Substrate processing method and processing liquid evaluation method

Abstract

To provide a substrate processing method that can properly process a substrate, and a process liquid evaluation method that can appropriately evaluate process liquids.SOLUTION: The present invention relates a substrate processing method and a process liquid evaluation method. The substrate processing method is for processing a substrate W on which a pattern P is formed. The substrate processing method includes a process liquid supply step, a solidified film formation step, and a sublimation step. In the process liquid supply step, a process liquid L is supplied to the substrate W. The process liquid L contains a sublimable substance and a solvent. In the solidified film formation step, the solvent evaporates from the process liquid L on the substrate W. In the solidified film formation step, a solidified film G is formed on the substrate W. The solidified film G contains a sublimable substance. A coefficient K is defined by interfacial free energies γLG, γGW, and γLW. The coefficient K is less than or equal to a threshold value TH.SELECTED DRAWING: Figure 13

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method and a processing liquid evaluation method. The substrate may be, for example, a semiconductor wafer, a liquid crystal display substrate, an organic electroluminescence (EL) 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. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method. Specifically, the substrate processing method of Patent Document 1 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 a substrate. The processing liquid contains a sublimable substance and a solvent. In the solidified film forming step, the solvent is evaporated 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 sublimable substance. In the sublimation step, the solidified film is sublimated. The solidified film changes into a gas without passing through a liquid state. The substrate is dried by the sublimation of the solidified film. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-9988 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 processed properly, for example, even with conventional substrate processing methods, there are cases where the pattern formed on the substrate collapses.

[0005] The present invention has been made in view of the above circumstances, and has a first object to provide a substrate processing method capable of appropriately processing a substrate, and a second object to provide a processing liquid evaluation method capable of appropriately evaluating a processing liquid. [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 is formed, the method comprising: a processing liquid supplying step of supplying a processing liquid containing a 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 sublimable substance on the substrate, and a sublimation step of sublimating the solidified film, wherein a coefficient K defined by the following formula is equal to or less than a threshold value. K = γLG + γGW - γLW however, K: Coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

[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 contains a 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 sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by the sublimation of the solidified film.

[0008] The coefficient K is defined by the interfacial free energies γLG, γGW, and γLW. The coefficient K is equal to or less than a threshold value. The coefficient K being equal to or less than the threshold value is appropriately referred to as the "first condition." The substrate, the treatment liquid, and the solidified film satisfy the first condition. Therefore, in the solidified film formation process, the solidified film is suitably formed on the substrate. Specifically, in the solidified film formation process, the solidified film spreads smoothly on the substrate. Therefore, in the solidified film formation process, the solvent is efficiently removed from the substrate. In the solidified film formation process, the treatment liquid is efficiently eliminated from the substrate. Therefore, in the sublimation process, the substrate is dried while the pattern formed on the substrate is suitably protected.

[0009] As described above, according to the present substrate processing method, the substrate is processed appropriately.

[0010] In the above-described substrate processing method, the threshold value is preferably a preset constant. The first condition is simple. Therefore, it is easy to manage the substrate processing method so as to satisfy the first condition. Therefore, it is easy to execute the substrate processing method.

[0011] In the above-described substrate processing method, the threshold value is preferably 17 mN / m. In other words, in the above-described substrate processing method, the coefficient K is preferably 17 mN / m or less. In the solidified film forming step, the solidified film spreads more smoothly on the substrate.

[0012] In the above-described substrate processing method, the threshold value is preferably a variable, which allows the first condition to be set more appropriately, thereby enabling the substrate to be processed more appropriately.

[0013] In the above-described substrate processing method, the threshold value is preferably a variable that depends on the aspect ratio of the pattern. The first condition is more appropriately set depending on the aspect ratio of the pattern. Therefore, the substrate is more appropriately processed regardless of the aspect ratio of the pattern.

[0014] In the above-described substrate processing method, it is preferable that the threshold value decreases as the aspect ratio increases. The larger the aspect ratio, the easier the pattern collapses. The smaller the threshold value, the smoother the solidified film spreads on the substrate. Therefore, the smaller the threshold value, the more reliably the pattern is protected. Therefore, even when the aspect ratio is large, the pattern is suitably protected. Regardless of the aspect ratio, the substrate is processed appropriately.

[0015] In the above-described substrate processing method, it is preferable that the coefficient K is set in accordance with the state of the surface of the substrate. The coefficient K is set appropriately regardless of the state of the surface of the substrate. Therefore, the substrate is processed appropriately regardless of the state of the surface of the substrate.

[0016] In the above-described substrate processing method, it is preferable that the coefficient K is set based on the surface state of the substrate in at least one of the processing liquid supply step and the solidified film formation step. The coefficient K is set appropriately regardless of the surface state of the substrate in the processing liquid supply step. Therefore, the substrate is processed appropriately regardless of the surface state of the substrate in the processing liquid supply step. The coefficient K is set appropriately regardless of the surface state of the substrate in the solidified film formation step. Therefore, the substrate is processed appropriately regardless of the surface state of the substrate in the solidified film formation step.

[0017] In the above-described substrate processing method, it is preferable that the interfacial free energy γ and the interfacial free energy γ are each set according to the surface condition of the substrate. Therefore, the interfacial free energy γ and the interfacial free energy γ are each set appropriately regardless of the surface condition of the substrate. Therefore, when the coefficient K is set, the surface condition of the substrate is suitably taken into consideration. Therefore, the coefficient K is set appropriately regardless of the surface condition of the substrate.

[0018] In the above-described substrate processing method, it is preferable that the interfacial free energy γ and the interfacial free energy γ are each set based on the state of the surface of the substrate in at least one of the processing liquid supply step and the solidified film formation step. The interfacial free energy γ and the interfacial free energy γ are appropriately set regardless of the state of the surface of the substrate in the processing liquid supply step. Thus, the coefficient K is appropriately set regardless of the state of the surface of the substrate in the processing liquid supply step. The interfacial free energy γ and the interfacial free energy γ are appropriately set regardless of the state of the surface of the substrate in the solidified film formation step. Thus, the coefficient K is appropriately set regardless of the state of the surface of the substrate in the solidified film formation step.

[0019] In the above-described substrate processing method, the surface free energy of the substrate when the surface of the substrate is hydrophobic is defined as a first surface free energy, and the surface free energy of the substrate when the surface of the substrate is hydrophilic is defined as a second surface free energy. Preferably, when the surface of the substrate is hydrophobic in the processing liquid supplying step, the interfacial free energy γ and the interfacial free energy γ are each set based on the first surface free energy, and when the surface of the substrate is hydrophilic in the processing liquid supplying step, the interfacial free energy γ and the interfacial free energy γ are each set based on the second surface free energy. When the surface of the substrate is hydrophobic in the processing liquid supplying step, the interfacial free energy γ and the interfacial free energy γ are each set appropriately. When the surface of the substrate is hydrophilic in the processing liquid supplying step, the interfacial free energy γ and the interfacial free energy γ are each set appropriately. In summary, the interfacial free energy γ and the interfacial free energy γ are each set appropriately regardless of the state of the surface of the substrate in the processing liquid supplying step.

[0020] In the above-described substrate processing method, the surface free energy of the substrate when the surface of the substrate is hydrophobic is defined as a first surface free energy, and the surface free energy of the substrate when the surface of the substrate is hydrophilic is defined as a second surface free energy. When the surface of the substrate is hydrophobic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are preferably set based on the first surface free energy, and when the surface of the substrate is hydrophilic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are preferably set based on the second surface free energy. When the surface of the substrate is hydrophobic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are preferably set appropriately. When the surface of the substrate is hydrophilic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are preferably set appropriately. In summary, the interfacial free energy γ and the interfacial free energy γ are preferably set appropriately regardless of the state of the surface of the substrate in the solidified film formation process.

[0021] The present invention is 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 sublimable substance and a solvent onto 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 sublimable substance on the substrate; a sublimation step of sublimating the solidified film; and a modification step of modifying the surface of the substrate before the processing liquid supplying step when a coefficient K defined by the following formula is greater than a threshold value. K = γLG + γGW - γLW however, K: Coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

[0022] 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 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 sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by the sublimation of the solidified film.

[0023] The substrate processing method further includes a modification process. The modification process is performed when the coefficient K is greater than a threshold value. The coefficient K is defined by the interfacial free energies γLG, γGW, and γLW. The modification process is performed before the processing liquid supply process. The modification process modifies the surface of the substrate. When the coefficient K is greater than the threshold value, the surface of the substrate is modified in the modification process, and then the processing liquid is supplied to the substrate in the processing liquid supply process. Therefore, even when the coefficient K is greater than the threshold value, a solidified film is suitably formed on the substrate in the solidified film formation process. Specifically, in the solidified film formation process, the solidified film spreads smoothly on the substrate. Therefore, in the solidified film formation process, the solvent is efficiently removed from the substrate. In the solidified film formation process, the processing liquid is efficiently removed from the substrate. Therefore, in the sublimation process, the substrate is dried while the pattern formed on the substrate is suitably protected.

[0024] As described above, according to the present substrate processing method, the substrate is processed appropriately.

[0025] In the above-described substrate processing method, the modifying step preferably reduces the coefficient K. In the solidified film forming step, the solidified film is more suitably formed on the substrate.

[0026] In the above-described substrate processing method, the coefficient K is preferably reduced to a value lower than the threshold value by the modifying step. In the solidified film forming step, the solidified film is more suitably formed on the substrate.

[0027] In the substrate processing method described above, the surface of the substrate is preferably modified to be either hydrophilic or hydrophobic in the modification step. In the modification step, the surface of the substrate can be modified to be flexible. Therefore, in the solidified film forming step, the solidified film is more suitably formed on the substrate.

[0028] In the substrate processing method described above, the surface of the substrate is preferably modified to be hydrophobic in the modification step. In the modification step, the surface of the substrate can be suitably modified. Therefore, in the solidified film formation step, the solidified film is more suitably formed on the substrate.

[0029] In the above-described substrate processing method, it is preferable that the modification step is not performed when the coefficient K is equal to or less than the threshold value. This can effectively shorten the time required for the substrate processing method. When the coefficient K is equal to or less than the threshold value, even if the modification step is not performed, a solidified film is suitably formed on the substrate in the solidified film forming step. Therefore, even if the coefficient K is equal to or less than the threshold value, the substrate is suitably processed.

[0030] The present invention is a substrate processing method for processing a substrate having a pattern formed thereon, the method comprising: a selection step of selecting a processing liquid containing a sublimable substance and a solvent based on a coefficient K defined by the following formula; a processing liquid supply step of supplying the processing liquid selected by the selection step to the substrate; a solidified film formation step of evaporating the solvent from the processing liquid on the substrate to form a solidified film containing the sublimable substance on the substrate; and a sublimation step of sublimating the solidified film. K = γLG + γGW - γLW however, K: Coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

[0031] The substrate processing method is for processing a substrate on which a pattern is formed. The substrate processing method includes a selection step, a processing liquid supply step, a solidified film formation step, and a sublimation step. In the selection step, a processing liquid is selected. The processing liquid contains a sublimable substance and a solvent. In the processing liquid supply step, the processing liquid selected in the selection step is supplied to the substrate. In the solidified film formation step, the solvent evaporates from the processing liquid on the substrate. In the solidified film formation step, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by sublimation of the solidified film.

[0032] Here, in the selection process, a treatment liquid is selected based on the coefficient K. The coefficient K is defined by the interfacial free energies γLG, γGW, and γLW. Therefore, in the selection process, a treatment liquid is appropriately selected. Therefore, in the solidified film formation process, a solidified film is suitably formed on the substrate. Specifically, in the solidified film formation process, the solidified film spreads smoothly on the substrate. Therefore, in the solidified film formation process, the solvent is efficiently removed from the substrate. In the solidified film formation process, the treatment liquid is efficiently eliminated from the substrate. Therefore, in the sublimation process, the substrate is dried in a state in which the pattern formed on the substrate is suitably protected.

[0033] As described above, according to the present substrate processing method, the substrate is processed appropriately.

[0034] In the above-described substrate processing method, the selection step preferably selects the processing liquid that makes the coefficient K equal to or less than a threshold value. In other words, in the above-described substrate processing method, the selection step preferably selects the processing liquid that satisfies the requirement that the coefficient K is equal to or less than a threshold value. In the selection step, the processing liquid is more appropriately selected.

[0035] In the above-described substrate processing method, the coefficient K is preferably set in accordance with the surface condition of the substrate. The coefficient K is set appropriately regardless of the surface condition of the substrate. Therefore, in the selection step, a processing liquid is selected in accordance with the surface condition of the substrate. In the selection step, a processing liquid is selected appropriately regardless of the surface condition of the substrate. Therefore, in the processing liquid supply step, solidified film formation step, and sublimation step, the substrate is processed appropriately regardless of the surface condition of the substrate.

[0036] In the above-described substrate processing method, the coefficient K is preferably set based on the state of the surface of the substrate in at least one of the processing liquid supply step and the solidified film formation step. The substrate is appropriately processed regardless of the state of the surface of the substrate in the processing liquid supply step. The substrate is appropriately processed regardless of the state of the surface of the substrate in the solidified film formation step.

[0037] The present invention also provides a processing liquid evaluation method for evaluating a processing liquid for processing a substrate having a pattern formed thereon, the processing liquid containing a sublimable substance and a solvent, and the processing liquid becoming a solidified film containing the sublimable substance as the solvent evaporates from the processing liquid, the processing liquid evaluation method including: an acquisition step of acquiring a coefficient K defined by the following formula; and an evaluation step of evaluating the processing liquid based on the coefficient K: K = γLG + γGW - γLW however, K: Coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

[0038] The processing liquid evaluation method is for evaluating a processing liquid. The processing liquid is for processing a substrate on which a pattern is formed. The processing liquid includes a sublimable substance and a solvent. When the solvent evaporates from the processing liquid, the processing liquid becomes a solidified film. The solidified film includes the sublimable substance. The processing liquid evaluation method includes an acquisition step and an evaluation step. The acquisition step acquires a coefficient K. The coefficient K is defined by interfacial free energies γLG, γGW, and γLW. The evaluation step evaluates the processing liquid based on the coefficient K. Thus, the processing liquid is suitably evaluated from the viewpoint of the quality of substrate processing.

[0039] As described above, the present treatment liquid evaluation method allows treatment liquids to be appropriately evaluated, and is useful for selecting a treatment liquid.

[0040] In the above-described treatment liquid evaluation method, it is preferable that the coefficient K is acquired in the acquisition step in accordance with the surface condition of the substrate. In the acquisition step, the coefficient K is acquired appropriately regardless of the surface condition of the substrate. Therefore, in the evaluation step, the treatment liquid is evaluated taking into account the surface condition of the substrate. In the evaluation step, the treatment liquid is evaluated appropriately regardless of the surface condition of the substrate.

