Substrate processing method and processing solution

Abstract

To provide a substrate processing method and a processing liquid capable of properly drying a substrate.SOLUTION: The present invention relates to a substrate processing method and a processing liquid. The substrate processing method includes a processing liquid supply step, a solidified film formation step, and a sublimation step. The processing liquid supply step supplies a processing liquid to the substrate. The processing liquid contains a sublimable substance, a solvent, and a surfactant. The solidified film formation step evaporates the solvent and the surfactant from the processing liquid on the substrate. The solidified film formation step forms a solidified film containing the sublimable substance on the substrate. The sublimation step sublimates the solidified film. The octanol / water partition coefficient LOGPow of the surfactant is -1 or more and 1 or less. The vapor pressure Pc of the surfactant at room temperature is 0.9 times or more and 3 times or less the vapor pressure Pb of the solvent at room temperature.SELECTED DRAWING: Figure 4

Description

[Technical field]

[0001] The present invention relates to a substrate processing method for processing a substrate and a processing liquid used for drying the substrate, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic electroluminescence (EL), a substrate for a flat panel display (FPD), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method for drying a substrate. Specifically, the substrate processing method of Patent Document 2 includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. The processing liquid supplying step supplies a processing liquid to a substrate. The processing liquid contains a solvent, a sublimable substance, and an adsorbent. The adsorbent is, for example, a surfactant. The solidified film forming step evaporates the solvent. The solidified film forming step forms a solidified film containing the sublimable substance on the substrate. The sublimation step sublimes the solidified film. The solidified film changes into a gas without passing through a liquid state. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2020-4948 Summary of the Invention [Problem to be solved by the invention]

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

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

[0006] In order to solve the above problems, the inventors have conducted intensive research. First, the inventors have examined the cause of the inability to properly dry the substrate. As a result, the inventors have speculated that the cause of the inability to properly dry the substrate is the treatment liquid used to dry the substrate. For example, the inventors have speculated that the cause of the inability to properly dry the substrate is the selection of the sublimable substance, the solvent, and the surfactant. Therefore, the inventors have searched for a more appropriate treatment liquid. The inventors have searched for the conditions that the treatment liquid should satisfy.

[0007] The present invention was obtained through further intensive research based on these findings, and has the following configuration: That is, the present invention is a substrate processing method for processing a substrate, comprising a processing liquid supplying step of supplying a processing liquid containing a sublimable substance, a solvent, and a surfactant to a substrate, a solidified film forming step of evaporating the solvent and the surfactant 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 the octanol / water partition coefficient of the surfactant is -1 or more and 1 or less, and the vapor pressure of the surfactant at room temperature is 0.9 times or more and 3 times or less than the vapor pressure of the solvent at room temperature.

[0008] The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. The processing liquid supplying step supplies a processing liquid to a substrate. The processing liquid includes a sublimable substance, a solvent, and a surfactant. The solidified film forming step evaporates the solvent and the surfactant from the processing liquid on the substrate. The solidified film forming step forms a solidified film on the substrate. The solidified film includes a sublimable substance. The sublimation step sublimes the solidified film.

[0009] The treatment liquid satisfies the first condition: First condition: the octanol / water partition coefficient of the surfactant is −1 or more and 1 or less.

[0010] Therefore, the processing liquid has an appropriate affinity for the substrate, and therefore the processing liquid can be appropriately supplied to the substrate in the processing liquid supplying step.

[0011] The treatment liquid satisfies the second condition: Second condition: the vapor pressure of the surfactant at room temperature is 0.9 times or more the vapor pressure of the solvent at room temperature and is 3 times or less the vapor pressure of the solvent at room temperature.

[0012] The vapor pressure of the surfactant at room temperature is three times or less than the vapor pressure of the solvent at room temperature. Therefore, the vapor pressure of the surfactant at room temperature is not excessively high. Therefore, the processing liquid supplying step can more appropriately supply the processing liquid to the substrate.

