177] The above-described treatment liquid supplying process, solidified film forming process, and sublimation process are examples of drying processes. The above-described treatment liquid supplying process, solidified film forming process, and sublimation process correspond to examples of using treatment liquid g. Treatment liquid g is used in an environment at room temperature. Treatment liquid g is used in an environment at normal pressure.

[0178] Step S18: Rotation stop process The rotation driver 14 stops the rotation of the substrate holder 13. The substrate W held by the substrate holder 13 stops rotating. The substrate W comes to a standstill. The processing unit 11 finishes processing the substrate W.

[0179] <1-7. Technical significance of processing solution g> The technical significance of treatment solution g will be explained using Experimental Examples 1, 2, and 3 and a comparative example.

[0180] The only difference between Experimental Examples 1-3 and the Comparative Example is the sub-sublimable substance, and the conditions other than the sub-sublimable substance are the same between Experimental Examples 1-3 and the Comparative Example.

[0181] The conditions of Experimental Example 1 will be described. In Experimental Example 1, the substrate W is processed in a processing liquid supply step, a solidified film formation step, and a sublimation step. More specifically, the substrate W is processed in a chemical liquid supply step, a rinse liquid supply step, a replacement liquid supply step, a processing liquid supply step, a solidified film formation step, and a sublimation step.

[0182] The chemical used in the chemical supplying step is hydrofluoric acid. Hydrofluoric acid is a mixture of hydrogen fluoride and water. The volume ratio of hydrogen fluoride to water is as follows: Hydrogen fluoride:water = 1:10 (volume ratio)

[0183] The rinse liquid used in the rinse liquid supply step is deionized water (DIW).

[0184] The substitute liquid used in the substitute liquid supplying step is isopropyl alcohol.

[0185] The processing solution g used in the processing solution supplying step consists of a main sublimable substance, a sub-sublimable substance, and a solvent. The main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is camphor. The solvent is isopropyl alcohol (IPA).

[0186] The volume ratio of cyclohexanone oxime contained in treatment solution g to isopropyl alcohol contained in treatment solution g is as follows: Cyclohexanone oxime: isopropyl alcohol = 1:40 (volume ratio)

[0187] In other words, the ratio of volume QA to volume QC is: QA:QC=1:40 (volume ratio)

[0188] The volume ratio of cyclohexanone oxime contained in treatment solution g to camphor contained in treatment solution g is as follows: Cyclohexanone oxime: camphor = 100:5 (volume ratio)

[0189] In other words, the volume ratio of the volume QA to the volume QB is as follows: QA:QB=100:5 (volume ratio)

[0190] In the solidified film forming step, the substrate W is rotated at a rotation speed of 1500 rpm.

[0191] In the sublimation step, a dry gas is supplied to the substrate W while the substrate W is rotated at a rotation speed of 1500 rpm.

[0192] The conditions for Experimental Example 2 are as follows: In Experimental Example 2, the sub-sublimable substance is acetoxime.

[0193] The volume ratio of cyclohexanone oxime contained in treatment solution g to acetoxime contained in treatment solution g is as follows: Cyclohexanone oxime:acetoxime = 100:5 (volume ratio)

[0194] The conditions of Experimental Example 3 will be explained. In Experimental Example 3, the sub-sublimable substances are camphor and acetoxime. Specifically, the sub-sublimable substances consist of a first sub-sublimable substance and a second sub-sublimable substance. The first sub-sublimable substance is camphor. The second sub-sublimable substance is acetoxime. The volume ratio of cyclohexanone oxime contained in treatment solution g to camphor contained in treatment solution g and acetoxime contained in the treatment solution is as follows: Cyclohexanone oxime: camphor: acetoxime = 100:2.5:2.5 (volume ratio)

[0195] In other words, in Experimental Example 3, the ratio of the volume QA to the volume QB1 to the volume QB2 is as follows: QA:QB1:QB2=100:2.5:2.5 (volume ratio)

[0196] The conditions of the comparative example will be explained. In the comparative example, the processing solution g used in the processing solution supplying step consists of a main sublimable substance and a solvent. That is, the processing solution g does not contain a side sublimable substance. Specifically, the processing solution g consists of cyclohexanone oxime and isopropyl alcohol. The processing solution g does not contain camphor. The processing solution g does not contain acetoxime.

[0197] Each substrate W processed in Experimental Examples 1-3 and Comparative Example was evaluated by its collapse rate. The collapse rate is the probability that the pattern WP on the substrate W will collapse when the substrate W is processed. In other words, the collapse rate is the probability that the protrusion T on the substrate W will collapse when the substrate W is processed.

[0198] Examples of collapse rates are as follows. The collapse rates include, for example, an average collapse rate Da (%), a maximum collapse rate Db (%), and a minimum collapse rate Dc (%). The average collapse rate Da is the average value of multiple local collapse rates di. The maximum collapse rate Db is the maximum value of multiple local collapse rates di. The minimum collapse rate Dc is the minimum value of multiple local collapse rates di. Each local collapse rate di (%) is the collapse rate in each local area Ei. i is any natural number from 1 to NE. NE is the number of local areas Ei. The number NE is a natural number greater than or equal to 2. Each local area Ei is a microscopic region on the substrate W. Each local area Ei is magnified 50,000 times using a scanning electron microscope, for example. An observer observes the pattern WP (protrusion T) in each local area Ei. The observer evaluates each protrusion T in each local area Ei one by one. Specifically, the observer determines for each convex portion T whether the convex portion T has collapsed. Here, the number of convex portions T determined in each local area Ei is defined as NPi. The number of convex portions T determined to have collapsed in each local area Ei is defined as NTi. The number NTi is equal to or less than the number NPi. The local collapse rate di is the ratio of the number NTi to the number NPi. The local collapse rate di is defined, for example, by the following equation: di=NTi / NPi*100 (%)

[0199] Fig. 11 is a table showing the collapse rates of the substrates W processed in Experimental Examples 1-3 and the Comparative Example. Fig. 12 is a graph showing the collapse rates of the substrates W processed in Experimental Examples 1-3 and the Comparative Example.

[0200] The average collapse rates Da of Experimental Examples 1-3 are each lower than the average collapse rate Da (=1.07) of the Comparative Example. The maximum collapse rates Db of Experimental Examples 1-3 are each lower than the maximum collapse rate Db (=2.87) of the Comparative Example. The minimum collapse rates Dc of Experimental Examples 1-3 are each lower than the minimum collapse rate Dc (=0.30) of the Comparative Example.

[0201] The maximum collapse rate Db (=0.75) of Experimental Example 2 is lower than the average collapse rate Da of the comparative example.

[0202] The maximum collapse rate Db (=0.20) of Experimental Example 3 is lower than the average collapse rate Da of the comparative example. The maximum collapse rate Db (=0.20) of Experimental Example 3 is lower than the minimum collapse rate Dc of the comparative example.

[0203] The average collapse rate Da (=0.03) of Experimental Example 3 is lower than the minimum collapse rate Dc of the comparative example.

[0204] The average collapse rate Da of Experimental Example 3 is lower than the average collapse rate Da of Experimental Examples 1 and 2. The maximum collapse rate Db of Experimental Example 3 is lower than the maximum collapse rate Db of Experimental Examples 1 and 2. The minimum collapse rate Dc of Experimental Example 3 is lower than the minimum collapse rate Dc of Experimental Examples 1 and 2.

[0205] The difference between the maximum collapse rate Db and the minimum collapse rate Dc is called the difference F. The difference F of Experimental Example 1 is 1.98%. The difference F of Experimental Example 2 is 0.72%. The difference F of Experimental Example 3 is 0.20%. The difference F of the comparative example is 2.57%. The differences F of Experimental Examples 1-3 are each smaller than the difference F of the comparative example.

[0206] The difference F in Experimental Example 3 is smaller than the difference F in Experimental Examples 1 and 2.

[0207] When Experimental Examples 1 to 3 are not distinguished, they are collectively referred to as Experimental Examples.

[0208] In summary, for example, in the experimental example, local collapse of the pattern WP was less than in the comparative example. For example, in the experimental example, partial collapse of the pattern WP was less than in the comparative example. In the experimental example, the pattern WP was protected more appropriately than in the comparative example. In the experimental example, the substrate W was dried in a state in which the pattern WP was suitably protected. In the experimental example, the substrate W was processed more appropriately than in the comparative example.

[0209] <1-8. Mechanism of Pattern WP Collapse> The present inventors speculate that the mechanism of collapse of the pattern WP in the comparative example is as follows.

[0210] 13, 14, 15, 16, and 17 are diagrams illustrating the mechanism of collapse of the pattern WP. Figures 13-16 are diagrams each illustrating a substrate W in a solidified film forming step. Figure 17 is a diagram illustrating a substrate W in a sublimation step.

[0211] See Figure 13. The processing solution g contains a primary sublimable substance. The processing solution g does not contain a secondary sublimable substance.

[0212] In the solidified film forming process, the processing solution g on the substrate W generates a plurality of crystal nuclei mA. The crystal nuclei mA are generated in the processing solution g. The crystal nuclei mA are made of a main sublimable substance. The crystal nuclei mA are derived from the main sublimable substance. In this specification, the crystal nuclei mA of the main sublimable substance are referred to as main crystal nuclei mA.