[0041] In the above-described treatment liquid evaluation method, it is preferable that the coefficient K includes a first coefficient when the surface of the substrate is hydrophobic and a second coefficient when the surface of the substrate is hydrophilic, the first coefficient and the second coefficient are acquired in the acquisition step, and the treatment liquid is evaluated based on the first coefficient and the second coefficient in the evaluation step. In the acquisition step, the first coefficient and the second coefficient are acquired. The first coefficient corresponds to the coefficient K when the surface of the substrate is hydrophobic. The second coefficient corresponds to the coefficient K when the surface of the substrate is hydrophilic. In the evaluation step, the treatment liquid is evaluated based on the first coefficient. In the evaluation step, the treatment liquid is evaluated based on the second coefficient. Thus, in the evaluation step, the treatment liquid is evaluated taking into account the state of the surface of the substrate. In the evaluation step, the treatment liquid is appropriately evaluated regardless of the state of the surface of the substrate.

[0042] In the above-described treatment liquid evaluation method, the obtaining step preferably includes a first step of preparing a first substrate having a hydrophobic surface and a second substrate having a hydrophilic surface, a second step of obtaining the coefficient K based on the first substrate, and a third step of obtaining the coefficient K based on the second substrate. In the obtaining step, the coefficient K is obtained appropriately regardless of the surface condition of the substrate.

[0043] In the above-described treatment liquid evaluation method, it is preferable that the coefficient K is acquired based on the state of the surface of the substrate and the composition of the treatment liquid in the acquisition step. In the acquisition step, the coefficient K is appropriately acquired.

[0044] In the above-described treatment liquid evaluation method, it is preferable that in the obtaining step, the coefficient K is selected from preset information related to the coefficient K. In the obtaining step, the coefficient K can be easily obtained.

[0045] In the above-described treatment liquid evaluation method, it is preferable that the evaluation step classifies the treatment liquid that causes the coefficient K to be equal to or less than a threshold value into a first class, and classifies the treatment liquid that causes the coefficient K to be greater than the threshold value into a second class. In other words, it is preferable that the above-described treatment liquid evaluation method sets a first condition that the coefficient K is equal to or less than a threshold value, and that the evaluation step classifies the treatment liquid that satisfies the first condition into the first class, and classifies the treatment liquid that does not satisfy the first condition into the second class. In the evaluation step, the treatment liquid is classified into either the first class or the second class based on the coefficient K. Thus, in the evaluation step, the treatment liquid is clearly evaluated. [Effects of the Invention]

[0046] According to the substrate processing method of the present invention, the substrate is processed appropriately. According to the processing liquid evaluation method of the present invention, the processing liquid is evaluated appropriately. [Brief explanation of the drawings]

[0047] [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 illustrating a configuration of a processing unit. [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] FIG. 2 is an enlarged view schematically showing the 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] 3 is a flowchart showing the procedure of a substrate processing method according to the first embodiment. [Figure 12] 10 is a table showing coefficients and average collapse rates in each example. [Figure 13] 10 is a graph showing the relationship between the coefficient and the average collapse rate in each example. [Figure 14] 10 is a flowchart showing the procedure of a substrate processing method according to a second embodiment. [Figure 15] FIG. 10 is a diagram illustrating the configuration of a processing unit according to a third embodiment. [Figure 16] 10 is a flowchart showing the procedure of a substrate processing method according to a third embodiment. [Figure 17] 10 is a flowchart showing the procedure of a treatment liquid evaluation method according to a fourth embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0048] The substrate processing method and processing liquid evaluation method of the present invention will be described below with reference to the drawings.

[0049] 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.

[0050] 1 is a diagram schematically showing a part of a substrate W. The substrate W has a pattern P. The pattern P is formed on a surface WS of the substrate W. The pattern P has, for example, an uneven shape.

[0051] The pattern P has, for example, a plurality of protrusions A. The protrusions A are parts of the substrate W. The protrusions A are structures. The protrusions A are made of, for example, at least one of a single crystal silicon film, a silicon oxide film (SiO2), a silicon nitride film (SiN), and a polysilicon film. Each protrusion A protrudes upward, for example. The plurality of protrusions A are arranged laterally, for example. The plurality of protrusions A are spaced apart from one another.

[0052] The protrusions A define recesses B. The recesses B are spaces. The recesses B are located between two adjacent protrusions A. The recesses B are open, for example, upward.

[0053] <1-2. 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.

[0054] 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.

[0055] 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.

[0056] 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).

[0057] 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 substrates W. The transport mechanism 5 is configured to access the carriers C placed on the carrier platform 4.

[0058] 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.

[0059] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 is configured to receive the substrate W from the transport mechanism 5 and to hand over the substrate W to the transport mechanism 5.

[0060] 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.

[0061] 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.

[0062] Each processing unit 11 includes a substrate holder 13. The substrate holder 13 holds a substrate W.

[0063] The transport mechanism 8 is configured to access each processing unit 11. The transport mechanism 8 is configured to deliver a substrate W to the substrate holder 13 and to take a substrate W from the substrate holder 13.

[0064] 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 communicably connected to 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.

[0065] 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 working 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 includes, for example, transport condition information and processing condition information. The transport condition information defines conditions related to the transport of the substrate W by the transport mechanisms 5 and 8. The processing condition information defines conditions related to the processing of the substrate W in the processing unit 11. The processing condition information is also called a processing recipe.

[0066] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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 takes the substrates W from each substrate holder 13. Then, the transport mechanism 8 hands the substrates W over to the transport mechanism 5.

[0071] 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.

[0072] <1-3. 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.

[0073] 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.

[0074] The interior of the housing 12 is maintained at, for example, room temperature. Therefore, the substrate W is processed in, for example, a room temperature environment. Here, room temperature includes room temperature. Room temperature is, for example, a temperature in the range of 5°C or higher and 35°C or lower. Room temperature is, for example, a temperature in the range of 10°C or higher and 30°C or lower. Room temperature is, for example, a temperature in the range of 15°C or higher and 25°C or lower.

[0075] The interior of the housing 12 is maintained at, for example, atmospheric pressure. Therefore, the substrate W is processed, for example, in an atmospheric pressure environment. 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 is indicated as absolute pressure based on absolute vacuum.

[0076] 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.

[0077] The substrate holding part 13 is positioned below the substrate W that it holds. The substrate holding part 13 contacts 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 contact the upper surface WS1 of the substrate W. Here, the upper surface WS1 faces upward. The upper surface WS1 is part of the front surface WS.

[0078] 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, for example, around a rotational axis D. The rotational axis D passes through the center of the substrate W, for example. The rotational axis D extends, for example, in the vertical direction Z.

[0079] The processing unit 11 includes supply units 15a, 15b, 15c, 15d, 15e, and 15f. Each of the supply units 15a-15f supplies a liquid or a gas to the substrate W held by the substrate holding unit 13. Specifically, each of the supply units 15a-15f supplies a liquid or a gas to the upper surface WS1 of the substrate W held by the substrate holding unit 13.

[0080] The supply unit 15a supplies the processing liquid L. The supply unit 15b supplies the chemical liquid. The supply unit 15c supplies the cleaning liquid. The supply unit 15d supplies the rinse liquid. The supply unit 15e supplies the substitute liquid. The supply unit 15f supplies the drying gas.

[0081] The treatment liquid L supplied by the supply unit 15a contains a sublimable substance and a solvent.

[0082] A sublimable substance has sublimability. "Sublimability" refers to the property of a simple substance, compound, or mixture undergoing a phase transition from solid to gas or from gas to solid without passing through a liquid state. The sublimable substance preferably has a vapor pressure of 0.1 Pa or more at room temperature. For example, the sublimable substance contains at least one of cyclohexanone oxime, camphor, pinacoline oxime, acetophenone oxime, cyclopentanone oxime, 4-tert-butylphenol, 4-nitrotoluene, and ε-caprolactam. For example, the sublimable substance consists solely of cyclohexanone oxime. For example, the sublimable substance consists solely of camphor.

[0083] The solvent is liquid at room temperature. The solvent dissolves the sublimable substance. Therefore, the sublimable substance in the treatment liquid L is dissolved in the solvent. That is, the treatment liquid L includes the solvent and the sublimable substance dissolved in the solvent. The sublimable substance corresponds to the solute of the treatment liquid L. The solvent preferably has a relatively high vapor pressure at room temperature. For example, the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature. The solvent is, for example, an organic solvent. The solvent is, for example, an alcohol. The solvent includes at least one of isopropyl alcohol (IPA), methanol, ethanol, 1-propanol, isobutanol, propylene glycol monomethyl ether acetate (PGMEA), 1-ethoxy-2-propanol (PGEE), acetone, and 1-butanol. For example, the solvent consists solely of isopropyl alcohol. For example, the solvent consists solely of methanol.

[0084] The treatment liquid L may, for example, consist of only a sublimable substance and a solvent. For example, the treatment liquid L may consist of only cyclohexanone oxime and isopropyl alcohol. For example, the treatment liquid L may consist of only camphor and methanol.

[0085] The processing liquid L is used to dry the substrate W. The processing liquid L has a function of assisting in drying the substrate W. For this reason, the processing liquid L may be called a "drying auxiliary liquid."

[0086] The chemical liquid supplied by the supply unit 15b is, for example, an etching liquid, which contains, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0087] The cleaning liquid supplied by the supply unit 15c is, for example, SC1. SC1 is a mixture of ammonia, hydrogen peroxide, and deionized water. SC1 is also called "APM" or "ammonia hydrogen peroxide mixture."

[0088] The rinse liquid supplied by the supply unit 15d is, for example, deionized water (DIW).

[0089] The substitute liquid supplied by the supply unit 15e is, for example, an organic solvent or isopropyl alcohol (IPA).

[0090] The dry gas supplied by the supply unit 15f preferably has a dew point lower than room temperature. The dry gas preferably does not condense at room temperature. The dry gas includes at least one of air and an inert gas. The air is, for example, compressed air. The inert gas is, for example, nitrogen gas.

[0091] The supply unit 15a includes a nozzle 16a. Similarly, the supply units 15b-15f include nozzles 16b-16f, respectively. The nozzle 16a discharges the processing liquid L. The nozzle 16b discharges the chemical liquid. The nozzle 16c discharges the cleaning liquid. The nozzle 16d discharges the rinse liquid. The nozzle 16e discharges the substitute liquid. The nozzle 16f discharges the drying gas.

[0092] Each of the nozzles 16a-16f is installed inside the housing 12. Each of the nozzles 16a-16f is movable between a processing position and a standby position. The processing position is, for example, a position above the substrate W held by the substrate holder 13. The standby position is, for example, a position not above the substrate W held by the substrate holder 13.

[0093] The processing liquid L is used inside the housing 12. As described above, the inside of the housing 12 is kept at, for example, room temperature. Therefore, the processing liquid L is used in, for example, a room temperature environment. The inside of the housing 12 is kept at, for example, normal pressure. Therefore, the processing liquid L is used in, for example, a normal pressure environment. The chemical liquid, the cleaning liquid, the rinse liquid, the replacement liquid, and the drying gas are also used in, for example, a room temperature and normal pressure environment.

[0094] The supply unit 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is open, the nozzle 16a discharges the processing liquid L. When the valve 18a is closed, the nozzle 16a does not discharge the processing liquid L. Similarly, the supply units 15b-15f include pipes 17b-17f and valves 18b-18f, respectively. The pipes 17b-17f are connected to the nozzles 16b-16f, respectively. The valves 18b-18f are provided on the pipes 17b-17f, respectively. The valves 18b-18f control the discharge of the chemical liquid, the cleaning liquid, the rinse liquid, the substitute liquid, and the drying gas, respectively.

[0095] At least a portion of pipe 17a may be provided outside of housing 12. Pipes 17b-17f may be arranged in the same manner as pipe 17a. Valve 18a may be provided outside of housing 12. Valves 18b-18f may be arranged in the same manner as valve 18a.

[0096] The supply unit 15a is connected to a supply source 19a. The supply source 19a is connected to, for example, a pipe 17a. The supply source 19a supplies the processing liquid L to the supply unit 15a. Similarly, the supply units 15b-15f are connected to supply sources 19b-19f, respectively. The supply sources 19b-19f are connected to, for example, pipes 17b-17f, respectively. The supply source 19b supplies the chemical liquid to the supply unit 15b. The supply source 19c supplies the cleaning liquid to the supply unit 15c. The supply source 19d supplies the rinse liquid to the supply unit 15d. The supply source 19e supplies the replacement liquid to the supply unit 15e. The supply source 19f supplies the drying gas to the supply unit 15f.

[0097] The supply source 19a is provided outside the housing 12. Similarly, the supply sources 19b-19f are each provided outside the housing 12.

[0098] The supply source 19a may supply the processing liquid L to a plurality of processing units 11. Alternatively, the supply source 19a may supply the processing liquid L to only one processing unit 11. The same applies to the supply sources 19b-19f.

[0099] The supply source 19a may be a component of the substrate processing apparatus 1. For example, the supply source 19a may be located inside the substrate processing apparatus 1. Alternatively, the supply source 19a may not be a component of the substrate processing apparatus 1. For example, the supply source 19a may be located outside the substrate processing apparatus 1. Similarly, each of the supply sources 19b-19f may be a component of the substrate processing apparatus 1. Alternatively, each of the supply sources 19b-19f may not be a component of the substrate processing apparatus 1.

[0100] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12. The cup is disposed to the side of the substrate holding part 13. The cup surrounds the outside of the substrate holding part 13. The cup catches liquid splashed from the substrate W held by the substrate holding part 13.

[0101] See Figure 3. The control unit 10 controls the rotary drive unit 14. The control unit 10 controls the supply units 15a-15f. The control unit 10 controls the valves 18a-18f.

[0102] The control unit 10 is communicably connected to, for example, the supply source 19a and controls, for example, the supply source 19a.

[0103] <1-4. Configuration of supply source 19a> 4, the supply source 19a includes a generation unit 20. The generation unit 20 generates the treatment liquid L. The generation unit 20 stores the treatment liquid L.

[0104] The production unit 20 includes a tank 21 and supply units 22a and 22b. The supply unit 22a supplies a sublimable substance to the tank 21. The supply unit 22b supplies a solvent to the tank 21. The sublimable substance and the solvent are mixed in the tank 21. The treatment liquid L is produced in the tank 21. The treatment liquid L is stored in the tank 21.