[0013] Furthermore, the vapor pressure of the surfactant at room temperature is 0.9 times or more the vapor pressure of the solvent at room temperature. Therefore, the vapor pressure of the surfactant at room temperature is not excessively low. Therefore, in the solidified film formation process, the surfactant evaporates properly. Since the surfactant evaporates properly, the sublimable substance precipitates properly. Therefore, the solidified film formation process can properly form a solidified film on the substrate.

[0014] In summary, since the processing liquid satisfies the first and second conditions, the processing liquid supplying step can appropriately supply the processing liquid to the substrate. Since the processing liquid satisfies the second condition, the solidified film forming step can appropriately form a solidified film on the substrate. Therefore, according to the above-mentioned substrate processing method, the substrate can be appropriately dried.

[0015] In the above-described substrate processing method, the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature.

[0016] The treatment liquid satisfies the third condition. Third condition: The vapor pressure of the solvent at room temperature is higher than the vapor pressure of the sublimable substance at room temperature.

[0017] Therefore, the solvent evaporates more easily than the sublimable substance, and thus the sublimable substance precipitates more appropriately as the solvent evaporates, so that the solidified film forming step can more appropriately form the solidified film on the substrate.

[0018] In the above-described substrate processing method, the vapor pressure of the surfactant at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature.

[0019] The treatment liquid satisfies the fourth condition. Fourth condition: The vapor pressure of the surfactant at room temperature is higher than the vapor pressure of the sublimable substance at room temperature.

[0020] Therefore, the surfactant evaporates more easily than the sublimable substance, and thus the sublimable substance precipitates more appropriately as the surfactant evaporates, so that the solidified film forming step can more appropriately form the solidified film on the substrate.

[0021] In the above-mentioned substrate processing method, the sublimable substance is any one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following a1) to a20): a1) The solvent is methanol and the surfactant is acetone. a2) The solvent is ethanol and the surfactant is methanol. a3) The solvent is isopropyl alcohol and the surfactant is methanol. a4) The solvent is isopropyl alcohol and the surfactant is ethanol. a5) The solvent is isopropyl alcohol and the surfactant is tert-butanol. a6) The solvent is tert-butanol and the surfactant is methanol. a7) The solvent is tert-butanol and the surfactant is ethanol. a8) The solvent is tert-butanol and the surfactant is isopropyl alcohol. a9) The solvent is 1-propanol and the surfactant is ethanol. a10) The solvent is 1-propanol, and the surfactant is isopropyl alcohol. a11) The solvent is 1-propanol, and the surfactant is tert-butanol. a12) The solvent is isobutanol and the surfactant is 1-propanol. a13) The solvent is 1-ethoxy-2-propanol, and the surfactant is 1-propanol. a14) The solvent is 1-ethoxy-2-propanol, and the surfactant is isobutanol. a15) The solvent is 1-butanol, and the surfactant is 1-propanol. a16) The solvent is 1-butanol and the surfactant is isobutanol. a17) The solvent is 1-butanol, and the surfactant is 1-ethoxy-2-propanol. a18) The solvent is propylene glycol monomethyl ether acetate and the surfactant is isobutanol. a19) The solvent is propylene glycol monomethyl ether acetate and the surfactant is 1-ethoxy-2-propanol. a20) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-butanol. It is preferable.

[0022] When the sublimable substance, the solvent, and the surfactant are specified as above, the processing liquid satisfactorily satisfies the first and second conditions, and therefore the substrate processing method can appropriately dry the substrate.

[0023] In the above-mentioned substrate processing method, it is preferable that the substrate has a pattern formed on the surface of the substrate. Even when the substrate has a pattern, the substrate processing method can properly dry the substrate while protecting the pattern.

[0024] The present invention relates to a processing liquid used for drying a substrate, the processing liquid comprising a sublimable substance, a solvent, and a surfactant, the surfactant having an octanol / water partition coefficient of -1 or more and 1 or less, and the surfactant having a vapor pressure at room temperature of 0.9 or more and 3 or less times the vapor pressure of the solvent at room temperature.