[0213] The primary crystal nuclei mA are solid. The primary crystal nuclei mA are fine particles.

[0214] See Figure 14. The main crystal nuclei mA grow into crystals MA on the substrate W. The main crystal nuclei mA change into crystals MA in the processing solution g. The crystals MA are made of a main sublimable substance. In this specification, the crystals MA of the main sublimable substance are called main crystals MA.

[0215] The primary crystals MA are solid. The primary crystals MA have a larger grain size than the primary crystal nuclei mA. The primary crystals MA constitute the solidified film K. In other words, the solidified film K contains the primary crystals MA. However, the solidified film K does not contain any secondary sublimable material.

[0216] As the main crystal nuclei mA grow into main crystals MA, the main crystal nuclei mA disappear. In Figure 14, the disappeared main crystal nuclei mA are indicated by dashed lines.

[0217] As the main crystal MA grows, it absorbs main crystal nuclei mA other than the main crystal nuclei mA from which the main crystal MA originates. As a result, the number of main crystal MA is less than the number of main crystal nuclei mA generated. In Figure 14, the main crystal nuclei mA absorbed by the main crystal MA are shown by dashed lines.

[0218] Furthermore, some of the primary crystals MA may absorb other primary crystals MA, where the other primary crystals MA are, for example, adjacent to some of the primary crystals MA, where the other primary crystals MA grow slower than some of the primary crystals MA, or where the other primary crystals MA are, for example, smaller than some of the primary crystals MA, resulting in a further reduction in the number of primary crystals MA.

[0219] See Figure 15. The primary crystals MA continue to grow on the substrate W. The grain size of the primary crystals MA on the substrate W becomes excessively large.

[0220] Eventually, the main crystals MA come into contact with each other on the substrate W. For example, two main crystals MA that are adjacent to each other come into contact with each other.

[0221] After the primary crystals MA come into contact with each other, minute spaces L may be formed. The minute spaces L may be, for example, grain boundaries. The minute spaces L may be, for example, cracks. The minute spaces L may be, for example, gaps.

[0222] The primary crystal MA does not exist in the minute space L. The solidified film K does not exist in the minute space L.

[0223] The minute space L is located, for example, inside the solidified film K. The minute space L is located, for example, below the solidified film K.

[0224] The minute space L is located, for example, around the main crystal MA. The minute space L is in contact with the main crystal MA, for example.

[0225] The minute space L is located between multiple main crystals MA. The minute space L is located, for example, below two main crystals MA that are in contact with each other. The minute space L is located, for example, around the pattern WP. The minute space L is in contact with the pattern WP. The minute space L is located, for example, around the protrusion T. The minute space L is in contact with the protrusion T, for example.

[0226] As described above, the grain size of the main crystals MA is excessively large. Furthermore, the number of main crystals MA is small. Therefore, the minute section L is excessively large. For example, the minute space L is larger than one recess A. For example, the length of the minute space L in the vertical direction Z is larger than the height HP of the pattern WP.

[0227] As a result, the main crystal MA does not enter at least one recess A. A recess A without the main crystal MA is generated. The solidified film K is not formed in at least one recess A. A recess A without the solidified film K is generated.

[0228] Specifically, the multiple recesses A are classified into first recesses A1 and second recesses A2. The first recesses A1 are recesses A where the solidified film K is substantially present. The second recesses A2 are recesses A where the solidified film K is substantially absent. When the solidified film K does not contain a sub-sublimable substance, the recesses A include the second recesses A2 in addition to the first recesses A1. When the solidified film K does not contain a sub-sublimable substance, the second recesses A2 are generated.

[0229] The multiple protrusions T are classified into first protrusions T1 and second protrusions T2. The first protrusions T1 are protrusions T that do not contact the second recesses A2. That is, the first protrusions T1 contact the first recesses A1. The first recesses A1 contact both the first side and the second side of the second protrusions T2. The second protrusions T2 are protrusions T that contact the second recesses A2. For example, the second recesses A2 contact either the first side or the second side of the second protrusions T2. Alternatively, the second recesses A2 contact both the first side and the second side of the second protrusions T2. When the solidified film K does not contain a sub-sublimable substance, the protrusions T include the second protrusions T2 in addition to the first protrusions T1. If the solidified film K does not contain a sub-sublimable substance, the second convex portion T2 is generated.

[0230] The processing liquid g remains in the minute space L.

[0231] Referring to FIG. 16, the processing liquid g in the minute space L gradually decreases. The gas J enters the minute space L. The processing liquid g and the gas J exist in the minute space L. The processing liquid g and the gas J in the minute space L form a gas-liquid interface R. The gas-liquid interface R is located, for example, at the second recess A2.

[0232] The gas-liquid interface R located in the second recess A2 intersects with the second protrusion T2. ​​Therefore, the treatment liquid g exerts a significant force on the second protrusion T2. ​​Specifically, the second protrusion T2 is subjected to the surface tension of the treatment liquid g.

[0233] The second recess A2 does not have the solidified film K. Therefore, the solidified film K does not support at least either the first side or the second side of the second protrusion T2. ​​Therefore, when the second protrusion T2 is subjected to the surface tension of the processing liquid g, the second protrusion T2 collapses very easily.

[0234] See Fig. 17. In the sublimation step, the solidified film K is sublimated. The substrate W is dried by the sublimation of the solidified film K. The second protrusion T2 remains collapsed.

[0235] In summary, if the solidified film K does not contain a sub-sublimable substance, the main crystals MA contained in the solidified film K will be excessively large. As a result, excessively large microscopic spaces L may be formed between the main crystals MA. In this case, some of the convex portions T correspond to the second convex portions T2. The second convex portions T2 are not properly supported by the solidified film K. The positions of the second convex portions T2 are distributed locally. If the processing liquid g remaining in the microscopic space L forms an air-liquid interface R that intersects with the second convex portions T2, the second convex portions T2 will collapse. In other words, local collapse of the pattern WP occurs.

[0236] The present inventors presume that the collapse of the pattern WP occurred in the comparative example due to the mechanism described above.

[0237] In the above-described mechanism, the reduction of the processing liquid g in the microspace L occurred in the solidified film formation process. The generation of the gas-liquid interface R in the microspace L occurred in the solidified film formation process. The collapse of the pattern WP (first convex portion T1) occurred in the solidified film formation process. However, this is not limited to this. The reduction of the processing liquid g in the microspace L may occur in at least one of the solidified film formation process and the sublimation process. The generation of the gas-liquid interface R in the microspace L may occur in at least one of the solidified film formation process and the sublimation process. The collapse of the pattern WP (first convex portion T1) may occur in at least one of the solidified film formation process and the sublimation process. Even in these cases, the second convex portion T2 collapses very easily.

[0238] <1-9. Pattern WP Protection Mechanism> The present inventors have investigated the mechanism of protection of the pattern WP in the experimental example. Four mechanisms related to the protection of the pattern WP are explained below. The present inventors have inferred that at least one of the four mechanisms worked in the experimental example.

[0239] <1-9-1. First example of the mechanism for protecting pattern WP> 18(a) to 18(d) are diagrams illustrating a first example of a mechanism for protecting the pattern WP, and are diagrams each schematically illustrating the substrate W in the solidified film forming step.

[0240] Referring to Figure 18(a), the processing solution g contains a primary sublimable substance and a secondary sublimable substance.

[0241] In the solidified film formation process, the processing solution g on the substrate W generates multiple main crystal nuclei mA and multiple sub-crystal nuclei mB. The main crystal nuclei mA and the sub-crystal nuclei mB are each generated in the processing solution g. The main crystal nuclei mA are made of a main sublimable substance. The main crystal nuclei mA are derived from the main sublimable substance. The sub-crystal nuclei mB are made of a sub-sublimable substance. The sub-crystal nuclei mB are derived from the sub-sublimable substance. The main crystal nuclei mA and the sub-crystal nuclei mB are each solid. The main crystal nuclei mA and the sub-crystal nuclei mB are each fine particles.

[0242] The sub-crystal nuclei mB are generated, for example, at positions between a plurality of main crystal nuclei mA, and are generated, for example, substantially simultaneously with the main crystal nuclei mA.

[0243] See Figure 18(b). The main crystal nuclei mA grow into main crystals MA on the substrate W. The main crystal nuclei mA change into main crystals MA in the processing solution g. The main crystals MA are made of a main sublimable substance. The main crystals MA are solid. The main crystals MA are larger than the main crystal nuclei mA.

[0244] The sub-crystal nuclei mB grow into sub-crystals MB on the substrate W. The sub-crystal nuclei mB change into sub-crystals MB in the processing solution g. The sub-crystals MB are made of a sub-sublimable substance. The sub-crystals MB are solid. The sub-crystals MB are larger than the sub-crystal nuclei mB.

[0245] For example, the transformation from the sub-crystal nuclei mB to the sub-crystal MB occurs substantially simultaneously with the transformation from the main crystal nuclei mA to the main crystal MA.