[0105] Specifically, the supply unit 22a includes a pipe 23a and a valve 24a. The pipe 23a is connected to the tank 21. The valve 24a is provided on the pipe 23a. When the valve 24a is open, the supply unit 22a supplies the sublimable substance to the tank 21. When the valve 24a is closed, the supply unit 22a does not supply the sublimable substance to the tank 21. Similarly, the supply unit 22b includes a pipe 23b and a valve 24b. The pipe 23b is connected to the tank 21. The valve 24b is provided on the pipe 23b. The valve 24b controls the supply of the solvent to the tank 21.

[0106] Supply unit 22a is connected to supply source 25a. Supply source 25a is connected to, for example, pipe 23a. Supply source 25a sends a sublimable substance to supply unit 22a. Similarly, supply unit 22b is connected to supply source 25b. Supply source 25b is connected to, for example, pipe 23b. Supply source 25b sends a solvent to supply unit 22b.

[0107] The supply source 19a includes a liquid delivery unit 26. The liquid delivery unit 26 delivers the treatment liquid L from the generation unit 20 to the supply unit 15a. The liquid delivery unit 26 includes, for example, a pipe 27, a pump 28, a filter 29, and a joint 30. The pipe 27 is connected to the tank 21. The pump 28 is provided on the pipe 27. The filter 29 is provided on the pipe 27. The joint 30 is connected to the pipe 27. The joint 30 is further connected to the pipe 17a.

[0108] The pump 28 sends the processing liquid L from the tank 21 to the pipe 17a through the pipe 27. The filter 29 filters the processing liquid L flowing through the pipe 27. The filter 29 removes foreign matter from the processing liquid L.

[0109] See Fig. 3. The control unit 10 controls the generation unit 20. The control unit 10 controls the supply units 22a and 22b. The control unit 10 controls the valves 24a and 24b. The control unit 10 controls the liquid delivery unit 26. The control unit 10 controls the pump 28.

[0110] <1-5. First Operation Example of Supply Source 19a and Processing Unit 11> 4 and 5. FIG. 5 is a flowchart showing the procedure of the substrate processing method of the first embodiment. FIG. 5 shows the procedure of a first operation example. In the first operation example, the substrate processing method includes step S1 and steps S11-S18. Step S1 is performed by the supply source 19a. Steps S11-S18 are substantially performed by the processing unit 11. Step S1 is performed in parallel with steps S11-S18. The supply source 19a and the processing unit 11 operate under the control of the control unit 10.

[0111] Step S1: Processing liquid generation process A processing liquid L is produced.

[0112] The production unit 20 produces the treatment liquid L in a tank 21. The production unit 20 stores the treatment liquid L in the tank 21.

[0113] Step S11: Rotation start process The substrate W starts to rotate.

[0114] The substrate holding unit 13 holds the substrate W. The substrate W is held in a substantially horizontal position. The rotation drive unit 14 starts to rotate the substrate holding unit 13. The substrate W rotates integrally with the substrate holding unit 13. In steps S12-S17, the substrate W continues to rotate, for example.

[0115] Step S12: Chemical solution supply process A chemical solution is supplied to the substrate W.

[0116] The supply unit 15b supplies a chemical solution to the substrate W held by the substrate holding unit 13. The chemical solution is supplied to the upper surface WS1 of the substrate W. For example, the chemical solution etches the substrate W. For example, the chemical solution removes a native oxide film from the substrate W. Then, the supply unit 15b stops supplying the chemical solution to the substrate W.

[0117] When the chemical solution is hydrofluoric acid, the chemical solution terminates the upper surface WS1 of the substrate W with hydrogen. For example, the hydrogen bonds with atoms (e.g., silicon atoms) located on the upper surface WS1 of the substrate W. As a result, the upper surface WS1 of the substrate W is modified to be hydrophobic.

[0118] Step S13: First Rinse Liquid Supply Process A rinse liquid is supplied to the substrate W.

[0119] The supply unit 15c supplies a rinse liquid to the substrate W held by the substrate holder 13. The rinse liquid is supplied to the upper surface WS1 of the substrate W. The rinse liquid removes the chemical liquid from the substrate W. The chemical liquid on the substrate W is replaced with the rinse liquid. Then, the supply unit 15c stops supplying the rinse liquid to the substrate W.

[0120] Even after the rinsing liquid supply step, the substrate W is still terminated with hydrogen, so that the upper surface WS1 of the substrate W remains hydrophobic even after the first rinsing liquid supply step.

[0121] Step S14: Substitute liquid supply process A substitute liquid is supplied to the substrate W.

[0122] The supply unit 15d supplies the substitute liquid to the substrate W held by the substrate holder 13. The substitute liquid is supplied to the upper surface WS1 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. Then, the supply unit 15d stops supplying the substitute liquid to the substrate W.

[0123] Even after the substitute liquid supplying step, the substrate W is still terminated with hydrogen, so that the upper surface WS1 of the substrate W remains hydrophobic even after the substitute liquid supplying step.

[0124] Step S15: Processing liquid supply process In the processing liquid supplying step, the upper surface WS1 of the substrate W is hydrophobic.

[0125] The liquid delivery unit 26 supplies the processing liquid L from the generation unit 20 to the supply unit 15a. The supply unit 15a supplies the processing liquid L to the substrate W held by the substrate holder 13. The processing liquid L is supplied to the upper surface WS1 of the substrate W. The processing liquid L removes the replacement liquid from the substrate W. The replacement liquid on the substrate W is replaced with the processing liquid L. Then, the liquid delivery unit 26 stops supplying the processing liquid L to the supply unit 15a. The supply unit 15a stops supplying the processing liquid L to the substrate W.

[0126] 6 is a diagram schematically illustrating the substrate W in the processing liquid supply step. When the substrate W is held by the substrate holding part 13, the pattern P is located on the upper surface WS1 of the substrate W. When the substrate W is held by the substrate holding part 13, the pattern P faces upward.

[0127] The processing liquid L on the substrate W forms a liquid film M. The liquid film M is located on the substrate W. The liquid film M is located on the upper surface WS1. The liquid film M covers the upper surface WS1.

[0128] The pattern P comes into contact with the treatment liquid L. The protrusions A come into contact with the treatment liquid L.

[0129] The entire pattern P is immersed in the liquid film M. The entire protrusion A is immersed in the liquid film M. The liquid film M has an upper surface M1. The upper surface M1 is located at a higher position than the pattern P. The upper surface M1 is located at a higher position than the protrusion A. The recess B is filled with the liquid film M. The entire recess B is filled with only the liquid film M.

[0130] The substitute liquid has already been removed from the substrate W by the processing liquid L. Therefore, the substitute liquid does not exist on the substrate W. The substitute liquid does not remain in the recess B.

[0131] The liquid film M is in contact with the gas J. The upper surface M1 is in contact with the gas J. The pattern P is not in contact with the gas J. The pattern P is not exposed to the gas J. The protrusion A is not in contact with the gas J. The protrusion A is not exposed to the gas J. The gas J corresponds to the atmosphere inside the housing 12.

[0132] In the processing liquid supplying step, the height position of the upper surface M1 may further be adjusted. For example, the height position of the upper surface M1 may be adjusted while the supply unit 15a is supplying the processing liquid L to the substrate W. For example, the height position of the upper surface M1 may be adjusted after the supply unit 15a has stopped supplying the processing liquid L. For example, the height position of the upper surface M1 may be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface M1 may be adjusted by adjusting the rotation time of the substrate W. Adjusting the height position of the upper surface M1 corresponds to adjusting the thickness of the liquid film M.

[0133] Even after the processing liquid supplying step, the substrate W is still terminated with hydrogen, so that the upper surface WS1 of the substrate W remains hydrophobic even after the processing liquid supplying step.

[0134] Step S16: Solidified film formation process In the solidified film forming step, the upper surface WS1 of the substrate W is hydrophobic. The solvent evaporates from the processing liquid L on the substrate W. A solidified film is formed on the substrate W. The solidified film includes a sublimable substance.

[0135] 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. Therefore, the solvent evaporates smoothly from the processing liquid L on the substrate W. The solvent changes smoothly from a liquid to a gas.

[0136] As the solvent evaporates from the processing liquid L, the amount of solvent in the processing liquid L decreases. As the amount of solvent in the processing liquid L decreases, the concentration of the sublimable substance in the processing liquid L increases. Eventually, the sublimable substance in the processing liquid L begins to precipitate. The sublimable substance begins to precipitate from the processing liquid L. The sublimable substance changes from a solute in the processing liquid L to a solid. The solid sublimable substance forms a solidified film G. In other words, the solidified film G corresponds to the solid sublimable substance. The solidified film G contains the sublimable substance. The solidified film G does not contain the solvent. The solidified film G is solid. In this way, as the solvent evaporates from the processing liquid L and the sublimable substance precipitates from the processing liquid L, the processing liquid L changes into a solidified film G. As the processing liquid L changes into a solidified film G, the processing liquid L decreases. As the processing liquid L changes into a solidified film G, the liquid film M becomes thinner.

[0137] The solidified film G is formed on the substrate W.

[0138] Further solvent evaporates from the processing liquid L on the substrate W. The solidified film G increases on the substrate W. The solidified film G grows on the substrate W. The processing liquid L on the substrate W decreases further. The liquid film M becomes thinner.

[0139] Finally, all of the solvent is removed from the substrate W. All of the processing liquid L disappears from the substrate W. All of the liquid film M disappears from the substrate W. No liquid exists on the substrate W. The pattern P does not come into contact with the liquid. The protrusions A do not come into contact with the liquid.

[0140] The solidified film G covers the upper surface WS1 of the substrate W. The upper surface WS1 is in contact with the solidified film G. The pattern P is in contact with the solidified film G. The pattern P is supported by the solidified film G. The protrusion A is in contact with the solidified film G. The protrusion A is supported by the solidified film G. The recess B is filled with the solidified film G. The entire recess B is filled only with the solidified film G.

[0141] 8 is an enlarged view schematically showing the substrate W in the solidified film forming step. The growth of the solidified film G will be explained again.

[0142] When the solidified film G grows, the solidified film G and the processing liquid L are present on the substrate W at the same time. The substrate W and the processing liquid L are in contact with each other. The substrate W and the solidified film G are in contact with each other. The solidified film G and the processing liquid L are in contact with each other. A first interface, a second interface, and a third interface are formed at the same time. The first interface is the interface between the processing liquid L and the substrate W. The second interface is the interface between the solidified film G and the substrate W. The third interface is the interface between the processing liquid L and the solidified film G.

[0143] The first interface has an interfacial free energy γLW, the second interface has an interfacial free energy γGW, and the third interface has an interfacial free energy γLG.

[0144] Here, the coefficient K is defined by the interfacial free energies γLW, γGW, and γLG. Specifically, the coefficient K is defined by equation (1). K = γLG + γGW - γLW (1)

[0145] The inventors have found the following regarding the coefficient K: The lower the coefficient K, the more easily the sublimable substance deposits on the surface WS of the substrate W. The lower the coefficient K, the more easily the solidified film G comes into contact with the surface WS. The lower the coefficient K, the more easily the solidified film G spreads on the surface WS. The lower the coefficient K, the more easily the solidified film G extends along the surface WS. For example, the lower the coefficient K, the more easily the solidified film G extends in the directions Ua and Ub on the surface WS. The coefficient K is an index that indicates the ease with which the solidified film G spreads on the substrate W.

[0146] As described above, when the coefficient K is low, the solidified film G is likely to spread on the substrate W during the solidified film formation process. Therefore, the solidified film G spreads quickly on the substrate W. The solidified film G also spreads quickly in the recessed portion B. The rapid expansion of the solidified film G promotes evaporation of the solvent. The rapid expansion of the solidified film G promotes reduction of the processing liquid L. Therefore, the solvent evaporates quickly from the processing liquid L on the substrate W. The processing liquid L on the substrate W is rapidly reduced. Therefore, by the end of the solidified film formation process, all of the solvent is reliably removed from the substrate W. By the end of the solidified film formation process, all of the processing liquid L on the substrate W is reliably removed.

[0147] The control unit 10 is configured to acquire the coefficient K. The control unit 10 may acquire the coefficient K in various ways. For example, the control unit 10 reads out the coefficient K. For example, the control unit 10 selects the coefficient K. For example, the control unit 10 calculates the coefficient K. For example, the control unit 10 receives the coefficient K.

[0148] The coefficient K is set in advance, for example. The coefficient K is set based on, for example, experiments or analysis. The coefficient K is stored in, for example, a storage medium of the control unit 10. The control unit 10 reads out the coefficient K stored in the storage medium, for example.

[0149] The multiple coefficients K are set, for example, according to the composition of the processing liquid L. The multiple coefficients K are set, for example, according to the compositions of the multiple solidified films G. The multiple coefficients K are set, for example, according to the state of the surface WS of the substrate W. The multiple coefficients K are set, for example, for each of the multiple pieces of processing condition information. The control unit 10 may select one coefficient K from the multiple coefficients K.

[0150] Here, the state of the surface WS of the substrate W refers to, for example, the affinity between the substrate W and water. The state of the surface WS refers to, for example, the affinity between the surface WS and water.

[0151] The control unit 10 may calculate the coefficient K based on, for example, the composition of the processing liquid L. The control unit 10 may calculate the coefficient K based on, for example, the composition of the solidified film G. The control unit 10 may calculate the coefficient K based on, for example, the state of the surface WS of the substrate W. The control unit 10 may calculate the coefficient K based on, for example, the state of the surface WS of the substrate W in at least one of the processing liquid supply step and the solidified film formation step. Here, the control unit 10 may identify at least one of the composition of the processing liquid L and the composition of the solidified film G based on processing condition information. The control unit 10 may identify the composition of the solidified film G based on the composition of the processing liquid L. The control unit 10 may estimate the state of the surface WS of the substrate W in at least one of the processing liquid supply step and the solidified film formation step based on the composition of the chemical liquid and the composition of the cleaning liquid. The control unit 10 may identify the composition of the chemical liquid and the composition of the cleaning liquid based on processing condition information.

[0152] For example, the control unit 10 may receive the coefficient K from an internal device of the substrate processing apparatus 1. The internal device of the substrate processing apparatus 1 is, for example, an input unit (not shown). A user may provide the coefficient K to the control unit 10 via the input unit. For example, the control unit 10 may receive the coefficient K from outside the substrate processing apparatus 1. The external device of the substrate processing apparatus 1 is, for example, a host computer.

[0153] The control unit 10 is configured to monitor the coefficient K. This makes it possible to monitor the quality of the processing performed on the substrate W.

[0154] The control unit 10 is configured to manage the coefficient K. This makes it possible to manage the quality of the processing on the substrate W.

[0155] For example, the control unit 10 controls the coefficient K to be equal to or less than the threshold value TH.