[0025] The processing liquid is used to dry the substrate and contains a sublimable material, a solvent, and a surfactant.

[0026] The treatment liquid satisfies the first condition described above. Specifically, the octanol / water partition coefficient of the surfactant is -1 or more and 1 or less. Therefore, the treatment liquid has a suitable affinity for the substrate. Therefore, for example, when the treatment liquid is supplied to the substrate, the treatment liquid comes into sufficient contact with the substrate.

[0027] The processing liquid satisfies the second condition described above. Specifically, the vapor pressure of the surfactant at room temperature is 0.9 times or more and 3 times or less than the vapor pressure of the solvent at room temperature. Therefore, the vapor pressure of the surfactant at room temperature is not excessively high. Therefore, for example, when the processing liquid is supplied to a substrate, the processing liquid contacts the substrate sufficiently and reliably. Furthermore, the vapor pressure of the surfactant at room temperature is not excessively low. Therefore, the surfactant evaporates appropriately. Since the surfactant evaporates appropriately, the sublimable substance precipitates appropriately and the solidified film is formed appropriately.

[0028] As described above, the treatment liquid satisfies the first and second conditions, and therefore the treatment liquid can appropriately dry the substrate.

[0029] In the above-mentioned processing liquid, the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature. The processing liquid satisfies the above-mentioned third condition. Therefore, the solvent evaporates more easily than the sublimable substance. Therefore, by evaporating the solvent, the sublimable substance is more appropriately precipitated, and the solidified film is more appropriately formed.

[0030] In the above-mentioned treatment liquid, the vapor pressure of the surfactant at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature. The treatment liquid satisfies the above-mentioned fourth condition. Therefore, the surfactant evaporates more easily than the sublimable substance. Therefore, by evaporating the surfactant, the sublimable substance is more appropriately precipitated, and the solidified film is more appropriately formed.

[0031] In the above-mentioned treatment liquid, the sublimable substance is any one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following a1) to a20): a1) The solvent is methanol and the surfactant is acetone. a2) The solvent is ethanol and the surfactant is methanol. a3) The solvent is isopropyl alcohol and the surfactant is methanol. a4) The solvent is isopropyl alcohol and the surfactant is ethanol. a5) The solvent is isopropyl alcohol and the surfactant is tert-butanol. a6) The solvent is tert-butanol and the surfactant is methanol. a7) The solvent is tert-butanol and the surfactant is ethanol. a8) The solvent is tert-butanol and the surfactant is isopropyl alcohol. a9) The solvent is 1-propanol and the surfactant is ethanol. a10) The solvent is 1-propanol, and the surfactant is isopropyl alcohol. a11) The solvent is 1-propanol, and the surfactant is tert-butanol. a12) The solvent is isobutanol and the surfactant is 1-propanol. a13) The solvent is 1-ethoxy-2-propanol, and the surfactant is 1-propanol. a14) The solvent is 1-ethoxy-2-propanol, and the surfactant is isobutanol. a15) The solvent is 1-butanol, and the surfactant is 1-propanol. a16) The solvent is 1-butanol and the surfactant is isobutanol. a17) The solvent is 1-butanol, and the surfactant is 1-ethoxy-2-propanol. a18) The solvent is propylene glycol monomethyl ether acetate and the surfactant is isobutanol. a19) The solvent is propylene glycol monomethyl ether acetate and the surfactant is 1-ethoxy-2-propanol. a20) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-butanol. It is preferable.

[0032] When the sublimable substance, the solvent, and the surfactant are specified as above, the treatment liquid satisfactorily satisfies the first and second conditions, and therefore the substrate can be appropriately dried by using the treatment liquid.