[0246] The sub-crystals MB grow, for example, at positions between the plurality of main crystals MA.

[0247] The sub-crystals MB grow, for example, in substantially the same manner as the main crystals MA. The sub-crystals MB grow, for example, substantially simultaneously with the main crystals MA. Therefore, the size of the sub-crystals MB is, for example, substantially the same as the size of the main crystals MA. The grain size of the sub-crystals MB is, for example, substantially the same as the grain size of the main crystals MA.

[0248] The main crystals MA and the sub-crystals MB constitute the solidified film K. In other words, the solidified film K includes the main crystals MA and the sub-crystals MB.

[0249] When the primary crystal MA grows, it absorbs primary crystal nuclei mA other than the primary crystal nuclei mA from which the primary crystal MA originates. As a result, the number of primary crystal MA is less than the number of primary crystal nuclei mA generated.

[0250] Furthermore, some of the main crystals MA may absorb other main crystals MA, so that the number of main crystals MA is further reduced.

[0251] When the subcrystal MB grows, it absorbs subcrystal nuclei mB other than the original subcrystal nuclei mB from which the subcrystal MB grew. As a result, the number of subcrystal MBs is less than the number of subcrystal nuclei mB.

[0252] Furthermore, some sub-crystal MBs may absorb other sub-crystal MBs, which further reduces the number of sub-crystal MBs.

[0253] 18(c), the main crystal MA and the sub-crystal MB each continue to grow on the substrate W. The main crystal MA and the sub-crystal MB each become larger on the substrate W. The size of the sub-crystal MB is substantially the same as the size of the main crystal MA.

[0254] Eventually, the sub-crystal MB comes into contact with the main crystal MA on the substrate W. For example, the main crystal MA and the sub-crystal MB that are adjacent to each other come into contact with each other.

[0255] Here, no absorption occurs between the main crystal MA and the sub-crystal MB, and one of the main crystal MA and the sub-crystal MB does not absorb the other of the main crystal MA and the sub-crystal MB.

[0256] After the main crystal MA and the sub-crystal MB come into contact with each other, a minute space L may be formed. The minute space L may be, for example, a grain boundary. The minute space L may be, for example, a crack. The minute space L may be, for example, a gap.

[0257] The main crystal MA does not exist in the minute space L. The sub-crystal MB does not exist in the minute space L. The solidified film K does not exist in the minute space L.

[0258] The minute space L is located inside the solidified film K. The minute space L is located below the solidified film K, for example.

[0259] The minute space L is located around the main crystal MA. The minute space L is in contact with the main crystal MA. The minute space L is located around the sub-crystal MB. The minute space L is in contact with the sub-crystal MB.

[0260] The minute space L is located between the main crystal MA and the sub-crystal MB. The minute space L is located, for example, below the main crystal MA and the sub-crystal MB that are in contact with each other. The minute space L is located, for example, around the pattern WP. The minute space L is in contact with the pattern WP. The minute space L is located, for example, around the protrusion T. The minute space L is in contact with the protrusion T, for example.

[0261] Here, the main crystal MA and the sub-crystal MB are each relatively small, the main crystal MA is not excessively large, and the sub-crystal MB is also not excessively large.

[0262] For example, the grain size of the main crystals MA shown in Fig. 18(c) is smaller than the grain size of the main crystals MA shown in Fig. 15. Specifically, the size of the main crystals MA when the solidified film K contains a sub-sublimable substance is smaller than the size of the main crystals MA when the solidified film K does not contain a sub-sublimable substance.

[0263] For example, the particle size of the sub-crystals MB shown in Fig. 18(c) is smaller than the particle size of the main crystals MA shown in Fig. 15. Specifically, the size of the sub-crystals MB when the solidified film K contains a sub-sublimable substance is smaller than the size of the main crystals MA when the solidified film K does not contain a sub-sublimable substance.

[0264] Since the main crystal MA and the sub-crystal MB are each relatively small, the microspace L is relatively small. The microspace L is not excessively large. The microspace L when the solidified film K contains the sub-crystal MB is smaller than the microspace L when the solidified film K does not contain the sub-crystal MB. For example, the size of the microspace L shown in FIG. 18(c) is smaller than the size of the microspace L shown in FIG. 15.

[0265] When there is no distinction between the main crystals MA and the sub-crystals MB, they are simply called crystals M. When the solidified film K contains a sub-sublimable substance, the number of crystals M is the sum of the number of main crystals MA and the number of sub-crystals MB. When the solidified film K does not contain a sub-sublimable substance, the number of crystals M is only the number of main crystals MA. Therefore, when the solidified film K contains a sub-sublimable substance, the number of crystals M is greater than the number of crystals M when the solidified film K does not contain a sub-sublimable substance.

[0266] Since the number of crystals M contained in the solidified film K is relatively large, the minute space L is even smaller.

[0267] Furthermore, the sub-crystals MB grow at positions between the plurality of main crystals MA, so that the sub-crystals MB make the minute space L smaller more effectively.

[0268] For example, the minute space L is smaller than one recessed portion A. For example, the length of the minute space L in the vertical direction Z in the experimental example is smaller than the height HP of the pattern WP.

[0269] As a result, the crystals M enter all of the recesses A. A solidified film K is formed in all of the recesses A.

[0270] Therefore, when the solidified film K contains a sub-sublimable substance, all the recesses A correspond to the first recesses A1. When the solidified film K contains a sub-sublimable substance, the recesses A do not include the second recesses A2.

[0271] When the solidified film K contains a sub-sublimable substance, all the projections T correspond to the first projections T1. When the solidified film K contains a sub-sublimable substance, the projections T do not include the second projections T2.

[0272] The processing liquid g may remain in the minute space L. The processing liquid g may remain in some of the first recesses A1.

[0273] See FIG. 18(d). The processing liquid g in the minute space L gradually decreases. The gas J may enter the minute space L. The processing liquid g and the gas J may exist in the minute space L. The processing liquid g and the gas J in the minute space L may form a gas-liquid interface R. The gas-liquid interface R may be located, for example, at the first recess A1. The gas-liquid interface R may intersect with the first protrusion T1.

[0274] If the gas-liquid interface R intersects with the first convex portion T1, the treatment liquid g will exert a significant force on the first convex portion T1. Specifically, the first convex portion T1 will be subjected to the surface tension of the treatment liquid g.

[0275] The first recess A1 has a solidified film K. Therefore, the solidified film K supports both the first side of the first protrusion T1 and the second side of the first protrusion T1.

[0276] Therefore, even if the first convex portions T1 are subjected to the surface tension of the processing liquid g, the first convex portions T1 are unlikely to collapse. The solidified film K effectively protects the first convex portions T1 from the processing liquid g.

[0277] As described above, all of the protrusions T correspond to the first protrusions T1. Therefore, the solidified film K preferably supports all of the protrusions T. The solidified film K preferably protects all of the protrusions T. For example, the solidified film K prevents localized collapse of the pattern WP. For example, the solidified film K prevents partial collapse of the pattern WP.

[0278] For convenience, refer to Figures 9 and 10. In the sublimation process, the solidified film K is sublimated. The substrate W is dried by the sublimation of the solidified film K. Even after the substrate W is dried, the pattern WP is not collapsed. Even after the substrate W is dried, the pattern WP maintains its proper shape.

[0279] In summary, when the solidified film K contains a main sublimable substance and a sub-sublimable substance, at least one of the main crystals MA and the sub-crystals MB contained in the solidified film K is small. Therefore, even if a minute space L is formed between the main crystals MA and the sub-crystals MB, the minute space L is small. In this case, the entire convex portion T corresponds to the first convex portion T1. The first convex portion T1 is properly supported by the solidified film K. Even if the processing liquid g remaining in the minute space L forms an air-liquid interface R where it intersects with the first convex portion T1, the first convex portion T1 will not collapse. In other words, collapse of the pattern WP is suppressed. Local collapse of the pattern WP is also suppressed. Therefore, the pattern WP is properly protected.

[0280] The inventors presume that the pattern WP was properly protected in the experimental example by the above-mentioned mechanism.

[0281] In the above-described mechanism, the reduction of the processing liquid g in the microspace L occurs in the solidified film formation process. The generation of the gas-liquid interface R in the microspace L occurs in the solidified film formation process. However, this is not limited to this. The reduction of the processing liquid g in the microspace L may occur in at least one of the solidified film formation process and the sublimation process. The generation of the gas-liquid interface R in the microspace L may occur in at least one of the solidified film formation process and the sublimation process. Even in these cases, the pattern WP is appropriately protected.

[0282] <1-9-2. Second example of Pattern WP protection mechanism> A second example of the mechanism of protection of the pattern WP will now be described. In the first example, the generation of the sub-crystal nuclei mB was substantially simultaneous with the generation of the main crystal nuclei mA. In the first example, the growth of the sub-crystals MB was substantially simultaneous with the growth of the main crystals MA. In contrast, in the second example, the generation of the main crystal nuclei mA precedes the generation of the sub-crystal nuclei mB. In the second example, the growth of the main crystals MA precedes the growth of the sub-crystals MB.