[0156] Here, the threshold value TH is, for example, set in advance, is, for example, a constant, or is set based on, for example, experiments or analysis.

[0157] The control unit 10 is configured to acquire the threshold value TH. The control unit 10 may acquire the threshold value TH in various ways. For example, the control unit 10 reads the threshold value TH. For example, the control unit 10 selects the threshold value TH. For example, the control unit 10 calculates the threshold value TH. For example, the control unit 10 receives the threshold value TH.

[0158] The threshold value TH is set in advance, for example. The threshold value TH is set based on, for example, experiments or analysis. The threshold value TH is stored in, for example, a storage medium of the control unit 10. The control unit 10 reads out the threshold value TH stored in, for example, the storage medium.

[0159] Step S17: Sublimation process The solidified film G sublimes, and the substrate W is dried.

[0160] The supply unit 15f supplies a dry gas to the substrate W held by the substrate holder 13. The dry gas is supplied to the upper surface WS1 of the substrate W. The dry gas is supplied to the solidified film G. The solidified film G is exposed to the dry gas. Therefore, the solidified film G sublimes smoothly. The solidified film G changes into a gas without passing through a liquid state. The solidified film G is removed from the substrate W by the sublimation of the solidified film G. Then, the supply unit 15f stops supplying the dry gas to the solidified film G.

[0161] 9 is a diagram schematically showing the substrate W in the sublimation step. As the solidified film G sublimes, the solidified film G decreases in thickness. As the solidified film G sublimes, the solidified film G becomes thinner.

[0162] Pattern P begins to be exposed to gas J. Convex portion A begins to be exposed to gas J. Gas J begins to enter concave portion B.

[0163] It should be noted that when the solidified film G sublimes, it does not change into a liquid. Therefore, in the sublimation process, no liquid is generated on the substrate W. Therefore, in the sublimation process, the pattern P is not subjected to a significant force. In the sublimation process, the protrusion A is not subjected to a significant force. The significant force is, for example, the surface tension of the liquid.

[0164] FIG. 10 is a diagram showing a substrate W during the sublimation process. FIG. 10 shows a schematic diagram of the substrate W, for example, at the end of the sublimation process. Finally, the entire solidified film G is removed from the substrate W. No liquid is present on the substrate W. The entire pattern P is exposed to the gas J. The entire protrusion A is exposed to the gas J. The entire recess B is filled only with the gas J. The substrate W is dried.

[0165] The above-described treatment liquid supplying step, solidified film forming step, and sublimation step are examples of drying treatment.

[0166] Step S18: Rotation stop process The substrate W stops rotating.

[0167] The rotation driver 14 stops the rotation of the substrate holder 13. The substrate W stops together with the substrate holder 13. The substrate W comes to a standstill. The processing unit 11 finishes processing the substrate W.

[0168] <1-6. Second Operation Example of Supply Source 19a and Processing Unit 11> See Figures 4 and 11. Figure 11 is a flowchart showing the procedure of the substrate processing method of the first embodiment. Figure 11 shows the procedure of a second operation example. In the second operation example, the substrate processing method includes step S1 and steps S11-S18. For convenience, step S1 is not shown in Figure 11. In the second operation example, the substrate processing method further includes steps S21 and S22. Steps S21 and S22 are performed after step S13. Steps S21 and S22 are performed before step S14.

[0169] The operations of steps S1 and S11-S18 are substantially common between the first and second operation examples. Therefore, a description of the operations of steps S1, S11, and S17-S18 will be omitted. The operations of steps S12, S21, S22, S14, S15, and S16 will be described.

[0170] Step S12: Chemical solution supply process A chemical solution is supplied to the substrate W. When the chemical solution is hydrofluoric acid, the surface WS of the substrate W is modified to be hydrophobic.

[0171] Step S13: First Rinse Liquid Supply Process The rinse liquid is supplied to the substrate W. Even after the first rinse liquid supplying step, the surface WS of the substrate W remains hydrophobic.

[0172] Step S21: Cleaning liquid supply process A cleaning liquid is supplied to the substrate W.

[0173] The supply unit 15d supplies the cleaning liquid to the substrate W. The cleaning liquid is supplied to the upper surface WS1 of the substrate W. The cleaning liquid removes the rinse liquid from the substrate W. The rinse liquid on the substrate W is replaced with the cleaning liquid. For example, the cleaning liquid cleans the substrate W. Then, the supply unit 15d stops supplying the cleaning liquid to the substrate W.

[0174] When the cleaning liquid is SC1, the cleaning liquid forms an oxide film on the upper surface WS1 and terminates the upper surface WS1 with a hydroxy group. For example, the hydroxy group bonds with atoms (e.g., silicon atoms) located on the upper surface WS1 of the substrate W. As a result, the upper surface WS1 of the substrate W is modified to be hydrophilic. The upper surface WS1 of the substrate W is modified from hydrophobic to hydrophilic. For example, the affinity between the substrate W and water at the end of the cleaning liquid supply process is higher than the affinity between the substrate W and water at the start of the cleaning liquid supply process. For example, the affinity between the substrate W and water at the end of the cleaning liquid supply process is higher than the affinity between the substrate W and water at the end of the chemical liquid supply process.

[0175] Step S22: Second Rinse Liquid Supply Process A rinse liquid is supplied to the substrate W.

[0176] The supply unit 15c supplies a rinse liquid to the substrate W held by the substrate holder 13. The rinse liquid is supplied to the upper surface WS1 of the substrate W. The rinse liquid removes the cleaning liquid from the substrate W. The cleaning liquid on the substrate W is replaced with the rinse liquid. Then, the supply unit 15c stops supplying the rinse liquid to the substrate W.

[0177] Even after the second rinse liquid supplying step, the substrate W is still terminated with hydroxy groups, and therefore, the substrate W remains hydrophilic even after the second rinse liquid supplying step.

[0178] Step S14: Substitute liquid supply process The substitute liquid is supplied to the substrate W. Even after the substitute liquid supplying step, the substrate W is still terminated with hydroxy groups, so that the upper surface WS1 of the substrate W remains hydrophilic even after the substitute liquid supplying step.

[0179] Step S15: Processing liquid supply process In the processing liquid supplying step, the upper surface WS1 of the substrate W is hydrophilic. The processing liquid L is supplied to the substrate W. Even after the processing liquid supplying step, the substrate W is still terminated with hydroxy groups. Therefore, even after the processing liquid supplying step, the upper surface WS1 of the substrate W is hydrophilic.

[0180] Step S16: Solidified film formation process In the solidified film forming step, the upper surface WS1 of the substrate W has hydrophilic properties. The solvent evaporates from the processing liquid L on the substrate W. A solidified film G is formed on the substrate W.

[0181] As described above, in the second operation example, the upper surface WS1 of the substrate W changes from hydrophobic to hydrophilic. The affinity between the substrate W and water in the processing liquid supply process of the second operation example is higher than the affinity between the substrate W and water in the processing liquid supply process of the first operation example. The affinity between the substrate W and water in the solidified film formation process of the second operation example is higher than the affinity between the substrate W and water in the solidified film formation process of the first operation example.

[0182] <1-7. Technical significance of coefficient K> The technical significance of the coefficient K will be explained using Examples 1a, 1b, 2a, 2b, 3a, 3b, 4a, and 4b. Hereinafter, the upper surface WS1 will be referred to as the surface WS for convenience.

[0183] Examples 1a, 1b, 2a, 2b, 3a, 3b, 4a, and 4b differ from one another in terms of the state of the surface WS of the substrate W and the composition of the processing liquid.

[0184] The conditions of Example 1a will be described. In Example 1a, the substrate W is processed by the substrate processing method of the first operation example. Specifically, in Example 1a, the substrate W is subjected to a series of processes including a chemical liquid supplying step, a first rinse liquid supplying step, a replacement liquid supplying step, a processing liquid supplying step, a solidified film forming step, and a sublimation step.

[0185] In the chemical supplying step, the chemical is hydrofluoric acid. The hydrofluoric acid is a mixture of hydrogen fluoride and deionized water. The volume ratio of hydrogen fluoride to deionized water is as follows: Hydrogen fluoride: deionized water = 1:10 (volume ratio)

[0186] In the first rinse liquid supplying step, the rinse liquid is deionized water.

[0187] In the substitution liquid supplying step, the substitution liquid is isopropyl alcohol.

[0188] In the treatment liquid supplying step, the treatment liquid is composed of a sublimable substance and a solvent. The sublimable substance is cyclohexanone oxime. The solvent is isopropyl alcohol. The volume ratio of the sublimable substance to the solvent is as follows: Sublimable substance:solvent=1:40 (volume ratio)

[0189] In the solidified film forming step, the substrate W is rotated at a rotation speed of 1500 rpm.

[0190] In the sublimation step, the substrate W is rotated at a rotation speed of 1500 rpm. Furthermore, in the sublimation step, a dry gas is supplied to the substrate W. The dry gas is air.

[0191] In the processing liquid supply step and the solidified film formation step of Example 1a, the surface WS of the substrate W is hydrophobic. That is, the state of the surface WS in the processing liquid supply step and the solidified film formation step is hydrophobic. The subscript "a" in Example 1a means that the state of the surface WS in the processing liquid supply step and the solidified film formation step is hydrophobic.

[0192] The conditions of Example 1b will be described. In Example 1b, the substrate W is processed by the substrate processing method of the second operation example. Specifically, in Example 2, the substrate W is subjected to a series of processes including a chemical liquid supplying step, a first rinsing liquid supplying step, a cleaning liquid supplying step, a second rinsing liquid supplying step, a replacement liquid supplying step, a processing liquid supplying step, a solidified film forming step, and a sublimation step.

[0193] In the cleaning solution supplying step, the cleaning solution is SC1. SC1 is a mixture of ammonia, hydrogen peroxide, and deionized water. The volume ratio of ammonia, hydrogen peroxide, and deionized water is as follows: Ammonia: hydrogen peroxide: deionized water = 1:8:60 (volume ratio)

[0194] In the second rinse liquid supplying step, the rinse liquid is deionized water.

[0195] Other than this, the conditions of Example 1b are the same as those of Example 1a.

[0196] In the processing liquid supply step and the solidified film formation step of Example 2, the surface WS of the substrate W is hydrophilic. That is, the state of the surface WS in the processing liquid supply step and the solidified film formation step is hydrophilic. The subscript "b" in Example 1b means that the state of the surface WS in the processing liquid supply step and the solidified film formation step is hydrophilic.

[0197] The conditions for Examples 2a and 2b are explained below. In the treatment liquid supplying step, the treatment liquid is composed of a sublimable substance and a solvent. The sublimable substance is cyclohexanone oxime. The solvent is methanol. The volume ratio of the sublimable substance to the solvent is as follows: Sublimable substance:solvent=1:40 (volume ratio) Other conditions for Example 2a are the same as those for Example 1a. Other conditions for Example 2b are the same as those for Example 1b.

[0198] The conditions of Examples 3a and 3b are explained below. In the treatment liquid supplying step, the treatment liquid is composed of a sublimable substance and a solvent. The sublimable substance is camphor. The solvent is isopropyl alcohol. The volume ratio of the sublimable substance to the solvent is as follows: Sublimable substance:solvent=1:110 (volume ratio) Other conditions for Example 3a are the same as those for Example 1a. Other conditions for Example 3b are the same as those for Example 1b.

[0199] The conditions of Examples 4a and 4b are explained below. In the treatment liquid supplying step, the treatment liquid is composed of a sublimable substance and a solvent. The sublimable substance is camphor. The solvent is methanol. The volume ratio of the sublimable substance to the solvent is as follows: Sublimable substance:solvent = 1:100 (volume ratio) Other conditions for Example 4a are the same as those for Example 1a. Other conditions for Example 4b are the same as those for Example 1b.

[0200] Each of the substrates W treated in Examples 1a, 1b, 2a, 2b, 3a, 3b, 4a, and 4b was evaluated by the average collapse rate E.

[0201] The average collapse rate E is calculated as follows. The average collapse rate E is the average value of multiple local collapse rates ei. The local collapse rate ei is the collapse rate in a local area Fi. i is any natural number from 1 to NF. The number NF is the number of local areas Fi. The number NF is a natural number greater than or equal to 2. Each local area Fi is a microscopic region on the substrate W. Each local area Fi is magnified 50,000 times using a scanning electron microscope, for example. An observer observes the pattern P (protrusions A) in each local area Fi. The observer observes each protrusion A in each local area Fi one by one. Specifically, the observer classifies each protrusion A into either a collapsed protrusion A or an uncollapsed protrusion A. Here, the number of protrusions A observed in a local area Fi is defined as NAi. The number of collapsed protrusions A in a local area Fi is defined as NBi. The number NBi is less than or equal to the number NAi. The local collapse rate ei is the ratio of the number NBi to the number NAi. The local collapse rate ei is defined, for example, by the following formula: ei=NBi / NAi*100 (%) The average collapse rate E is the sum of the local collapse rates ei divided by the number NF.

[0202] Furthermore, the coefficient K in Examples 1a, 1b, 2a, 2b, 3a, 3b, 4a, and 4b was obtained.

[0203] An example of a procedure for acquiring the coefficient K will be described. The procedure for acquiring the coefficient K includes, for example, a preparation step, a measurement step, and a calculation step. The procedure for acquiring the coefficient K will be described using the coefficient K in Examples 3a and 3b as an example.

[0204] <<Preparation process>> A first substrate Wa and a second substrate Wb are prepared as the substrates W. The first substrate Wa simulates the substrate W in the processing liquid supply step of Example 3a. For example, the first substrate Wa is a substrate W that has been subjected to a process that includes only a chemical liquid supply step, a first rinse liquid supply step, a substitute liquid supply step, and a spin-drying step. Here, in the spin-drying step, the substrate W is rotated to shake off the liquid (e.g., substitute liquid) on the substrate W, thereby drying the substrate W. The surface WS of the first substrate Wa is hydrophobic. The second substrate Wb simulates the substrate W in the processing liquid supply step of Example 3b. For example, the second substrate Wb is a substrate W that has been subjected to a process that includes only a chemical liquid supply step, a first rinse liquid supply step, a cleaning liquid supply step, a second rinse step, a substitute liquid supply step, and a spin-drying step. The surface WS of the second substrate Wb is hydrophilic.

[0205] Furthermore, a solidified film G and a processing liquid L are prepared. The solidified film G is, for example, a simulation of the solidified film G in Examples 3a and 3b. The solidified film G is, for example, made of solid camphor. The solidified film G prepared to obtain the coefficient K does not have to be formed on the substrate W. The solidified film G has, for example, a block or plate shape. The processing liquid L is, for example, the processing liquid used in Examples 3a and 3b. The processing liquid L is, for example, made of camphor and isopropyl alcohol.