[0033] In the above-mentioned treatment liquid, the sublimable substance is at least one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following b1) to b9): b1) The solvent is methanol and the surfactant is acetone. b2) The solvent is ethanol and the surfactant is methanol. b3) The solvent is isopropyl alcohol, and the surfactant is at least one of methanol, ethanol, and tert-butanol. b4) the solvent is tert-butanol, and the surfactant is at least one of methanol, ethanol, and isopropyl alcohol; b5) the solvent is 1-propanol, and the surfactant is at least one of ethanol, isopropyl alcohol, and tert-butanol; b6) The solvent is isobutanol and the surfactant is 1-propanol. b7) The solvent is 1-ethoxy-2-propanol, and the surfactant is at least one of 1-propanol and isobutanol. b8) The solvent is 1-butanol, and the surfactant is at least one of 1-propanol, isobutanol, and 1-ethoxy-2-propanol. b9) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is at least one of isobutanol, 1-ethoxy-2-propanol, and 1-butanol. It is preferable.

[0034] When the sublimable substance, the solvent, and the surfactant are specified as above, the treatment liquid satisfactorily satisfies the first and second conditions, and therefore the substrate can be appropriately dried by using the treatment liquid.

[0035] In the above-mentioned treatment liquid, the sublimable substance is at least one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following c1) to c9): c1) The solvent is methanol and the surfactant is acetone. c2) The solvent is at least one of ethanol, isopropyl alcohol, and tert-butanol, and the surfactant is methanol. c3) The solvent is at least one of isopropyl alcohol, tert-butanol, and 1-propanol, and the surfactant is ethanol. c4) The solvent is at least one of isopropyl alcohol and 1-propanol, and the surfactant is tert-butanol. c5) The solvent is at least one of tert-butanol and 1-propanol, and the surfactant is isopropyl alcohol. c6) The solvent is at least one of isobutanol, 1-ethoxy-2-propanol, and 1-butanol, and the surfactant is 1-propanol. c7) The solvent is at least one of 1-ethoxy-2-propanol, 1-butanol, and propylene glycol monomethyl ether acetate, and the surfactant is isobutanol. c8) The solvent is at least one of 1-butanol and propylene glycol monomethyl ether acetate, and the surfactant is 1-ethoxy-2-propanol. c9) The solvent is propylene glycol monomethyl ether acetate and the surfactant is 1-butanol. It is preferable.

[0036] When the sublimable substance, the solvent, and the surfactant are specified as above, the treatment liquid satisfactorily satisfies the first and second conditions, and therefore the substrate can be appropriately dried by using the treatment liquid.

[0037] In the above-mentioned treatment liquid, it is preferable that the volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. By using the treatment liquid, the substrate can be dried more appropriately.

[0038] In the above-mentioned processing liquid, the volume of the sublimable substance contained in the processing liquid is preferably 1% or more of the volume of the solvent contained in the processing liquid. In the above-mentioned processing liquid, the volume of the sublimable substance contained in the processing liquid is preferably 10% or less of the volume of the solvent contained in the processing liquid. By using the processing liquid, the substrate can be dried more appropriately.

[0039] In the above-mentioned treatment liquid, it is preferable that the volume of the surfactant contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. By using the treatment liquid, the substrate can be dried more appropriately.

[0040] In the above-mentioned processing liquid, the volume of the surfactant contained in the processing liquid is preferably 0.01% or more and 10% or less of the volume of the solvent contained in the processing liquid. In the above-mentioned processing liquid, the volume of the surfactant contained in the processing liquid is preferably 10% or less of the volume of the solvent contained in the processing liquid. By using the processing liquid, the substrate can be dried more appropriately.

[0041] The present invention is a substrate processing apparatus for processing a substrate, comprising: a substrate holding section for holding a substrate; a processing liquid generation unit for generating a processing liquid containing a sublimable substance, a solvent, and a surfactant; and a processing liquid supply section for supplying the processing liquid to a substrate held by the substrate holding section, wherein an octanol / water partition coefficient of the surfactant is -1 or more and 1 or less, and the vapor pressure of the surfactant at room temperature is 0.9 or more and 3 or less times the vapor pressure of the solvent at room temperature.