[0283] 19(a) to 19(d) are diagrams illustrating a second example of the mechanism for protecting the pattern WP, and are diagrams each illustrating a substrate W in a solidified film forming step.

[0284] Referring to Figure 19(a), the processing solution g contains a main sublimable substance and a sub-sublimable substance.

[0285] In the solidified film forming step, the processing solution g on the substrate W generates a plurality of main crystal nuclei mA. However, the processing solution g on the substrate W has not yet generated sub-crystal nuclei mB.

[0286] 19(b), the main crystal nuclei mA grow on the substrate W into main crystals MA.

[0287] The processing solution g on the substrate W generates a plurality of sub-crystal nuclei mB. The sub-crystal nuclei mB are generated after the main crystal nuclei mA. In other words, the main crystal nuclei mA are generated before the sub-crystal nuclei mB.

[0288] 19(c), the primary crystal MA continues to grow on the substrate W.

[0289] The sub-crystal nuclei mB grow into sub-crystal MB on the substrate W. The transformation from the sub-crystal nuclei mB to the sub-crystal MB occurs later than the transformation from the main crystal nuclei mA to the main crystal MA. For example, while the main crystal MA is growing, the sub-crystal nuclei mB transform into the sub-crystal MB. For example, after the main crystal MA has grown, the sub-crystal nuclei mB transform into the sub-crystal MB.

[0290] In this way, the main crystals MA grow before the sub-crystals MB. The main crystals MA grow faster than the sub-crystals MB. Therefore, the size of the main crystals MA is larger than the size of the sub-crystals MB.

[0291] 19(d), the primary crystal MA continues to grow on the substrate W. The secondary crystal MB also continues to grow on the substrate W.

[0292] The sub-crystals MB grow later than the main crystals MA. More specifically, the sub-crystals MB begin to grow after the main crystals MA have begun to grow. The sub-crystals MB grow slower than the main crystals MA. Therefore, the size of the sub-crystals MB is smaller than the size of the main crystals MA.

[0293] Eventually, the sub-crystal MB comes into contact with the main crystal MA on the substrate W. For example, adjacent main crystal MA and sub-crystal MB come into contact with each other. After the main crystal MA and sub-crystal MB come into contact with each other, a minute space L may be formed.

[0294] Here, the sub-crystals MB are not excessively large. The sub-crystals MB are smaller. Specifically, the size of the sub-crystals MB when the main crystals MA grow before the sub-crystals MB is smaller than the size of the sub-crystals MB when the sub-crystals MB grow substantially simultaneously with the main crystals MA. For example, the size of the sub-crystals MB shown in FIG. 19(d) is smaller than the size of the sub-crystals MB shown in FIG. 18(c).

[0295] Because the sub-crystal MB is smaller, even if a microspace L is formed, the microspace L is smaller. The microspace L is not excessively large. Specifically, the size of the microspace L when the main crystal MA grows before the sub-crystal MB is smaller than the size of the microspace L when the sub-crystal MB grows substantially simultaneously with the main crystal MA. For example, the size of the microspace L shown in FIG. 19(d) is smaller than the size of the microspace L shown in FIG. 18(c).

[0296] Furthermore, the sub-crystals MB grow slower than the main crystals MA, so that the sub-crystals MB make the minute space L smaller more effectively.

[0297] Since the microscopic space L is smaller, the protrusions T are properly supported by the solidified film K. Specifically, the crystals M enter all of the recesses A. The solidified film K is formed in all of the recesses A. Therefore, all of the recesses A correspond to the first recesses A1. All of the protrusions T correspond to the first protrusions T1. Therefore, all of the protrusions T are properly supported by the solidified film K.

[0298] The protrusions T are unlikely to collapse because they are properly supported by the solidified film K. Even if an air-liquid interface R that intersects with the protrusions T is formed, the protrusions T are unlikely to collapse. Therefore, the pattern WP is properly protected.

[0299] <1-9-3. Third example of the mechanism for protecting pattern WP> A third example of the mechanism of protection of the pattern WP will be described. In this example, the generation of the main crystal nuclei mA occurs later than the generation of the sub-crystal nuclei mB. In this example, the growth of the main crystal MA occurs later than the growth of the sub-crystal MB.

[0300] 20(a) to 20(d) are diagrams illustrating a third example of the mechanism for protecting the pattern WP, and are diagrams each illustrating a substrate W in a solidified film forming step.

[0301] Referring to Figure 20(a), the processing solution g contains a main sublimable substance and a sub-sublimable substance.

[0302] In the solidified film forming step, the processing solution g on the substrate W generates a plurality of sub-crystal nuclei mB. However, the processing solution g on the substrate W has not yet generated main crystal nuclei mA.

[0303] 20(b), the sub-crystal nuclei mB grow on the substrate W into sub-crystals MB.

[0304] The processing solution g on the substrate W generates a plurality of main crystal nuclei mA. The main crystal nuclei mA are generated after the sub-crystal nuclei mB. In other words, the sub-crystal nuclei mB are generated before the main crystal nuclei mA.

[0305] 20(c), the sub-crystal MB continues to grow on the substrate W.

[0306] The main crystal nuclei mA grow into main crystals MA on the substrate W. The transformation from the main crystal nuclei mA to the main crystals MA occurs later than the transformation from the sub-crystal nuclei mB to the sub-crystals MB. For example, the main crystal nuclei mA transform into the main crystals MA while the sub-crystals MB are growing. For example, the main crystal nuclei mA transform into the main crystals MA after the sub-crystals MB have grown.

[0307] In this way, the sub-crystals MB grow before the main crystals MA. The sub-crystals MB grow faster than the main crystals MA. Therefore, the size of the sub-crystals MB is larger than the size of the main crystals MA.

[0308] 20(d), the primary crystal MA continues to grow on the substrate W. The secondary crystal MB also continues to grow on the substrate W.

[0309] The main crystal MA grows later than the sub-crystal MB. In other words, the main crystal MA starts to grow after the sub-crystal MB starts to grow. The main crystal MA grows slower than the sub-crystal MB. Therefore, the size of the main crystal MA is smaller than the size of the sub-crystal MB.

[0310] Eventually, the sub-crystal MB comes into contact with the main crystal MA on the substrate W. For example, adjacent main crystal MA and sub-crystal MB come into contact with each other. After the main crystal MA and sub-crystal MB come into contact with each other, a minute space L may be formed.

[0311] Here, the main crystal MA is not excessively large. The main crystal MA is smaller. Specifically, the size of the main crystal MA when the sub-crystal MB grows before the main crystal MA is smaller than the size of the main crystal MA when the sub-crystal MB grows substantially simultaneously with the main crystal MA. For example, the size of the main crystal MA shown in FIG. 20(d) is smaller than the size of the main crystal MA shown in FIG. 18(c).

[0312] Because the main crystal MA is smaller, even if a microspace L is formed, the microspace L is smaller. The microspace L is not excessively large. Specifically, the size of the microspace L when the subcrystal MB grows before the main crystal MA is smaller than the size of the microspace L when the subcrystal MB grows substantially simultaneously with the main crystal MA. For example, the size of the microspace L shown in FIG. 20(d) is smaller than the size of the microspace L shown in FIG. 18(c).

[0313] Furthermore, the main crystal MA grows slower than the sub-crystal MB, so that the main crystal MA effectively reduces the microscopic space L.

[0314] Since the minute space L is smaller, the protrusion T is properly supported by the solidified film K. In the third example of the mechanism, the pattern WP is properly supported by the solidified film K, as in the second example of the mechanism.

[0315] The protrusions T are unlikely to collapse because they are properly supported by the solidified film K. Even if an air-liquid interface R that intersects with the protrusions T is formed, the protrusions T are unlikely to collapse. Therefore, the pattern WP is properly protected.

[0316] <1-9-4. Fourth example of the mechanism for protecting pattern WP> A fourth example of the mechanism of protection of the pattern WP will be described. In the fourth example, the sub-crystal nuclei mB include a first sub-crystal nucleus mB1 and a second sub-crystal nucleus mB2. In the fourth example, the sub-crystals MB include a first sub-crystal MB1 and a second sub-crystal MB2. The fourth example is particularly the mechanism in Experimental Example 3.

[0317] 21(a) to 21(c) are diagrams illustrating a fourth example of the mechanism for protecting the pattern WP, and are diagrams each illustrating a substrate W in a solidified film forming step.

[0318] Referring to Figure 21(a), the processing solution g contains a main sublimable substance and a sub-sublimable substance. The sub-sublimable substance contains a first sub-sublimable substance and a second sub-sublimable substance. That is, the processing solution g contains a main sub-sublimable substance, a first sub-sublimable substance and a second sub-sublimable substance.

[0319] In the solidified film formation process, the processing solution g on the substrate W generates a plurality of main crystal nuclei mA and a plurality of sub-crystal nuclei mB. The sub-crystal nuclei mB include first sub-crystal nuclei mB1 and second sub-crystal nuclei mB2. The first sub-crystal nuclei mB1 are made of the first sub-sublimable substance. The first sub-crystal nuclei mB1 are derived from the first sub-sublimable substance. The second sub-crystal nuclei mB2 are made of the second sub-sublimable substance. The second sub-crystal nuclei mB2 are derived from the second sub-sublimable substance.