[0206] Furthermore, a first standard solution and a second standard solution are prepared, where the values ​​of the surface free energies γ1 and γ2, the dispersion components γ1d and γ2d, and the polar components γ1p and γ2p for the first and second standard solutions are known. γ1: Surface free energy of the first standard solution γ1d: Dispersion component of the surface free energy γ1 of the first standard liquid γ1p: Polar component of the surface free energy γ1 of the first standard solution γ2: Surface free energy of the second standard solution γ2d: Dispersion component of the surface free energy γ2 of the second standard liquid γ2p: Polar component of the surface free energy γ2 of the second standard solution

[0207] The first standard solution is, for example, diiodomethane, and the second standard solution is, for example, glycerin.

[0208] <<Measurement process>> The contact angles θ1a, θ1b, θ2a, θ2b, θ3, θ4, and θ5 were measured. θ1a: contact angle between the first standard liquid and the first substrate Wa θ1b: contact angle between the first standard liquid and the second substrate Wb θ2a: Contact angle between the second standard liquid and the first substrate Wa θ2b: contact angle between the second standard liquid and the second substrate Wb θ3: Contact angle between the first standard liquid and the solidified film G θ4: Contact angle between the second standard liquid and the solidified film G θ5: Contact angle between the treatment liquid L and the solidified film G

[0209] The contact angles θ1a, θ1b, θ2a, θ2b, θ3, θ4, and θ5 are each measured, for example, by a contact angle method. The contact angles θ1a, θ1b, θ2a, θ2b, θ3, θ4, and θ5 are each measured, for example, using a contact angle meter. The contact angles θ1a, θ1b, θ2a, θ2b, θ3, θ4, and θ5 are each measured, for example, in an environment at room temperature. The contact angles θ1a, θ1b, θ2a, θ2b, θ3, θ4, and θ5 are each measured, for example, in an environment at normal pressure.

[0210] Furthermore, the surface free energy γL was measured. γL: Surface free energy of treatment liquid L

[0211] The surface free energy γL is measured, for example, by the hanging drop method. The surface free energy γL is measured, for example, in an environment at room temperature. The surface free energy γL is measured, for example, in an environment at normal pressure.

[0212] <<Calculation process>> The coefficient K is calculated based on the value measured in the measurement step. For convenience, the coefficient K in Example 3a will be calculated below.

[0213] In calculating the coefficient K, in addition to equation (1), equations (2) to (4) are used. γ = γd + γp (2) γAB=γA-γBcosθ (3) γA + γB - γAB = 2(γAd γBd) 1 / 2 +2(γAp·γBp) 1 / 2 ···(4)

[0214] Based on the contact angles θ1a and θ2a, the surface free energy γW, dispersion component γWd, and polar component γWp are calculated. In this calculation, the known surface free energies γ1 and γ2, dispersion components γ1d and γ2d, and polar components γ1p and γ2p are used. γW: Surface free energy of substrate W γWd: Dispersion component of the surface free energy γW of the substrate W γWp: Polar component of the surface free energy γW of the substrate W

[0215] This calculation uses equations (2), (3), and (4). For example, equation (5) is derived from equations (3) and (4). γB(1+cosθ)=2(γAd·γBd) 1 / 2 +2(γAp·γBp) 1 / 2 ···(5) In equation (5), substitute the surface free energy γ1 for γB, the dispersion component γ1d for γBd, the polar component γ1p for γBp, and the contact angle θ1a for θ. This results in the first equation. In equation (5), substitute the surface free energy γ2 for γB, the dispersion component γ2d for γBd, the polar component γ2p for γBp, and the contact angle θ2a for θ. This results in the second equation. From the first and second equations, the values ​​of γAd and γAp are calculated. The value of γAd corresponds to the value of the dispersion component γWd. The value of γAp corresponds to the value of the polar component γWp. Furthermore, in equation (2), substitute the dispersion component γWd for γd and the polar component γWp for γp. This results in the value of γ. The value of γ corresponds to the value of the surface free energy γW. That is, the sum of the dispersive component γWd and the polar component γWp is equal to the surface free energy γW.

[0216] Based on the contact angles θ3 and θ4, the surface free energy γG, dispersion component γGd, and polar component γGp are calculated. In this calculation, the known surface free energies γ1 and γ2, dispersion components γ1d and γ2d, and polar components γ1p and γ2p are used. γG: Surface free energy of solidified film G γGd: Dispersion component of the surface free energy γG of the solidified film G γGp: Polar component of the surface free energy γG of solidified film G

[0217] This calculation uses equations (2), (3), and (4). The calculation of the surface free energy γG, the dispersion component γGd, and the polar component γGp is ​​similar to the calculation of the surface free energy γW, the dispersion component γWd, and the polar component γWp.

[0218] Calculate the interfacial free energy γGW. In this calculation, the calculated surface free energies γG, γW, dispersion components γGd, γWd, and polar components γGp, γWp are used.

[0219] This calculation uses equation (4). For example, in equation (4), the surface free energies γG and γW are substituted for γA and γB, respectively, the dispersion components γGd and γWd are substituted for γAd and γBd, respectively, and the polar components γGp and γWp are substituted for γAp and γBp, respectively. This calculates the value of γAB. The value of γAB corresponds to the value of the interfacial free energy γGW.

[0220] The interfacial free energy γ is calculated based on the contact angle θ and the surface free energy γ. In this calculation, the calculated surface free energy γ is used.

[0221] In this calculation, equation (3) is used. For example, in equation (3), the surface free energy γG is substituted for γA, the surface free energy γL is substituted for γB, and the contact angle θ5 is substituted for θ. This calculates the value of γAB. The value of γAB corresponds to the value of the interfacial free energy γLG.

[0222] The dispersion component γLd and polar component γLp are calculated based on the surface free energy γL. In this calculation, the calculated surface free energy γG, interfacial free energy γLG, dispersion component γGd, and polar component γGp are used. γLd: Dispersion component of the surface free energy γL of the treatment liquid L γLp: Polar component of the surface free energy γL of the treatment liquid L

[0223] In this calculation, equations (2) and (4) are used. In equation (4), the surface free energy γL is substituted for γA, the surface free energy γG is substituted for γB, the interfacial free energy γLG is substituted for γAB, the dispersion component γGd is substituted for γBd, and the polar component γGp is ​​substituted for γBp. This leads to the third equation. From equation (2), γAd and γAp in the third equation have the following relationship: γAd+γAp=γL Using this relationship, the values ​​of γAd and γAp are calculated from the third equation. The value of γAd corresponds to the value of the dispersion component γLd. The value of γAp corresponds to the value of the polar component γLp.

[0224] The interfacial free energy γLW is calculated based on the surface free energy γL. In this calculation, the calculated surface free energy γW, dispersion components γLd, γWd, and polar components γLp, γWp are used.

[0225] In this calculation, equation (4) is used. The calculation of the interfacial free energy γ is similar to the calculation of the interfacial free energy γ.

[0226] Finally, the coefficient K is calculated. In this calculation, the calculated interfacial free energies γLG, γGW, and γLW are used. In this calculation, equation (1) is used.

[0227] Through the above procedure, the coefficient K of the embodiment 3a is obtained.

[0228] When calculating the coefficient K in Example 3b, the "contact angle θ1a" and "contact angle θ1b" in the above explanation are changed to "contact angle θ1b" and "contact angle θ2b", respectively.

[0229] When the contact angles θ1a and θ1b are not distinguished from each other, the contact angles θ1a and θ1b are simply referred to as the "contact angle θ1." When the contact angles θ2a and θ2b are not distinguished from each other, the contact angles θ2a and θ2b are simply referred to as the "contact angle θ2." The surface free energy γW, the dispersion component γWd, and the polar component γWp are calculated based on the contact angles θ1 and θ2. The interfacial free energies γGW and γLW are calculated based on the surface free energy γW, the dispersion component γWd, and the polar component γWp. Therefore, the interfacial free energies γGW and γLW are set according to the surface free energy γW of the substrate W. The interfacial free energies γGW and γLW are set according to the contact angles θ1 and θ2.

[0230] Here, the contact angles θ1 and θ2 are indices that indicate the state of the surface WS of the substrate W. Therefore, the interfacial free energies γGW and γLW are set in accordance with the state of the surface WS of the substrate W.

[0231] For example, the contact angles θ1 and θ2 are indices that indicate the state of the surface WS of the substrate W in the processing liquid supply step. Therefore, the interfacial free energies γGW and γLW are set based on the state of the surface WS of the substrate W in the processing liquid supply step.

[0232] For example, the contact angles θ1 and θ2 are also indicators of the state of the surface WS of the substrate W in the solidified film formation process. Therefore, the interfacial free energies γGW and γLW are set based on the state of the surface WS of the substrate W in the solidified film formation process.

[0233] A more specific explanation will be given. For convenience, the surface free energy γW of the first substrate Wa is referred to as the "first surface free energy γW." The surface WS of the first substrate Wa is hydrophobic. Therefore, the first surface free energy γW corresponds to the surface free energy γW of the substrate W when the surface WS is hydrophobic. When obtaining the coefficient K in Example 3a, the interfacial free energy γGW and the interfacial free energy γLW are each set based on the first surface free energy γW. Therefore, when the surface WS of the substrate W is hydrophobic in the processing liquid supply step, the interfacial free energy γGW and the interfacial free energy γLW are each set based on the first surface free energy γW. When the surface WS of the substrate W is hydrophobic in the solidified film formation step, the interfacial free energy γGW and the interfacial free energy γLW are each set based on the first surface free energy γW.

[0234] For convenience, the surface free energy γW of the second substrate Wb is referred to as the "second surface free energy γWb." The surface WS of the second substrate Wb is hydrophilic. The second surface free energy γWb corresponds to the surface free energy γW of the substrate W when the surface WS is hydrophilic. When obtaining the coefficient K in Example 3a, the interfacial free energy γGW and the interfacial free energy γLW are each set based on the second surface free energy γWb. Therefore, when the surface WS of the substrate W is hydrophilic in the processing liquid supply process, the interfacial free energy γGW and the interfacial free energy γLW are each set based on the second surface free energy γWb. When the surface WS of the substrate W is hydrophilic in the solidified film formation process, the interfacial free energy γGW and the interfacial free energy γLW are each set based on the second surface free energy γWb.

[0235] The coefficient K is calculated based on the interfacial free energies γGW and γLW. As described above, the interfacial free energies γGW and γLW are set according to the contact angles θ1 and θ2. The contact angles θ1 and θ2 are indices that indicate the state of the surface WS of the substrate W. Therefore, the coefficient K is set according to the state of the surface WS of the substrate W. When obtaining the coefficient K, the state of the surface WS of the substrate W is taken into consideration.

[0236] For example, the coefficient K is set based on the state of the surface WS of the substrate W in the processing liquid supply step, or based on the state of the surface WS of the substrate W in the solidified film forming step.

[0237] The coefficient K is calculated based on the interfacial free energies γGW and γLW. As described above, the interfacial free energies γGW and γLW are set according to the surface free energy γW of the substrate W. Therefore, the coefficient K is set according to the surface free energy γW of the substrate W. For example, when the coefficient K of Example 3a is obtained, the coefficient K is set based on the first surface free energy γWa. Therefore, when the surface WS of the substrate W is hydrophobic in the processing liquid supply process, the coefficient K is set based on the first surface free energy γWa. When the surface WS of the substrate W is hydrophobic in the solidified film formation process, the coefficient K is set based on the first surface free energy γWa. For example, when the coefficient K of Example 3b is obtained, the coefficient K is set based on the second surface free energy γWb. Therefore, when the surface WS of the substrate W is hydrophilic in the processing liquid supply process, the coefficient K is set based on the second surface free energy γWb. When the surface WS of the substrate W is hydrophilic in the solidified film formation process, the coefficient K is set based on the second surface free energy γWb.

[0238] More specifically, the coefficient K includes the coefficient K of Example 3a and the coefficient K of Example 3b. For convenience, the coefficient K of Example 3a is referred to as the "first coefficient Ka." The coefficient K of Example 3b is referred to as the "second coefficient Kb." The first coefficient Ka corresponds to the coefficient K when the surface WS of the substrate W is hydrophobic. The second coefficient Kb corresponds to the coefficient K when the surface WS of the substrate W is hydrophilic. The coefficient K switches between the first coefficient Ka and the second coefficient Kb depending on the state of the surface WS of the substrate W. Specifically, when the surface WS of the substrate W is hydrophobic, the coefficient K is set to the first coefficient Ka. For example, when the surface WS of the substrate W is hydrophobic in the processing liquid supply process, the coefficient K is set to the first coefficient Ka. For example, when the surface WS of the substrate W is hydrophobic in the solidified film formation process, the coefficient K is set to the first coefficient Ka. On the other hand, when the surface WS of the substrate W is hydrophilic, the coefficient K is set to the second coefficient Kb. For example, when the surface WS of the substrate W has hydrophilicity in the processing liquid supply process, the coefficient K is set to the second coefficient Kb. For example, when the surface WS of the substrate W has hydrophilicity in the solidified film formation process, the coefficient K is set to the second coefficient Kb.

[0239] Figure 12 is a table showing the coefficient K for each example. The table in Figure 12 also shows the interfacial free energies γLW, γGW, and γLG for each example. The table in Figure 12 also shows the average collapse rate E for each example.

[0240] FIG. 13 is a graph showing the relationship between the coefficient K and the average collapse rate E in each example.

[0241] The coefficient K ranges from 2.16mN / m to 41.23mN / m. -3 It may also be written as "N / m". When coefficient K is 22.86mN / m or more, the average collapse rate E is 100%. When coefficient K is 20.99mN / m or less, the average collapse rate E is 78.6% or less. When coefficient K is 18.19mN / m or less, the average collapse rate E is 37.4% or less. When coefficient K is 17.35mN / m or less, the average collapse rate E is 9.95% or less. When coefficient K is 2.23mN / m or less, the average collapse rate E is 0.7% or less.

[0242] The following is found from Examples 1a, 1b, 2a, 2b, 3a, 3b, 4a, and 4b: As the coefficient K decreases, the average collapse rate E decreases. This fact supports the findings of the present inventors regarding the coefficient K. For example, this fact indicates that "the lower the coefficient K, the easier the solidified film G spreads on the substrate W in the solidified film formation process."

[0243] When the coefficient K decreases from 23 mN / m to 17 mN / m, the average collapse rate E decreases significantly.

[0244] When the coefficient K is 18 mN / m or less, the average collapse rate E is 40% or less. When the coefficient K is 18 mN / m or less, the substrate W is processed with adequate quality.

[0245] When the coefficient K is 17 mN / m or less, the average collapse rate E is 10% or less. When the coefficient K is 17 mN / m or less, the substrate W is processed with more suitable quality.

[0246] When the coefficient K is equal to or less than the threshold value TH, the average collapse rate E is appropriately reduced. The threshold value TH is preferably, for example, 18 mN / m. The threshold value TH is preferably, for example, 17 mN / m.

[0247] As mentioned above, there is a certain relationship between the coefficient K and the average collapse rate E. It is possible to estimate the average collapse rate E from the coefficient K without actually measuring it.

[0248] When the coefficient K is 23 mN / m or more, the entire pattern P collapses. The reason for this is presumed to be as follows.

[0249] When the coefficient K is high, the sublimable substance is less likely to deposit on the surface WS of the substrate W. For example, the sublimable substance is more likely to deposit in the bulk portion of the processing liquid L. Here, the bulk portion is the portion of the processing liquid L that is not in contact with the substrate W. The bulk portion is the portion of the processing liquid L that is inward from the interface between the substrate W and the processing liquid L. The bulk portion does not include the interface between the substrate W and the processing liquid L. Therefore, the solidified film G is less likely to contact the surface WS of the substrate W. The solidified film G is less likely to spread on the surface WS. The solidified film G is less likely to extend along the surface WS.

[0250] As described above, when the coefficient K is high, the solidified film G does not spread easily on the substrate W during the solidified film formation process. Therefore, the solidified film G does not spread quickly on the substrate W. The solidified film G also does not spread quickly in the recess B. Therefore, the solidified film G does not promote evaporation of the solvent. The solidified film G does not promote reduction of the processing liquid L. Therefore, the solvent does not evaporate quickly from the processing liquid L on the substrate W. The processing liquid L on the substrate W does not reduce quickly. As a result, even at the end of the solidified film formation process, the solvent still remains on the substrate W. Even at the end of the solidified film formation process, the processing liquid L still remains on the substrate W.

[0251] In the sublimation process, not only the solidified film G but also the processing liquid L exists on the substrate W. Even after the entire solidified film G has sublimated in the sublimation process, the processing liquid L still remains on the substrate W. After the entire solidified film G has sublimated, the pattern P is no longer supported by the solidified film G and is subjected to a significant force from the processing liquid L. The significant force is, for example, the surface tension of the processing liquid L. As a result, the pattern P falls over.

[0252] <1-8. Effects of the First Embodiment> The substrate processing method is for processing a substrate W on which a pattern P 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 L is supplied to the substrate W. The processing liquid L contains a sublimable substance and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid L on the substrate W. In the solidified film forming step, a solidified film G is formed on the substrate W. The solidified film G contains a sublimable substance. In the sublimation step, the solidified film G is sublimated. The substrate W is dried by the sublimation of the solidified film G.

[0253] The coefficient K is defined by equation (1). The coefficient K is equal to or less than the threshold value TH. The coefficient K being equal to or less than the threshold value TH is appropriately referred to as the "first condition." The substrate W, the processing liquid L, and the solidified film G satisfy the first condition. Therefore, in the solidified film formation process, the solidified film G is suitably formed on the substrate W. Specifically, in the solidified film formation process, the solidified film G spreads smoothly on the substrate W. Therefore, in the solidified film formation process, the solvent is efficiently removed from the substrate W. In the solidified film formation process, the processing liquid L is efficiently eliminated from the substrate W. Therefore, in the sublimation process, the substrate W is dried while the pattern P formed on the substrate W is suitably protected.

[0254] As described above, according to the substrate processing method of the first embodiment, the substrate is processed appropriately.

[0255] The threshold value TH is a preset constant. Therefore, the first condition is simple. Therefore, it is easy to manage the substrate processing method so as to satisfy the first condition. For example, it is easy to manage the state of the surface WS of the substrate W in the processing liquid supply process so as to satisfy the first condition. For example, it is easy to manage the composition of the processing liquid L and the composition of the solidified film G so as to satisfy the first condition. Therefore, it is easy to execute the present substrate processing method.

[0256] The threshold value TH is, for example, 17 mN / m. In other words, the coefficient K is 17 mN / m or less. Therefore, in the solidified film formation process, the solidified film G spreads more smoothly on the substrate W. Therefore, the pattern P is suitably protected by the solidified film G. Therefore, the collapse of the pattern P is suitably suppressed.

[0257] The coefficient K is set in accordance with the state of the surface WS of the substrate W. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W. Therefore, the substrate W is processed appropriately regardless of the state of the surface WS of the substrate W.

[0258] The coefficient K is set based on the state of the surface WS of the substrate W in the processing liquid supply process. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W in the processing liquid supply process. Therefore, the substrate W is processed appropriately regardless of the state of the surface WS of the substrate W in the processing liquid supply process.

[0259] The coefficient K is set based on the state of the surface WS of the substrate W in the solidified film formation process. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W in the solidified film formation process. Therefore, the substrate W is processed appropriately regardless of the state of the surface WS of the substrate W in the solidified film formation process.

[0260] The interfacial free energy γ and the interfacial free energy γ are each set according to the state of the surface WS of the substrate W. Therefore, the interfacial free energy γ and the interfacial free energy γ are each set appropriately regardless of the state of the surface WS of the substrate W. Therefore, when the coefficient K is set, the state of the surface WS of the substrate W is appropriately taken into consideration. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W.

[0261] The interfacial free energy γGW and the interfacial free energy γLW are each set based on the state of the surface WS of the substrate W in the processing liquid supply process. Therefore, the interfacial free energy γGW and the interfacial free energy γLW are each set appropriately regardless of the state of the surface WS of the substrate W in the processing liquid supply process. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W in the processing liquid supply process.

[0262] The interfacial free energy γGW and the interfacial free energy γLW are each set based on the state of the surface WS of the substrate W in the solidified film formation process. Therefore, the interfacial free energy γGW and the interfacial free energy γLW are each set appropriately regardless of the state of the surface WS of the substrate W in the solidified film formation process. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W in the solidified film formation process.

[0263] When the surface W of the substrate W is hydrophobic in the processing liquid supply process, the interfacial free energy γ and the interfacial free energy γ are each set based on the first surface free energy γ. Therefore, when the surface W of the substrate W is hydrophobic in the processing liquid supply process, the interfacial free energy γ and the interfacial free energy γ are each appropriately set.

[0264] When the surface W of the substrate W is hydrophilic in the processing liquid supply process, the interfacial free energy γ and the interfacial free energy γ are each set based on the second surface free energy γ Therefore, when the surface W of the substrate W is hydrophilic in the processing liquid supply process, the interfacial free energy γ and the interfacial free energy γ are each appropriately set.

[0265] In summary, regardless of the state of the surface WS of the substrate W in the processing liquid supply step, the interfacial free energy γ GW and the interfacial free energy γ LW are each set appropriately.

[0266] When the surface W of the substrate W is hydrophobic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are each set based on the first surface free energy γ. Therefore, when the surface W of the substrate W is hydrophobic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are each appropriately set.

[0267] When the surface W of the substrate W is hydrophilic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are each set based on the second surface free energy γ Therefore, when the surface W of the substrate W is hydrophilic in the solidified film formation process, the interfacial free energy γ and the interfacial free energy γ are each appropriately set.

[0268] In summary, regardless of the state of the surface WS of the substrate W in the solidified film formation step, the interfacial free energy γ GW and the interfacial free energy γ LW are each set appropriately.

[0269] 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.

[0270] 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, and the configuration of the supply source 19a. An example of the operation of the processing unit 11 of the second embodiment will be described below.

[0271] <2-1. Example of operation of processing unit 11> 14 is a flowchart showing the steps of a substrate processing method according to the second embodiment. The substrate processing method according to the second embodiment includes steps S1, S11, and S14-S18. For convenience, step S1 described in the first embodiment is not shown in FIG. 14.

[0272] Furthermore, the substrate processing method of the second embodiment includes steps S31 to S34. Steps S31 to S34 are performed, for example, after step S11. Steps S31 to S34 are performed, for example, before step S14. Step S31 is a comparison step. Step S32 is a modification selection step. Step S33 is a hydrophobization step. Step S34 is a hydrophilization step.

[0273] The hydrophobizing step corresponds to the modifying step in the present invention. The hydrophilizing step corresponds to the modifying step in the present invention. When there is no need to distinguish between the hydrophobizing step and the hydrophilizing step, the hydrophobizing step and the hydrophilizing step are collectively referred to as the "modifying step."

[0274] The operations of steps S1, S11, and S14-S18 are substantially common between the first and second embodiments. Therefore, a description of the operations of steps S1, S11, and S14-S18 will be omitted. The operations of steps S31-S34 will be described.

[0275] Step S31: Comparison process The coefficient K is compared with a threshold TH.

[0276] The coefficient K is defined by equation (1).

[0277] More specifically, the coefficient K compared with the threshold value TH is the coefficient K when the treatment liquid supplying step and the solidified film forming step are performed without performing the modification step. Hereinafter, the coefficient K when the modification step is not performed before the treatment liquid supplying step will be referred to as the "coefficient Ki." The coefficient Ki may also be referred to as the "initial coefficient Ki."

[0278] The coefficient Ki is set depending on the state of the surface WS of the substrate W. For example, the coefficient Ki is set based on the state of the surface WS of the substrate W in the processing liquid supply step when the modifying step is not performed before the processing liquid supply step. For example, the coefficient Ki is set based on the state of the surface WS of the substrate W in the solidified film formation step when the modifying step is not performed before the processing liquid supply step.

[0279] The control unit 10 is configured to acquire the coefficient Ki. The control unit 10 may acquire the coefficient Ki in various ways. For example, the control unit 10 reads out the coefficient Ki. For example, the control unit 10 selects the coefficient Ki. For example, the control unit 10 calculates the coefficient Ki. For example, the control unit 10 receives the coefficient Ki.

[0280] For example, the control unit 10 has information about the coefficient K. The information about the coefficient K is, for example, a table shown in FIG. 12. The information about the coefficient K is stored, for example, in a storage medium of the control unit 10. For example, the control unit 10 identifies the coefficient Ki from the information about the coefficient K. For example, the control unit 10 selects the coefficient Ki from the information about the coefficient K.

[0281] The control unit 10 acquires the coefficient Ki based on, for example, the state of the surface WS of the substrate W in the processing liquid supply step when the modifying step is not performed before the processing liquid supply step. The control unit 10 acquires the coefficient Ki based on, for example, the state of the surface WS of the substrate W in the solidified film formation step when the modifying step is not performed before the processing liquid supply step.

[0282] The control unit 10 is configured to obtain the threshold value TH. The control unit 10 may obtain the threshold value TH in various ways.

[0283] The control unit 10 compares the coefficient Ki with the threshold value TH. When the coefficient Ki is greater than the threshold value TH, the control unit 10 decides to perform the reforming process. When the coefficient Ki is greater than the threshold value TH, the control unit 10 proceeds to step S32. When the coefficient Ki is equal to or less than the threshold value TH, the control unit 10 decides to skip the reforming process. When the coefficient Ki is equal to or less than the threshold value TH, the control unit 10 proceeds to step S14. When the coefficient Ki is equal to or less than the threshold value TH, the reforming process is not performed.

[0284] Step S32: Modification selection process The content of the modification process is determined. The content of the modification process includes hydrophobization and hydrophilization. Either hydrophobization or hydrophilization is selected.

[0285] The control unit 10 determines whether the modification process is hydrophobization or hydrophilization. If hydrophobization is selected, the process proceeds to step S33. If hydrophilization is selected, the process proceeds to step S34.

[0286] For example, the control unit 10 determines the reforming process based on information about the coefficient K.

[0287] Here, the control unit 10 preferably specifies a reforming process that reduces the coefficient K. The control unit 10 preferably specifies a reforming process that reduces the coefficient K to a value lower than the coefficient Ki. The control unit 10 preferably specifies a reforming process that reduces the coefficient K to a value lower than the threshold value TH.

[0288] Step S33: Hydrophobization process The surface WS of the substrate W is modified to be hydrophobic.

[0289] The supply unit 15b supplies hydrofluoric acid to the substrate W. The hydrofluoric acid modifies the surface WS of the substrate W to make it hydrophobic.

[0290] The hydrophobizing step is, for example, substantially the same as the chemical solution supplying step described in the first embodiment.

[0291] Here, it is preferable that the coefficient K is reduced by the hydrophobicization process.

[0292] Specifically, it is preferable that the coefficient Km is lower than the coefficient Ki. Here, the coefficient Km is the coefficient K when the modification process is performed before the processing liquid supply process. The coefficient Km is the coefficient K when the processing liquid supply process and the solidified film formation process are performed after the modification process. The coefficient Km is set, for example, based on the state of the front surface WS of the substrate W in the processing liquid supply process when the modification process is performed before the processing liquid supply process. The coefficient Km is set, for example, based on the state of the front surface WS of the substrate W in the solidified film formation process when the modification process is performed before the processing liquid supply process. The coefficient Km may also be called a "correction coefficient Km."

[0293] It is more preferred that the coefficient K is reduced to a value lower than the threshold value TH by the hydrophobization process. Specifically, it is preferred that the coefficient Km is smaller than the threshold value TH.

[0294] Step S34: Hydrophilization process The surface WS of the substrate W is modified to be hydrophilic.

[0295] The supply unit 15c supplies SC1 to the substrate W. The SC1 modifies the surface WS of the substrate W to make it hydrophilic.

[0296] The hydrophilization step is substantially the same as the cleaning liquid supply step described in the first embodiment.

[0297] Here, it is preferable that the coefficient K is reduced by the hydrophilization step. Specifically, it is preferable that the coefficient Km is lower than the coefficient Ki.

[0298] It is more preferable that the coefficient K is reduced to a value lower than the threshold value TH by the hydrophilization process. Specifically, it is preferable that the coefficient Km is lower than the threshold value TH.

[0299] <2-2. Effects of the Second Embodiment> The substrate processing method is for processing a substrate W on which a pattern P 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 L is supplied to the substrate W. The processing liquid L contains a sublimable substance and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid L on the substrate W. In the solidified film forming step, a solidified film G is formed on the substrate W. The solidified film G contains a sublimable substance. In the sublimation step, the solidified film G is sublimated. The substrate W is dried by the sublimation of the solidified film G.