[0320] See Figure 21(b). The main crystal nuclei mA grow into main crystals MA on the substrate W. The first subcrystal nuclei mB1 grow into first subcrystals MB1 on the substrate W. The second subcrystal nuclei mB2 grow into second subcrystals MB2 on the substrate W. The first subcrystals MB1 are made of the first sub-sublimable material. The second subcrystals MB2 are made of the second sub-sublimable material.

[0321] The main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 constitute a solidified film K. In other words, the solidified film K includes the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2.

[0322] 21(c), the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 each continue to grow on the substrate W. Eventually, the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 come into contact with each other on the substrate W. After the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 come into contact with each other, a minute space L may be formed.

[0323] Here, the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 are not excessively large. The main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 are each smaller. Specifically, the size of the main crystal MA when the solidified film K contains the second sub-sublimable substance is smaller than the size of the main crystal MA when the solidified film K does not contain the second sub-sublimable substance. The size of the first sub-crystal MB1 when the solidified film K contains the second sub-sublimable substance is smaller than the size of the sub-crystal MB when the solidified film K does not contain the second sub-sublimable substance. The size of the second sub-crystal MB2 when the solidified film K contains the second sub-sublimable substance is smaller than the size of the sub-crystal MB when the solidified film K does not contain the second sub-sublimable substance. For example, the size of the main crystal MA shown in FIG. 21(c) is smaller than the size of the main crystal MA shown in FIG. 18(c). For example, the size of the first sub-crystal MB1 shown in Figure 21(c) is smaller than the size of the sub-crystal MB shown in Figure 18(c). For example, the size of the second sub-crystal MB2 shown in Figure 21(c) is smaller than the size of the sub-crystal MB shown in Figure 18(c).

[0324] Since the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 are each smaller, even if a microspace L is formed, the microspace L is smaller. The microspace L is not excessively large. Specifically, the size of the microspace L when the solidified film K contains the second sub-sublimable substance is smaller than the size of the microspace L when the solidified film K does not contain the second sub-sublimable substance. For example, the size of the microspace L shown in FIG. 21(c) is smaller than the size of the microspace L shown in FIG. 18(c).

[0325] Furthermore, the number of crystals M contained in the solidified film K is even greater because the crystals M include second sub-crystals MB2 in addition to the main crystals MA and the first sub-crystals MB1.

[0326] Since the number of crystals M contained in the solidified film K is larger, the minute space L is even smaller.

[0327] Since the minute space L is even smaller, the protrusion T is adequately protected by the solidified film K.

[0328] The protrusions T are unlikely to collapse because they are properly supported by the solidified film K. Even if an air-liquid interface R that intersects with the protrusions T is formed, the protrusions T are unlikely to collapse. Therefore, the pattern WP is properly protected.

[0329] <1-10. Effects of the First Embodiment> The substrate processing method is for processing a substrate W on which a pattern WP is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid g is supplied to the substrate W. The processing liquid g contains a main sublimable substance, a sub-sublimable substance, and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid g on the substrate W. In the solidified film forming step, a solidified film K is formed on the substrate W. The solidified film K contains a main sublimable substance and a sub-sublimable substance. In the sublimation step, the solidified film K sublimes. The substrate W is dried by the sublimation of the solidified film K. Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetoxime. Therefore, the substrate W is properly dried. Specifically, the substrate W is dried while the pattern WP is suitably protected. For example, the entire pattern WP is suitably protected. For example, even local or partial collapse of the pattern WP is preferably suppressed.

[0330] As described above, according to the substrate processing method of the first embodiment, the substrate W is dried appropriately.

[0331] The sub-sublimable substance includes a first sub-sublimable substance and a second sub-sublimable substance. The first sub-sublimable substance is camphor. The second sub-sublimable substance is acetoxime. Therefore, the pattern WP is more effectively protected. Therefore, the substrate W is more appropriately dried.

[0332] The volume QB of the sub-sublimable substance contained in the processing solution g is 0.5% or more and 20% or less of the volume QA of the main sublimable substance contained in the processing solution g. As such, the amount of the sub-sublimable substance contained in the processing solution g is relatively small. Therefore, the influence of the sub-sublimable substance on the thickness HG of the liquid film G is small. Therefore, it is easy to control the thickness HG in the processing solution supplying step. For example, in the processing solution supplying step, it is easy to control the height position of the upper surface G1 immediately before the liquid film G starts to change into a solidified film K. Therefore, it is easy to control the thickness HK of the solidified film K in the solidified film forming step. For example, in the solidified film forming step, it is easy to control the initial height position of the upper surface K1 of the solidified film K. As a result, the substrate W is dried more appropriately.

[0333] In the solidified film formation process, on the substrate W, the main crystal nuclei mA grow into main crystals MA of the main sublimable substance. In the solidified film formation process, on the substrate W, the sub crystal nuclei mB grow into sub crystals MB of the sub-sublimable substance. At least one of the main crystals MA and the sub crystals MB is relatively small. In other words, at least one of the main crystals MA and the sub crystals MB does not have an excessively large grain size. Therefore, even if a minute space L is formed between the main crystals MA and the sub crystals MB, the minute space L is relatively small. In other words, the minute space L is not excessively large. Therefore, the solidified film K can favorably support the pattern WP. Therefore, the substrate W is dried with the pattern WP favorably protected.

[0334] As described above, according to the substrate processing method of the first embodiment, the substrate W is dried appropriately.

[0335] In the solidified film formation process, the sub-crystals MB come into contact with the main crystals MA, so even if a minute space L is formed around the main crystals MA, the sub-crystals MB suitably reduce the minute space L.

[0336] In the solidified film forming process, the sub-crystals MB grow at positions between the multiple main crystals MA. Therefore, the sub-crystals MB effectively reduce the minute space L. Therefore, the pattern WP is more effectively protected.

[0337] In the solidified film forming step, the sub-crystal nuclei mB are generated at positions between the plurality of main crystal nuclei mA, and therefore the sub-crystals MB grow favorably at positions between the plurality of main crystals MA.

[0338] In the solidified film formation process, the main crystals MA grow before the sub-crystals MB, for example. Therefore, the sub-crystals MB are smaller than the main crystals MA. Therefore, the sub-crystals MB make the minute space L smaller more effectively.

[0339] In the solidified film formation process, the main crystal nuclei mA are generated, for example, before the sub-crystal nuclei mB, so it is easy for the main crystals MA to grow before the sub-crystals MB.

[0340] In the solidified film formation process, the sub-crystals MB grow, for example, before the main crystals MA. Therefore, the main crystals MA are smaller than the sub-crystals MB. Therefore, the main crystals MA make the minute space L smaller more effectively.

[0341] In the solidified film forming step, the sub-crystal nuclei mB are generated, for example, before the main crystal nuclei mA, so it is easy for the sub-crystals MB to grow before the main crystals MA.

[0342] The substrate processing apparatus 1 includes a substrate holding unit 13 and a first supply unit 15a. The substrate holding unit 13 holds a substrate W. The first supply unit 15a supplies a processing liquid g to the substrate W held by the substrate holding unit 13. The processing liquid g contains a main sublimable substance, a sub-sublimable substance, and a solvent. Therefore, when the processing liquid g is supplied to the substrate W, the solvent evaporates from the processing liquid g on the substrate W. A solidified film K is formed on the substrate W by evaporation of the solvent. The solidified film K contains a main sublimable substance and a sub-sublimable substance. Therefore, the solidified film K sublimes. The substrate is dried by the sublimation of the solidified film.

[0343] Here, the main sublimable substance is cyclohexanone oxime, and the secondary sublimable substance is at least one of camphor and acetoxime. Therefore, the substrate W is appropriately dried. Specifically, the substrate W is dried in a state in which the pattern WP is appropriately protected.

[0344] As described above, according to the substrate processing apparatus 1 of the first embodiment, the substrate W is dried appropriately.

[0345] The processing liquid g is used to dry the substrate W on which the pattern WP is formed. Specifically, the processing liquid g is a drying auxiliary liquid. The processing liquid g contains a main sublimable substance, a sub-sublimable substance, and a solvent.

[0346] Here, the primary sublimable substance is cyclohexanone oxime. The secondary sublimable substance is at least one of camphor and acetoxime. Therefore, the processing solution g makes it easier to properly dry the substrate W. Specifically, the processing solution g makes it easier to dry the substrate W while properly protecting the pattern WP. In this way, the processing solution g is useful for drying the substrate W.

[0347] As described above, the substrate W is properly dried using the processing liquid g.

[0348] 2. Second Embodiment The second embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are designated by the same reference numerals and detailed description thereof will be omitted.

[0349] <2-1. Configuration of processing unit 11> The second embodiment is substantially the same as the first embodiment in terms of the outline of the substrate processing apparatus 1. The configuration of the processing unit 11 of the second embodiment will be described below.

[0350] 22 is a diagram showing the configuration of a processing unit 11 and a first supply source 19a according to the second embodiment, and for the sake of convenience, the housing 12 is not shown in FIG.

[0351] The substrate processing apparatus 1 includes a temperature adjustment unit 50. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g on the substrate W.

[0352] The temperature adjustment unit 50 includes a first temperature adjustment unit 51 and a second temperature adjustment unit 52. The first temperature adjustment unit 51 and the second temperature adjustment unit 52 each adjust the temperature of the processing liquid g before the processing liquid g is discharged onto the substrate W.

[0353] For example, the first temperature adjustment unit 51 is attached to the first supply source 19a. The first temperature adjustment unit 51 adjusts the temperature of the processing liquid g in the first supply source 19a. For example, the first temperature adjustment unit 51 is attached to the tank 22. The first temperature adjustment unit 51 adjusts the temperature of the processing liquid g stored in the tank 22.

[0354] For example, the second temperature adjustment unit 52 is attached to the first supply unit 15a. The second temperature adjustment unit 52 adjusts the temperature of the treatment liquid g in the first supply unit 15a. For example, the second temperature adjustment unit 52 is attached to the pipe 17a. The second temperature adjustment unit 52 adjusts the temperature of the treatment liquid g flowing through the pipe 17a.

[0355] The temperature adjustment unit 50 further includes a third temperature adjustment unit 53 and a fourth temperature adjustment unit 54. The third temperature adjustment unit 53 and the fourth temperature adjustment unit 54 each adjust the temperature of the processing liquid g on the substrate W after the processing liquid g is discharged onto the substrate W.

[0356] For example, the third temperature adjustment unit 53 is disposed above the substrate W held by the substrate holding unit 13. The third temperature adjustment unit 53 adjusts the temperature of the substrate W. The third temperature adjustment unit 53 adjusts the temperature of the processing liquid g on the substrate W. The third temperature adjustment unit 53 adjusts the temperature of the liquid film G.

[0357] For example, the fourth temperature adjustment unit 54 is disposed below the substrate W held by the substrate holding unit 13. The fourth temperature adjustment unit 54 adjusts the temperature of the substrate W. The fourth temperature adjustment unit 54 adjusts the temperature of the processing liquid g on the substrate W via the substrate W.

[0358] The temperature adjustment unit 50 may include various devices for heating or cooling the processing liquid g.

[0359] For example, the temperature adjustment unit 50 may include a resistance heater, which is also called an electric heater, and includes an electric heating wire.

[0360] For example, the temperature adjustment unit 50 may include a lamp heater. The lamp heater is also called an optical heater. The lamp heater includes a light source that emits light.

[0361] For example, the temperature adjustment unit 50 may include a supply unit for supplying a temperature-adjusted fluid. The fluid is either a liquid or a gas. The liquid is, for example, water or deionized water. The gas is, for example, an inert gas. For example, the temperature adjustment unit 50 may supply a temperature-adjusted gas toward the upper surface of the substrate W. For example, the temperature adjustment unit 50 may supply a temperature-adjusted gas toward the lower surface of the substrate W. For example, the temperature adjustment unit 50 may supply a temperature-adjusted liquid toward the lower surface of the substrate W.

[0362] For example, the temperature adjustment unit 50 may include a heat exchanger.

[0363] Although not shown in the drawings, the control unit 10 controls the temperature adjustment unit 50. The control unit 10 controls the first to fourth temperature adjustment units 51-54.

[0364] The processing liquid condition information held by the control unit 10 defines, for example, a first temperature V (° C.). The first temperature V corresponds to a target value for the temperature of the processing liquid g.

[0365] The first temperature V is preferably lower than the melting point PA of the main sublimable substance and the melting point PB of the sub-sublimable substance. The first temperature V is preferably lower than the melting point PA of the main sublimable substance, the melting point PB1 of the first sub-sublimable substance, and the melting point PB2 of the second sub-sublimable substance.

[0366] The lowest melting point among the melting points PA and PB is referred to as the minimum melting point PL. The first temperature V is preferably lower than the minimum melting point PL.

[0367] The first temperature V is preferably a temperature close to the minimum melting point PL. The first temperature V is preferably as high as possible within a temperature range below the minimum melting point PL. For example, the difference between the first temperature V and the minimum melting point PL is preferably 10 degrees or less. The difference between the first temperature V and the minimum melting point PL is preferably 5 degrees or less. The difference between the first temperature V and the minimum melting point PL is preferably 1 degree or less.

[0368] When the minimum melting point PL is higher than room temperature, the first temperature V is preferably higher than room temperature.

[0369] <2-2. Example of Operation of First Supply Source 19a and Processing Unit 11> For convenience, reference will be made to FIG. 5. The substrate processing method of the second embodiment includes steps S1 and S11-S18 described in the first embodiment. The operations of steps S11-14, S17, and S18 are substantially common between the first and second embodiments. Therefore, a description of the operations of steps S11-14, S17, and S18 will be omitted. The operations of steps S1, S15, and S16 will be described.

[0370] Step S1: Processing liquid generation process In the treatment liquid generating step, the treatment liquid g is generated. Furthermore, in the treatment liquid generating step, the treatment liquid g is adjusted to a first temperature V.

[0371] The control unit 10 controls the first supply source 19a and the temperature adjustment unit 50. The control unit 10 controls the first supply source 19a and the temperature adjustment unit 50 based on the processing liquid condition information. The first supply source 19a generates the processing liquid g. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g in the first supply source 19a to a first temperature V. As a result, the processing liquid g in the first supply source 19a is maintained at the first temperature V.

[0372] Specifically, the production unit 21 produces a treatment liquid g. The treatment liquid g is stored in a bath 22. The first temperature adjustment unit 51 adjusts the temperature of the treatment liquid g in the bath 22 to a first temperature V.

[0373] In the second embodiment, the processing liquid g is generated in an environment at a first temperature V. In the second embodiment, the processing liquid g is stored in an environment at a first temperature V.

[0374] Step S15: Processing liquid supply process In the processing liquid supplying step, the processing liquid g is supplied to the substrate W. In the processing liquid supplying step, the processing liquid g on the substrate W is maintained at a first temperature V.

[0375] The control unit 10 controls the first supply source 19a, the first supply unit 15a, and the temperature adjustment unit 50. The control unit 10 controls the temperature adjustment unit 50 based on the processing liquid condition information. The first supply source 19a sends the processing liquid g to the first supply unit 15a. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g in the first supply unit 15a to a first temperature V. The first supply unit 15a supplies the processing liquid g having the first temperature V to the substrate W held by the substrate holder 13. Furthermore, the temperature adjustment unit 50 adjusts the temperature of the processing liquid g on the substrate W to the first temperature V. As a result, the processing liquid g on the substrate W is maintained at the first temperature V.

[0376] Specifically, the pressure-feeding unit 31 supplies the processing liquid g to the first supply unit 15a. The processing liquid g flows through the pipe 17a of the first supply unit 15a. The second temperature adjustment unit 52 adjusts the processing liquid g flowing through the pipe 17a to a first temperature V. The nozzle 16a of the first supply unit 15a ejects the processing liquid g having the first temperature V. The processing liquid g having the first temperature V is supplied to the upper surface of the substrate W. The third temperature adjustment unit 53 and the fourth temperature adjustment unit 54 each adjust the processing liquid g on the substrate W to the first temperature V.

[0377] Step S16: Solidified film formation process In the solidified film formation process, the processing liquid g on the substrate W is maintained at a first temperature V. That is, from the processing liquid supply process to the solidified film formation process, the processing liquid g on the substrate W is maintained at the first temperature V. In the solidified film formation process, the solvent evaporates from the processing liquid g on the substrate W. In the solidified film formation process, a solidified film K is formed on the substrate W. The solidified film K includes a primary sublimable substance and a secondary sublimable substance.

[0378] The control unit 10 controls the temperature adjustment unit 50. The control unit 10 controls the temperature adjustment unit 50 based on the processing liquid condition information. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g on the substrate W to a first temperature V. As a result, the processing liquid g on the substrate W is maintained at the first temperature V.

[0379] Specifically, the third temperature adjustment unit 53 and the fourth temperature adjustment unit 54 adjust the processing liquid g on the substrate W to a first temperature V, respectively.

[0380] The solvent evaporates from the processing liquid g on the substrate W while the processing liquid g on the substrate W is maintained at the first temperature V. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W.

[0381] The first temperature V is a temperature close to the minimum melting point PL. The first temperature V is as high as possible within the temperature range below the minimum melting point PL. Therefore, the solvent evaporates from the processing liquid g on the substrate W quickly.

[0382] The first temperature V is, for example, a temperature higher than room temperature, so that the solvent evaporates from the processing liquid g on the substrate W more quickly.

[0383] In the solidified film formation step, a solidified film K is formed on the substrate W while the processing liquid g on the substrate W is maintained at a first temperature V. Therefore, the first temperature V is lower than the lowest melting point PL. The main sublimable substance of the solidified film K does not melt. The main sublimable substance of the solidified film K does not change into a liquid. The secondary sublimable substance of the solidified film K does not melt. The secondary sublimable substance of the solidified film K does not change into a liquid. Therefore, the solidified film K does not melt. The solidified film K does not change into a liquid. Therefore, the solidified film K is suitably formed on the substrate W.