[0300] The substrate processing method further includes a modification process. The modification process is performed when the coefficient Ki is greater than the threshold value TH. The modification process is performed before the processing liquid supply process. The modification process modifies the surface WS of the substrate W. The modification process changes the coefficient Ki to a coefficient Km. When the coefficient Ki is greater than the threshold value TH, the surface WS of the substrate W is modified in the modification process, and then the processing liquid L is supplied to the substrate W in the processing liquid supply process. Therefore, even when the coefficient Ki is greater than the threshold value TH, the solidified film G is suitably formed on the substrate W in the solidified film formation process. Specifically, the solidified film G spreads smoothly on the substrate W in the solidified film formation process. Therefore, the solvent is efficiently removed from the substrate W in the solidified film formation process. The processing liquid L is efficiently eliminated from the substrate W in the solidified film formation process. Therefore, in the sublimation process, the substrate is dried while the pattern P formed on the substrate W is suitably protected.

[0301] As described above, according to the substrate processing method of the second embodiment, the substrate W is processed appropriately.

[0302] The coefficient K decreases through the modification process. Specifically, the coefficient Km is lower than the coefficient Ki. Therefore, the solidified film G is more suitably formed on the substrate W in the solidified film forming process.

[0303] The modification step reduces the coefficient K to a value lower than the threshold value TH, so that the solidified film G is more suitably formed on the substrate W in the solidified film formation step.

[0304] In the modification step, either a hydrophobic process or a hydrophilic process is performed. In the modification step, the surface WS of the substrate W is modified to be either hydrophilic or hydrophobic. Therefore, in the modification step, the surface WS of the substrate W can be flexibly modified. Therefore, in the solidified film formation step, the solidified film G is more suitably formed on the substrate W.

[0305] In the hydrophobizing step, the surface WS of the substrate W is modified to be hydrophobic. In the modification step, the surface WS of the substrate W can be suitably modified. Therefore, in the solidified film forming step, the solidified film G is more suitably formed on the substrate W.

[0306] The hydrophilization step modifies the surface WS of the substrate W to be hydrophilic. In the modification step, the surface WS of the substrate W can be suitably modified. Therefore, in the solidified film formation step, the solidified film G is formed on the substrate W more suitably.

[0307] When the coefficient Ki is equal to or less than the threshold value TH, the modification process is not performed. Specifically, when the coefficient Ki is equal to or less than the threshold value TH, the hydrophobic process is not performed, and the hydrophilic process is not performed either. This effectively reduces the time required for the substrate processing method. When the coefficient Ki is equal to or less than the threshold value TH, even if the modification process is not performed, the solidified film G is suitably formed on the substrate W in the solidified film forming process. Therefore, even if the coefficient Ki is equal to or less than the threshold value TH, the substrate W is suitably processed.

[0308] 3. Third Embodiment The third 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.

[0309] The third 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.

[0310] <3-1. Configuration of processing unit 11> Fig. 15 is a diagram showing the configuration of a processing unit 11 according to the third embodiment. For convenience, Fig. 15 shows a simplified view of a supply source 19a.

[0311] The processing unit 11 includes a supply unit 15g in addition to the supply units 15a-15f. The supply unit 15g supplies the processing liquid L to the substrate W held by the substrate holder 13.

[0312] Here, the composition of the treatment liquid L supplied by the supply unit 15g is different from the composition of the treatment liquid L supplied by the supply unit 15a. For convenience, the treatment liquid L supplied by the supply unit 15a will be referred to as "treatment liquid L1." The treatment liquid L supplied by the supply unit 15g will be referred to as "treatment liquid L2."

[0313] For example, the processing liquid L1 and the processing liquid L2 differ in terms of the composition of the sublimable substance, the composition of the solvent, or the compounding ratio of the sublimable substance to the solvent.

[0314] The supply unit 15g includes a nozzle 16g, a pipe 17g, and a valve 18g. The nozzle 16g is installed inside the housing 12. The nozzle 16g ejects the processing liquid L2 onto the substrate W. The pipe 17g is connected to the nozzle 16g. The valve 18g is provided in the pipe 17g. The valve 18g controls the supply of the processing liquid L2.

[0315] The supply unit 15g is connected to a supply source 19g, which is connected to, for example, a pipe 17g. The supply source 19g sends the processing liquid L2 to the supply unit 15g.

[0316] <3-2. Example of operation of processing unit 11> 16 is a flowchart showing the procedure of a substrate processing method according to a third embodiment. The substrate processing method includes steps S1, S11, and S14-S18. For convenience, step S1 is not shown in FIG. 16. The substrate processing method further includes step S41. Step S41 is performed, for example, after step S14. Step S41 is performed, for example, before step S15.

[0317] The operations of steps S1, S11, and S14-S18 are substantially common between the first and third embodiments. Therefore, a description of the operations of steps S1, S11, S14, and S16-S18 will be omitted. The operations of steps S41 and S15 will be described.

[0318] Step S41: Selection process Select processing liquid L.

[0319] The control unit 10 selects either the treatment liquid L1 or the treatment liquid L2 based on the coefficient K. The coefficient K is defined by the following equation (1).

[0320] Here, the coefficient K is set depending on the composition of the treatment liquid L. For example, the coefficient K includes a coefficient KL1 based on the treatment liquid L1 and a coefficient KL2 based on the treatment liquid L2.

[0321] Furthermore, each of the coefficients KL1 and KL2 is set depending on the state of the surface WS of the substrate W. For example, each of the coefficients KL1 and KL2 is set based on the state of the surface WS of the substrate W in the processing liquid supply step. For example, each of the coefficients KL1 and KL2 is set based on the state of the surface WS of the substrate W in the solidified film formation step.

[0322] The control unit 10 is configured to obtain the coefficient K. The control unit 10 may obtain the coefficient K in various ways.

[0323] It is preferable that the control unit 10 designates a treatment liquid L that makes the coefficient K equal to or less than the threshold value TH. In other words, it is preferable that the control unit 10 selects a treatment liquid L that satisfies the condition that the coefficient K is equal to or less than the threshold value TH. For example, if the coefficient KL1 is equal to or less than the threshold value TH, it is preferable that the control unit 10 selects treatment liquid L1. For example, if the coefficient KL2 is equal to or less than the threshold value TH, it is preferable that the control unit 10 selects treatment liquid L2.

[0324] Step S15: Processing liquid supply process The processing liquid L selected in the selection step is supplied to the substrate W.

[0325] If the processing liquid L1 is selected in the selection step, the processing liquid L1 is supplied to the substrate W in the processing liquid supply step. If the processing liquid L2 is selected in the selection step, the processing liquid L2 is supplied to the substrate W in the processing liquid supply step.

[0326] When the processing liquid L1 is selected in the selection step, the processing liquid L2 is not supplied to the substrate W in the processing liquid supply step. When the processing liquid L2 is selected in the selection step, the processing liquid L1 is not supplied to the substrate W in the processing liquid supply step.

[0327] <3-3. Effects of the Third Embodiment> The substrate processing method is for processing a substrate W on which a pattern P is formed. The substrate processing method includes a selection step, a processing liquid supply step, a solidified film formation step, and a sublimation step. In the selection step, a processing liquid L is selected. The processing liquid L contains a sublimable substance and a solvent. In the processing liquid supply step, the processing liquid L selected in the selection step is supplied to the substrate W. In the solidified film formation step, the solvent evaporates from the processing liquid L on the substrate W. In the solidified film formation step, a solidified film G is formed on the substrate W. The solidified film G contains a sublimable substance. In the sublimation step, the solidified film G is sublimated. The substrate W is dried by the sublimation of the solidified film G.

[0328] Here, in the selection step, the processing liquid L is selected based on the coefficient K. The coefficient K is defined by the interfacial free energies γLG, γGW, and γLW. Therefore, in the selection step, the processing liquid L is appropriately selected. Therefore, in the solidified film formation step, the solidified film G is suitably formed on the substrate W. Specifically, in the solidified film formation step, the solidified film G spreads smoothly on the substrate W. Therefore, in the solidified film formation step, the solvent is efficiently removed from the substrate W. In the solidified film formation step, the processing liquid L is efficiently eliminated from the substrate W. Therefore, in the sublimation step, the substrate W is dried in a state in which the pattern P formed on the substrate W is suitably protected.

[0329] As described above, according to the substrate processing method of the third embodiment, the substrate W is processed appropriately.

[0330] In the selection step, the treatment liquid L that makes the coefficient K equal to or less than the threshold value TH is selected. Therefore, in the selection step, the treatment liquid L is selected more appropriately.

[0331] The coefficient K is set in accordance with the state of the surface WS of the substrate W. Therefore, the coefficient K is set appropriately regardless of the state of the surface WS of the substrate W. Therefore, in the selection process, the processing liquid L is selected in accordance with the state of the surface WS of the substrate W. In the selection process, the processing liquid L is selected appropriately regardless of the state of the surface WS of the substrate W. Therefore, in the processing liquid supply process, solidified film formation process, and sublimation process, the substrate W is processed appropriately regardless of the state of the surface WS of the substrate W.

[0332] The coefficient K is set based on the state of the surface WS of the substrate W in the processing liquid supply step, so that the substrate W is appropriately processed regardless of the state of the surface WS of the substrate W in the processing liquid supply step.

[0333] The coefficient K is set based on the state of the surface WS of the substrate W in the solidified film forming process, so that the substrate W is appropriately processed regardless of the state of the surface WS of the substrate W in the solidified film forming process.

[0334] The coefficient K is set according to the composition of the processing liquid L. Therefore, the coefficient K is set appropriately regardless of the composition of the processing liquid L. Therefore, in the selection process, the processing liquid L is selected according to the composition of the processing liquid L. In the selection process, the processing liquid L is selected taking into account the composition of the processing liquid L. In the selection process, the processing liquid L is selected appropriately regardless of the composition of the processing liquid L. Therefore, in the processing liquid supply process, solidified film formation process, and sublimation process, the substrate W is processed appropriately regardless of the composition of the processing liquid L.

[0335] 4. Fourth Embodiment The fourth 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.

[0336] <4-1. Configuration and Operation Example of Fourth Embodiment> The fourth embodiment relates to a processing liquid evaluation method for evaluating a processing liquid L. The processing liquid L is used to process a substrate W on which a pattern P is formed. The processing liquid L is used for drying the substrate W on which the pattern P is formed. The processing liquid L contains a sublimable substance and a solvent. When the solvent evaporates from the processing liquid L, the processing liquid L becomes a solidified film G containing the sublimable substance.

[0337] 17 is a flowchart showing the procedure of the treatment liquid evaluation method of the fourth embodiment. The treatment liquid evaluation method includes an acquisition step and an evaluation step.

[0338] S51: Acquisition process A coefficient K is obtained. The coefficient K is defined by equation (1).

[0339] The coefficient K can be obtained in various ways.

[0340] For example, the coefficient K is obtained depending on the state of the surface WS of the substrate W.

[0341] For example, the coefficient K includes a first coefficient Ka and a second coefficient Kb. For example, in the acquisition step, the first coefficient Ka and the second coefficient Kb are acquired. Here, the first coefficient Ka corresponds to the coefficient K when the surface WS of the substrate W is hydrophobic. The second coefficient Kb corresponds to the coefficient K when the surface WS of the substrate W is hydrophilic. The first coefficient Ka and the second coefficient Kb are exemplified in the first embodiment.

[0342] For example, the substrate W includes a first substrate Wa and a second substrate Wb. For example, the obtaining process includes a first process, a second process, and a third process. In the first process, the first substrate Wa and the second substrate Wb are prepared. In the second process, the coefficient K is obtained based on the first substrate Wa. For example, in the second process, the coefficient K is calculated based on the first substrate Wa. In the third process, the coefficient K is obtained based on the second substrate Wb. For example, in the third process, the coefficient K is calculated based on the second substrate Wb. Here, the first substrate Wa corresponds to the substrate W having a hydrophobic surface WS. The second substrate Wb corresponds to the substrate W having a hydrophilic surface WS. The first substrate Wa and the second substrate Wb are exemplified in the first embodiment.

[0343] For example, the coefficient K is obtained based on the state of the surface WS of the substrate W and the composition of the processing liquid L.

[0344] For example, the coefficient K is obtained based on the state of the surface WS of the substrate W, the composition of the processing liquid L, and the composition of the solidified film G. Here, the composition of the solidified film G is estimated from the composition of the processing liquid L.

[0345] For example, the coefficient K is selected from preset information about the coefficient K. The preset information about the coefficient K is, for example, a table shown in FIG.

[0346] S52: Evaluation process The treatment liquid L is evaluated based on the coefficient K.

[0347] For example, the treatment liquid L is evaluated based on the first coefficient Ka. For example, the treatment liquid L is evaluated based on the second coefficient Kb.

[0348] For example, the processing liquid L is classified into multiple classes based on the coefficient K. Specifically, the processing liquid L that causes the coefficient K to be equal to or less than the threshold value TH is classified into a first class Q1. The processing liquid L that causes the coefficient K to be greater than the threshold value TH is classified into a second class Q2. In other words, the processing liquid L that satisfies the first condition is classified into the first class Q1. The processing liquid L that does not satisfy the first condition is classified into the second class Q2. Here, the first condition is that the coefficient K is equal to or less than the threshold value TH.

[0349] Please refer to FIG. 12. The table in FIG. 12 illustrates the classification of each treatment liquid L. The threshold value TH is set to 17 mN / m. For example, the coefficient K of Example 1a satisfies the first condition. Therefore, the treatment liquid L of Example 1a is classified into the first class Q1. For example, the coefficient K of Example 2a does not satisfy the first condition. Therefore, the treatment liquid L of Example 1b is classified into the second class Q2.

[0350] <4-2. Effects of the Fourth Embodiment> The processing liquid evaluation method is for evaluating a processing liquid L. The processing liquid L is used to process a substrate W on which a pattern P is formed. The processing liquid L contains a sublimable substance and a solvent. When the solvent evaporates from the processing liquid L, the processing liquid L becomes a solidified film G. The solidified film G contains a sublimable substance.

[0351] The processing liquid evaluation method includes an acquisition step and an evaluation step. The acquisition step acquires a coefficient K. The coefficient K is defined by interfacial free energies γLG, γGW, and γLW. The evaluation step evaluates the processing liquid L based on the coefficient K. Thus, the processing liquid L is suitably evaluated from the viewpoint of the quality of processing of the substrate W.

[0352] As described above, the present treatment liquid evaluation method allows for appropriate evaluation of the treatment liquid L. The present treatment liquid evaluation method is useful for selecting the treatment liquid L.

[0353] For example, even if the average collapse rate E is not actually measured, the average collapse rate E can be estimated based on the coefficient K. Even if the processing liquid L is not actually supplied to the substrate W, the quality of the processing using the processing liquid L on the substrate W can be estimated based on the coefficient K. Therefore, the processing liquid evaluation method is useful for screening the processing liquid L.