[0384] The treatments in the treatment liquid supplying step and the solidified film forming step described above correspond to examples of using the treatment liquid g. In the second embodiment, the treatment liquid g is used in an environment of a first temperature V.

[0385] <2-3. Effects of the Second Embodiment> The second embodiment also provides the same effects as the first embodiment. For example, the processing liquid g contains a main sublimable substance, a sub-sublimable substance, and a solvent. Therefore, the substrate W is appropriately dried while the pattern WP is suitably protected. Furthermore, the second embodiment provides the following effects.

[0386] From the processing liquid supply step to the solidified film formation step, the processing liquid g on the substrate W is maintained at the first temperature V. That is, from the processing liquid supply step to the solidified film formation step, changes in the temperature of the processing liquid g on the substrate W are suppressed. Therefore, in the solidified film formation step, the solvent evaporates smoothly from the processing liquid g on the substrate W. Therefore, in the solidified film formation step, an appropriate solidified film K is formed on the substrate W. Therefore, the solidified film K suitably protects the pattern WP from the processing liquid g.

[0387] Specifically, the smoother the evaporation of the solvent, the smaller the main crystals MA and sub-crystals MB in the solidified film K. Therefore, even if a minute space L is formed between the main crystals MA and the sub-crystals MB, the minute space L is smaller. Therefore, the solidified film K supports the pattern WP more favorably. The solidified film K protects the pattern WP from the processing solution g more favorably. Therefore, the substrate W is dried in a state in which the pattern WP is more favorably protected.

[0388] As described above, according to the substrate processing method of the second embodiment, the substrate is dried more appropriately.

[0389] The first temperature V is lower than the lowest melting point PL. Specifically, the first temperature V is lower than both the melting point PA of the main sublimable substance and the melting point PB of the sub-sublimable substance. Therefore, the main sublimable substance contained in the solidified film K easily maintains its solid state. The sub-sublimable substance contained in the solidified film K also easily maintains its solid state. Specifically, the main crystals MA and sub-crystals MB of the solidified film K each easily maintain their solid state. Therefore, the solidified film K is more appropriately formed in the solidified film formation process.

[0390] The first temperature V is close to the minimum melting point PL. Therefore, the solvent evaporates quickly from the processing liquid g on the substrate W. In other words, the evaporation rate of the solvent is suitably improved. Therefore, a more suitable solidified film K is formed on the substrate W. Therefore, the solidified film K more suitably protects the pattern WP from the processing liquid g.

[0391] Specifically, the faster the solvent evaporates, the smaller the main crystals MA and sub-crystals MB in the solidified film K become. Therefore, even if a minute space L is formed between the main crystals MA and the sub-crystals MB, the minute space L is smaller. Therefore, the solidified film K supports the pattern WP more favorably. The solidified film K protects the pattern WP from the processing solution g more favorably. Therefore, the substrate W is dried in a state in which the pattern WP is more favorably protected.

[0392] The first temperature V is higher than, for example, room temperature. Therefore, the solvent evaporates more quickly from the processing liquid g on the substrate W. Therefore, the solidified film K is more appropriately formed. Therefore, the solidified film K more effectively protects the pattern WP from the processing liquid g.

[0393] The above-described substrate processing apparatus 1 includes a temperature adjustment unit 50. The temperature adjustment unit 50 adjusts the processing liquid g on the substrate W to a first temperature V. Therefore, the processing liquid g on the substrate W is suitably maintained at the first temperature V. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W. Therefore, the solidified film K is more suitably formed. As a result, the solidified film K more suitably protects the pattern WP from the processing liquid g. The substrate W is dried with the pattern WP being suitably protected. That is, the substrate W is more suitably dried.

[0394] <3. Modified embodiment> The present invention is not limited to the first and second embodiments, and can be modified as follows.

[0395] (1) In the first and second embodiments, the main sublimable substance is, for example, cyclohexanone oxime. However, this is not limited to this. The main sublimable substance may be appropriately changed to another compound. For example, the main sublimable substance may be any one of camphor, acetoxime, acetophenone oxime, D-camphor, pinacoline oxime, 4-tert-butylphenol, and 4-nitrotoluene.

[0396] In this modified embodiment as well, the main sublimable substance is a substance different from the auxiliary sublimable substance. In this modified embodiment as well, it is preferable that the main sublimable substance dissolves in the solvent. In this modified embodiment as well, it is preferable that the main sublimable substance has a vapor pressure of 0.1 Pa or more at room temperature. In this modified embodiment as well, it is preferable that the melting point PA of the main sublimable substance is higher than the melting point PC of the solvent.

[0397] (2) In the first and second embodiments, the sub-sublimable substance is, for example, at least one of camphor and acetoxime. However, this is not limited thereto. The sub-sublimable substance may be changed to another compound as appropriate. For example, the sub-sublimable substance may be at least one of camphor, acetophenone oxime, cyclohexanone oxime, D-camphor, pinacoline oxime, 4-tert-butylphenol, and 4-nitrotoluene.

[0398] In this modified embodiment, the sub-sublimable substance is a substance different from the main sublimable substance. In this modified embodiment, it is also preferable that the sub-sublimable substance dissolves in a solvent. In this modified embodiment, it is also preferable that the sub-sublimable substance has a vapor pressure of 0.1 Pa or more at room temperature. In this modified embodiment, it is also preferable that the melting point PB of the sub-sublimable substance is higher than the melting point PC of the solvent.

[0399] (3) In the first and second embodiments, the sub-sublimable substance contains one or two types of compounds. However, this is not limited to this. The sub-sublimable substance may contain three or more types of compounds. For example, the sub-sublimable substance may contain a third sub-sublimable substance in addition to the first and second sub-sublimable substances.

[0400] (4) In the first and second embodiments, the solvent has a melting point of, for example, isopropyl alcohol. However, this is not limited to this. The solvent may be changed to another compound as appropriate. In this modified embodiment, the solvent also dissolves the main sublimable substance and the sub-sublimable substance. In this modified embodiment, the melting point PC of the solvent is also preferably lower than the melting point PA of the main sublimable substance and the melting point PB of the sub-sublimable substance.

[0401] (5) In the second embodiment, the temperature adjustment unit 50 includes first to fourth temperature adjustment units 51-54. However, this is not limited to this. The temperature adjustment unit 50 may be modified as appropriate. For example, any one of the first to fourth temperature adjustment units 51-54 may be omitted. Alternatively, any two of the first to fourth temperature adjustment units 51-54 may be omitted. Alternatively, any three of the first to fourth temperature adjustment units 51-54 may be omitted.

[0402] (6) In the first and second embodiments, the processing liquid g was generated before the processing liquid g was supplied to the first supply unit 15a. In the first and second embodiments, the first supply source 19a generated the processing liquid in the tank 22. However, this is not limited to this. For example, the processing liquid g may be generated when the processing liquid g is supplied to the first supply unit 15a. For example, the first supply source 19a may generate the processing liquid g in a flow path that supplies the processing liquid g to the first supply unit 15a.

[0403] 23 is a diagram showing the configuration of a processing unit 11 and a first supply source 19a according to a modified embodiment. Note that the same components as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.

[0404] The first supply source 19a includes a first tank 41, a second tank 42, and a third tank 43. The first tank 41 stores a main sublimable substance. For example, the first tank 41 may store a solvent together with the main sublimable substance. The second tank 42 stores a sub-sublimable substance. For example, the second tank 42 may store a solvent together with the sub-sublimable substance. The third tank 43 stores a solvent. For example, the third tank 43 stores only a solvent.

[0405] The first supply source 19a includes a mixer 44. The mixer 44 is connected in communication with the first tank 41, the second tank 42, and the third tank 43. The mixer 44 produces a treatment liquid g.

[0406] The mixer 44 is connected in communication with the first supply unit 15a and supplies the treatment liquid g to the first supply unit 15a.

[0407] Specifically, the mixing section 44 includes pipes 45a, 45b, and 45c and a joint 46. The pipe 45a is connected in communication with the first tank 41. The pipe 45b is connected in communication with the second tank 42. The pipe 45c is connected in communication with the third tank 43. The joint 46 is connected in communication with the pipes 45a, 45b, and 45c. The joint 46 is further connected in communication with the pipe 17a. The pipes 45a, 45b, and 45c are connected in communication with the pipe 17a via the joint 46.

[0408] The mixing section 44 includes pumps 47a, 47b, and 47c. The pumps 47a, 47b, and 47c are provided on the pipes 45a, 45b, and 45c, respectively. The pump 47a sends the main sublimable substance from the first tank 41 to the joint 46 through the pipe 45a. The pump 47b sends the sub-sublimable substance from the second tank 42 to the joint 46 through the pipe 45b. The pump 47c sends the solvent from the third tank 43 to the joint 46 through the pipe 45c.

[0409] The mixing section 44 includes filters 48a, 48b, and 48c. The filters 48a, 48b, and 48c are provided on the pipes 45a, 45b, and 45c, respectively. The main sublimable substance passes through the filter 48a. The filter 48a filters the main sublimable substance. The secondary sublimable substance passes through the filter 48b. The filter 48b filters the secondary sublimable substance. The solvent passes through the filter 48c. The filter 48c filters the solvent.

[0410] The mixing section 44 includes valves 49a, 49b, and 49c. The valves 49a, 49b, and 49c are provided in the pipes 45a, 45b, and 45c, respectively. The valve 49a adjusts the flow rate of the main sublimable substance flowing through the pipe 45a. The valve 49b adjusts the flow rate of the sub-sublimable substance flowing through the pipe 45b. The valve 49c adjusts the flow rate of the solvent flowing through the pipe 45c. Each of the valves 49a, 49b, and 49c may include, for example, a flow rate control valve. Each of the valves 49a, 49b, and 49c may include, for example, a flow rate control valve and an on-off valve.

[0411] An example of the operation of the first supply source 19a in the modified embodiment will be described. In the processing liquid supply step, the first supply source 19a generates processing liquid g and sends the processing liquid g to the first supply unit 15a. Specifically, the valves 49a, 49b, and 49c are opened. The pump 47a pumps the main sublimable substance from the first tank 41 to the joint 46. The pump 47b pumps the sub-sublimable substance from the second tank 42 to the joint 46. The pump 47c pumps the solvent from the third tank 43 to the joint 46. The main sublimable substance, the sub-sublimable substance, and the solvent are mixed in the joint 46. The main sublimable substance, the sub-sublimable substance, and the solvent become processing liquid g in the joint 46. Furthermore, the processing liquid g flows from the joint 46 to the first supply unit 15a. The nozzle 16a ejects the processing liquid g.

[0412] According to this modified embodiment, there is no need to store the processing liquid g before it is supplied to the first supply unit 15a. Therefore, the compounding ratio of the main sublimable substance, the sub-sublimable substance, and the solvent in the processing liquid can be controlled with high precision. As a result, the substrate W can be dried more appropriately.

[0413] Furthermore, the first supply source 19a does not include the tank 22. Therefore, the structure of the first supply source 19a is preferably simplified, and the first supply source 19a is preferably miniaturized.

[0414] (7) The substrate processing methods of the first and second embodiments include a chemical liquid supply step, a rinse liquid supply step, and a replacement liquid supply step. However, this is not limited to this. For example, at least one of the chemical liquid supply step, the rinse liquid supply step, and the replacement liquid supply step may be omitted. For example, all of the chemical liquid supply step, the rinse liquid supply step, and the replacement liquid supply step may be omitted.

[0415] (8) In the first and second embodiments, when the processing liquid supplying step is performed, a liquid (e.g., a substitute liquid) is present on the substrate W. That is, in the processing liquid supplying step, the processing liquid g is supplied to the substrate W in a wet state. However, this is not limited to this. For example, when the processing liquid supplying step is performed, a liquid (e.g., a substitute liquid) does not have to be present on the substrate W. For example, in the processing liquid supplying step, the processing liquid g may be supplied to the substrate W in a dry state.

[0416] (9) In the processing liquid supplying process of the first and second embodiments, the processing liquid g removes the substitute liquid from the substrate W. However, this is not limited to this. For example, in the processing liquid supplying process, the processing liquid g may clean the substrate W. For example, in the processing liquid supplying process, the processing liquid g may remove foreign matter adhering to the substrate W. For example, in the processing liquid supplying process, the processing liquid g may dissolve foreign matter adhering to the substrate W. The foreign matter may be, for example, resist residue.

[0417] (10) In the solidified film formation process of the first and second embodiments, a dry gas is not supplied to the substrate W. However, this is not limited to this. In the solidified film formation process, a dry gas may be supplied to the substrate W. In the solidified film formation process, a dry gas may be supplied to the processing liquid g on the substrate W. According to this modified embodiment, in the solidified film formation process, the processing liquid g on the substrate W is exposed to the dry gas. Therefore, in the solidified film formation process, the solvent evaporates efficiently from the processing liquid g on the substrate W. In the solidified film formation process, the solidified film K is efficiently formed on the substrate W.

[0418] (11) In the first and second embodiments, the pattern WP on the substrate W may be formed on the substrate W, for example, before the processing unit 11 processes the substrate W. Alternatively, the pattern WP may be formed on the substrate W, for example, in the chemical solution supplying step (step S12).

[0419] (12) The first and second embodiments and the modified embodiments described above in (1) to (11) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment. [Explanation of symbols]

[0420] 1... Substrate processing equipment 10...Control section 11... Processing unit 13... Board holding part 15 … Supply section 15a... First supply unit (processing liquid supply unit) 19a… 1st source 50 … Temperature control section 51 … 1st temperature control section 52…Second temperature control section 53 … 3rd temperature control section 54 … 4th temperature control section g... Processing liquid G: Liquid film of processing liquid G1: Upper surface of the liquid film HG: Liquid film thickness HK: Thickness of the solidified film HP: Height of the protrusion (height of the pattern) J...gas K: Solidified film K1: Top surface of solidified film L…Minute space MA … Main crystal MB … Sub-crystal MB1 … 1st sub-crystal MB2…Second secondary crystal mA … Main crystal nucleus mB … Secondary crystal nucleus mB1 … 1st secondary crystal nucleus mB2 … Second secondary crystal nucleus PA: Melting point of main sublimable substance PB: Melting point of sub-sublimable substance PB1: Melting point of the first sublimable substance PB2: Melting point of the second sublimable substance PC: Melting point of solvent PL: Lowest melting point (the lowest melting point among PA and PB) R … gas-liquid interface V … 1st temperature W: Substrate WP... Pattern T... convex part A ... recess

Claims

1. A substrate processing method for processing a substrate on which a pattern is formed, comprising: a processing liquid supplying step of supplying a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate; a solidified film forming step of evaporating the solvent from the treatment liquid on the substrate to form a solidified film containing the main sublimable substance and the sub-sublimable substance on the substrate; a sublimation step of sublimating the solidified film; Equipped with the main sublimable substance is cyclohexanone oxime, The sub-sublimable substance includes acetoxime. Substrate processing method.

2. A substrate processing method according to claim 1, The sub-sublimable substance further includes camphor. Substrate processing method.

3. A substrate processing method according to claim 1 or 2, comprising: The volume of the sub-sublimable substance contained in the treatment liquid is 0.5% or more and 20% or less of the volume of the main sublimable substance contained in the treatment liquid. Substrate processing method.

4. A substrate processing method for processing a substrate on which a pattern is formed, comprising: a processing liquid supplying step of supplying a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate; a solidified film forming step of evaporating the solvent from the treatment liquid on the substrate to form a solidified film containing the main sublimable substance and the sub-sublimable substance on the substrate; a sublimation step of sublimating the solidified film; Equipped with From the processing liquid supplying step to the solidified film forming step, the processing liquid on the substrate is maintained at a first temperature by a temperature adjusting unit. Substrate processing method.

5. The substrate processing method according to claim 4, comprising: The first temperature is lower than both the melting point of the main sublimable substance and the melting point of the sub-sublimable substance. Substrate processing method.

6. A substrate processing method according to claim 4 or 5, comprising: The first temperature is a temperature close to the lowest melting point of the primary sublimable substance and the secondary sublimable substance. Substrate processing method.

7. A substrate processing method according to claim 4, further comprising: The first temperature is higher than room temperature. Substrate processing method.

8. A substrate processing apparatus, a substrate holder that holds a substrate; a processing liquid supply unit that supplies a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate held by the substrate holding unit; Equipped with the main sublimable substance is cyclohexanone oxime, The sub-sublimable substance includes acetoxime. Substrate processing equipment.

9. In the substrate processing apparatus according to claim 8, The sub-sublimable substance further includes camphor. Substrate processing equipment.

10. A substrate processing apparatus, comprising: a substrate holder that holds a substrate; a processing liquid supply unit that supplies a processing liquid containing a main sublimable substance, a sub-sublimable substance, and a solvent to the substrate held by the substrate holding unit; a temperature control unit that adjusts the processing liquid on the substrate to a first temperature; Equipped with the temperature adjustment unit adjusts the processing liquid on the substrate to a first temperature from the time when the processing liquid supply unit supplies the processing liquid to the substrate held by the substrate holding unit until the solvent evaporates from the processing liquid on the substrate and a solidified film containing the main sublimable substance and the sub-sublimable substance is formed on the substrate.

11. The substrate processing apparatus according to claim 10, The first temperature is lower than both the melting point of the main sublimable substance and the melting point of the sub-sublimable substance. Substrate processing equipment.

12. The substrate processing apparatus according to claim 10 or 11, The first temperature is higher than room temperature. Substrate processing equipment.

13. A processing liquid used for drying a substrate on which a pattern has been formed, The treatment liquid is a primary sublimable material; a sub-sublimable material; A solvent; Including, the main sublimable substance is cyclohexanone oxime, The sub-sublimable substance includes acetoxime. Processing liquid.

14. The treatment solution according to claim 13, The sub-sublimable substance further includes camphor. Processing liquid.

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