[0354] In the acquisition step, the coefficient K is acquired in accordance with the state of the surface WS of the substrate W. Therefore, in the acquisition step, the coefficient K is acquired appropriately regardless of the state of the surface WS of the substrate W. Therefore, in the evaluation step, the processing liquid L is evaluated taking into account the state of the surface WS of the substrate W. In the evaluation step, the processing liquid L is evaluated appropriately regardless of the state of the surface WS of the substrate W.

[0355] The coefficient K includes a first coefficient Ka when the surface WS of the substrate W is hydrophobic, and a second coefficient Kb when the surface WS of the substrate W is hydrophilic. In the acquisition step, the first coefficient Ka and the second coefficient Kb are acquired. In the evaluation step, the processing liquid L is evaluated based on the first coefficient Ka and the second coefficient Kb. Specifically, in the evaluation step, the processing liquid L is evaluated based on the first coefficient Ka. In the evaluation step, the processing liquid L is evaluated based on the second coefficient Kb. Therefore, in the evaluation step, the processing liquid L is evaluated taking into account the state of the surface WS of the substrate W. In the evaluation step, the processing liquid L is appropriately evaluated regardless of the state of the surface WS of the substrate W.

[0356] The acquisition process includes a first process, a second process, and a third process. In the first process, a first substrate Wa having a hydrophobic surface WS and a second substrate Wb having a hydrophilic surface WS are prepared. In the second process, the coefficient K is acquired based on the first substrate Wa. In the third process, the coefficient K is acquired based on the second substrate Wb. Therefore, in the acquisition process, the coefficient K is appropriately acquired regardless of the state of the surface WS of the substrate W.

[0357] In the obtaining step, the coefficient K is obtained based on the state of the surface WS of the substrate W and the composition of the processing liquid L. Therefore, in the obtaining step, the coefficient K is obtained appropriately.

[0358] In the obtaining step, the coefficient K is obtained based on the state of the surface WS of the substrate W, the composition of the processing liquid L, and the composition of the solidified film G. Therefore, in the obtaining step, the coefficient K is obtained more appropriately.

[0359] In the acquisition step, the coefficient K is selected from preset information about the coefficient K. Therefore, in the acquisition step, the coefficient K is easily acquired.

[0360] In the evaluation process, the treatment liquid L is classified into a plurality of classes based on the coefficient K. For example, in the evaluation process, the treatment liquid L that causes the coefficient K to be equal to or less than the threshold value TH is classified into a first class Q1. For example, in the evaluation process, the treatment liquid L that causes the coefficient K to be greater than the threshold value TH is classified into a second class Q2. Therefore, in the evaluation process, the treatment liquid L is clearly evaluated.

[0361] <5. Modified embodiment> The present invention is not limited to the first, second, third and fourth embodiments, and can be modified and implemented as follows.

[0362] (1) The coefficient K is set, for example, based on the state of the surface WS of the substrate W in the processing liquid supply process. The coefficient K is set, for example, based on the state of the surface WS of the substrate W in the solidified film formation process. However, this is not limitative. The coefficient K may be set, for example, based on the state of the surface WS of the substrate W in at least one of the processing liquid supply process and the solidified film formation process.

[0363] (2) The threshold value TH is a constant. However, this is not limited to this. For example, the threshold value TH may be a variable. In this modified embodiment, the first condition can be set more appropriately. Here, the first condition is that the coefficient K is equal to or less than the threshold value TH. Therefore, the substrate W can be processed more appropriately.

[0364] Referring to FIG. 1, each protrusion A has a width AW and a height AH. The ratio R of the height AH to the width AW is called the "aspect ratio R of the protrusion A" or the "aspect ratio R of the pattern P." The threshold value TH may be, for example, a variable that depends on the aspect ratio R. In this modified embodiment, the first condition is set more appropriately depending on the aspect ratio R. Therefore, the substrate W can be processed more appropriately regardless of the aspect ratio R.

[0365] For example, the threshold value TH may decrease as the aspect ratio R increases. The larger the aspect ratio R, the easier the pattern P will collapse. On the other hand, the smaller the threshold value TH, the smoother the solidified film G will spread on the substrate W. Therefore, the smaller the threshold value TH, the more reliably the pattern P will be protected. Therefore, even when the aspect ratio R is large, the pattern P will be suitably protected. Regardless of the aspect ratio R, the substrate W will be processed appropriately.

[0366] In this modified embodiment, the control unit 10 may also acquire the threshold value TH in various ways. For example, the control unit 10 reads out the threshold value TH. For example, the control unit 10 selects the threshold value TH. For example, the control unit 10 calculates the threshold value TH. For example, the control unit 10 receives the threshold value TH.

[0367] (3) In the first embodiment, the procedure for obtaining the coefficient K is exemplified. However, this is not limiting. The procedure for obtaining the coefficient K may be changed as appropriate. For example, in the preparation step, the first substrate Wa may be a simulation of the substrate W in the solidified film formation step. For example, in the preparation step, the second substrate Wb may be a simulation of the substrate W in the solidified film formation step. For example, in the preparation step, the compositions of the first standard liquid and the second standard liquid may be changed as appropriate. For example, in the measurement step, the contact angle θ6a between the processing liquid L and the first substrate Wa and the contact angle θ6b between the processing liquid L and the second substrate Wb may be measured. For example, in the calculation step, an equation other than equations (2)-(5) may be used.

[0368] (4) See Fig. 14. In the modification step of the second embodiment, the surface WS of the substrate W is modified to be either hydrophilic or hydrophobic, although the modification is not limited to this.

[0369] For example, in the modification process, the surface WS of the substrate W may be modified to be only hydrophobic. When the coefficient Ki is greater than the threshold value TH, the control unit 10 may determine to perform the hydrophobization process. When the coefficient Ki is greater than the threshold value TH, the hydrophobization process may be performed before the processing liquid supply process. In this modified embodiment, the modification selection process and the hydrophilization process may be omitted. In this modified embodiment, the modification process is simplified.

[0370] Alternatively, the modification step may modify the surface WS of the substrate W to be only hydrophilic. Specifically, when the coefficient Ki is greater than the threshold value TH, the control unit 10 may determine to perform the hydrophilization step. When the coefficient Ki is greater than the threshold value TH, the hydrophilization step may be performed before the processing liquid supply step. In this modified embodiment, the modification selection step and the hydrophobization step may be omitted. In this modified embodiment, the modification step is simplified.

[0371] (5) In the substrate processing method of the second embodiment, the comparing step and the modification selection step are performed after the rotation start step. However, this is not limited to this. The timing of performing the comparing step and the modification selection step may be changed as appropriate. The comparing step and the modification selection step may be performed before the rotation start step.

[0372] (6) In the hydrophobization step of the second embodiment, hydrofluoric acid is used. However, the present invention is not limited to this. In the hydrophobization step, other hydrophobizing agents that modify the surface of the substrate W to be hydrophobic may be used instead of hydrofluoric acid.

[0373] (7) In the hydrophilization step of the second embodiment, SC1 was used. However, this is not limited to this. In the hydrophilization step, other hydrophilization agents that modify the surface of the substrate W to be hydrophobic may be used instead of SC1.

[0374] (8) See FIG. 16. In the selection process of the third embodiment, for example, if both the coefficient KL1 and the coefficient KL2 are equal to or less than the threshold value TH, the control unit 10 may select one of the treatment liquids L1 and L2 based on another criterion. The other criterion is, for example, at least one of the time required for the drying process and the cost of the treatment liquid L. The time required for the drying process includes, for example, the time required for the treatment liquid supply process, the time required for the solidified film formation process, and the time required for the sublimation process. The cost of the treatment liquid L includes, for example, the cost of the sublimable substance and the cost of the solvent.

[0375] (9) See FIG. 16. In the substrate processing method of the third embodiment, the selection step is performed after the rotation start step and the replacement liquid supply step. However, this is not limited to this. The timing of performing the selection step may be changed as appropriate. For example, the selection step may be performed before the replacement liquid supply step. For example, the selection step may be performed before the rotation start step.

[0376] (10) In the solidified film forming process of the first to third embodiments, a dry gas is not supplied to the substrate W. However, this is not limited to this. In the solidified film forming process, a dry gas may be supplied to the substrate W. In the solidified film forming process, a dry gas may be supplied to the processing liquid L on the substrate W.

[0377] According to this modified embodiment, in the solidified film formation process, the processing liquid L on the substrate W is exposed to a dry gas. Therefore, in the solidified film formation process, the solvent is more efficiently removed from the substrate W. In the solidified film formation process, the processing liquid L on the substrate W is more efficiently removed from the substrate W. Therefore, by the time the solidified film formation process is completed, all of the processing liquid L on the substrate W is more reliably removed. Therefore, in the sublimation process, the substrate W is dried with the pattern P more effectively protected.

[0378] (11) The substrate processing method of the first embodiment includes a chemical liquid supply step, a cleaning liquid supply step, a first rinse liquid supply step, a second 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 cleaning liquid supply step, the first rinse liquid supply step, the second rinse liquid supply step, and the replacement liquid supply step may be omitted. For example, all of the chemical liquid supply step, the cleaning liquid supply step, the first rinse liquid supply step, the second rinse liquid supply step, and the replacement liquid supply step may be omitted.

[0379] The substrate processing methods of the second and third embodiments include the replacement liquid supplying step, but are not limited to this. For example, the replacement liquid supplying step may be omitted.

[0380] The substrate processing method of the second embodiment may further include an additional rinsing step. For example, the additional rinsing step may be performed after the modifying step and before the replacing step. The additional rinsing step may be substantially the same as the first and second rinsing steps described in the first embodiment.

[0381] (12) In the first to third embodiments, when the processing liquid supplying step was performed, a liquid (e.g., a substitute liquid) was present on the substrate W. That is, in the processing liquid supplying step, the processing liquid L was supplied to the substrate W in a non-dried state. However, this is not limited to this. For example, when the processing liquid supplying step was performed, a liquid (e.g., a substitute liquid) may not be present on the substrate W. For example, in the processing liquid supplying step, the processing liquid L may be supplied to the substrate W in a dried state.

[0382] (13) In the first to third embodiments, the pattern P on the substrate W may be formed on the substrate W, for example, before the substrate W is processed in the processing unit 11. Alternatively, the pattern P may be formed on the substrate W, for example, in the chemical solution supplying step (step S12).

[0383] (14) The first to fourth embodiments and the modified embodiments described above in (1) to (13) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment. [Explanation of symbols]

[0384] 1... Substrate processing equipment 10...Control section 11... Processing unit 13... Board holding part 15a… Supply section 15b... Supply section 15c… Supply section K... coefficient Ka … First coefficient Kb: Second coefficient L: Processing liquid M…Liquid film G … Solidified film TH... threshold P... Pattern W: Substrate WS: Surface of the substrate WS1: Top surface of the board A... Convex part Wa... First board Wb…Second board γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW … Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate γW … surface free energy of the substrate γWa … surface free energy of the first substrate γWb: surface free energy of the second substrate

Claims

1. A substrate processing method for processing a substrate on which a pattern is formed, comprising: a treatment liquid supplying step of supplying a treatment liquid containing a sublimable substance and a solvent onto 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 sublimable substance on the substrate; a sublimation step of sublimating the solidified film; Equipped with A substrate processing method in which a coefficient K defined by the following formula is equal to or less than a threshold value. K=γLG+γGW−γLW however, K: coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

2. 2. The substrate processing method according to claim 1, The substrate processing method, wherein the threshold value is a preset constant.

3. 3. The substrate processing method according to claim 1, The method for processing a substrate, wherein the threshold value is 17 mN / m.

4. 4. The substrate processing method according to claim 1, The coefficient K is set depending on the state of the surface of the substrate. Substrate processing method.

5. 5. The substrate processing method according to claim 1, The interfacial free energy γGW and the interfacial free energy γLW are each set according to the state of the surface of the substrate. Substrate processing method.

6. A substrate processing method for processing a substrate on which a pattern is formed, comprising: a treatment liquid supplying step of supplying a treatment liquid containing a sublimable substance and a solvent onto 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 sublimable substance on the substrate; a sublimation step of sublimating the solidified film; a modifying step of modifying the surface of the substrate before the processing liquid supplying step when a coefficient K defined by the following formula is greater than a threshold value; Equipped with Substrate processing method. K=γLG+γGW−γLW however, K: coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

7. 7. The substrate processing method according to claim 6, The substrate processing method, wherein the coefficient K is decreased by the modifying step.

8. 8. The substrate processing method according to claim 6, In the modification step, the surface of the substrate is modified to be either hydrophilic or hydrophobic.

9. 9. The substrate processing method according to claim 6, When the coefficient K is equal to or less than the threshold value, the reforming process is not performed. Substrate processing method.

10. A substrate processing method for processing a substrate on which a pattern is formed, comprising: a selection step of selecting a treatment liquid containing a sublimable substance and a solvent based on a coefficient K defined by the following formula: a processing liquid supplying step of supplying the processing liquid selected in the selection step 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 sublimable substance on the substrate; a sublimation step of sublimating the solidified film; Equipped with Substrate processing method. K=γLG+γGW−γLW however, K: coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

11. The substrate processing method according to claim 10, In the selection step, the processing liquid that makes the coefficient K equal to or less than a threshold value is selected. Substrate processing method.

12. 1. A method for evaluating a processing liquid for processing a substrate on which a pattern is formed, comprising: the treatment liquid contains a sublimable substance and a solvent, When the solvent evaporates from the treatment liquid, the treatment liquid becomes a solidified film containing the sublimable substance, The processing liquid evaluation method includes: an acquisition step of acquiring a coefficient K defined by the following formula: an evaluation step of evaluating the treatment liquid based on the coefficient K; Equipped with Processing solution evaluation method. K=γLG+γGW−γLW however, K: coefficient γLG: Interfacial free energy at the interface between the treatment liquid and the solidified film γGW: Interfacial free energy at the interface between the solidified film and the substrate γLW: Interfacial free energy at the interface between the processing liquid and the substrate

13. The method for evaluating a treatment liquid according to claim 12, In the obtaining step, the coefficient K is obtained according to the state of the surface of the substrate. Processing solution evaluation method.

14. The method for evaluating a treatment liquid according to claim 12 or 13, The coefficient K is a first coefficient when the surface of the substrate is hydrophobic; and a second coefficient when the surface of the substrate is hydrophilic; and Including, In the obtaining step, the first coefficient and the second coefficient are obtained, In the evaluation step, the treatment liquid is evaluated based on the first coefficient and the second coefficient. Processing solution evaluation method.

15. 15. The method for evaluating a processing liquid according to claim 12, In the evaluation step, the processing liquid that causes the coefficient K to be equal to or less than a threshold value is classified into a first class, and the processing liquid that causes the coefficient K to be greater than the threshold value is classified into a second class.

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