[0042] The substrate processing apparatus includes a substrate holding section, a processing liquid generating unit, and a processing liquid supply section. The substrate holding section holds a substrate. The processing liquid generating unit generates a processing liquid. The processing liquid includes a sublimable substance, a solvent, and a surfactant. The processing liquid supply section supplies the processing liquid to the substrate held by the substrate holding section.

[0043] Here, the processing liquid generated by the processing liquid generating unit satisfies the above-mentioned first and second conditions. Therefore, the substrate processing apparatus can suitably perform the above-mentioned substrate processing method. That is, the substrate processing apparatus can suitably dry the substrate.

[0044] In the above-mentioned substrate processing apparatus, it is preferable that the vapor pressure of the solvent at room temperature is higher than the vapor pressure of the sublimable material at room temperature. The processing liquid generated by the processing liquid generating unit satisfies the above-mentioned third condition. Therefore, the substrate processing apparatus can more appropriately dry the substrate.

[0045] In the above-mentioned substrate processing apparatus, it is preferable that the vapor pressure of the surfactant at room temperature is higher than the vapor pressure of the sublimable substance at room temperature. The processing liquid generated by the processing liquid generating unit satisfies the above-mentioned fourth condition. Therefore, the substrate processing apparatus can more appropriately dry the substrate.

[0046] In the above-mentioned substrate processing apparatus, it is preferable that the substrate held by the substrate holder has a pattern formed on a surface of the substrate. Even when the substrate has a pattern, the substrate processing apparatus can appropriately dry the substrate while protecting the pattern.

[0047] In the above-described substrate processing apparatus, it is preferable to further comprise a gas supply unit that supplies a gas to the substrate held by the substrate holder, thereby making it possible to efficiently dry the substrate. Effect of the Invention

[0048] According to the substrate processing method and processing solution of the present invention, the substrate can be appropriately dried. [Brief description of the drawings]

[0049] [Figure 1] FIG. 2 is a plan view showing the inside of the substrate processing apparatus according to the first embodiment. [Diagram 2] FIG. 2 is a control block diagram of the substrate processing apparatus. [Diagram 3] FIG. 2 is a diagram showing the configuration of a processing unit and a processing liquid generation unit according to the first embodiment. [Figure 4] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Diagram 5] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 6] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 7] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 8] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 9] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 10] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 11] 1 is a table showing examples of sublimable substances, solvents, and surfactants contained in a treatment liquid. [Figure 12] 1 is a flowchart showing a procedure of a substrate processing method. [Figure 13] 4A to 4C are diagrams illustrating a substrate in a treatment liquid supplying step. [Figure 14] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 15] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 16] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Figure 17] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Figure 18] 1 is a table showing evaluations of the substrates processed in Experimental Examples 1 and 2 and Comparative Examples 1 to 3. [Figure 19] 4A to 4C are diagrams illustrating a substrate in a treatment liquid supplying step. [Figure 20] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 21] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Figure 22] 4A to 4C are diagrams illustrating a substrate in a treatment liquid supplying step. [Diagram 23] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 24] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Diagram 25] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 26] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Figure 27] FIG. 11 is a diagram showing the configuration of a processing unit and a processing liquid generation unit according to a second embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0050] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A substrate processing method, a substrate processing solution, and a substrate processing apparatus according to the present invention will now be described with reference to the drawings.

[0051] <1. First embodiment> <1-1. Overview of substrate processing equipment> 1 is a plan view showing the inside of a substrate processing apparatus according to a first embodiment. The substrate processing apparatus 1 performs processing on a substrate W. The processing includes a drying process.

[0052] The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL (Electroluminescence), a substrate for an FPD (Flat Panel Display), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell. The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in a plan view.

[0053] 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 a substrate W to the processing block 7. The processing block 7 processes the substrate W. The indexer unit 3 retrieves the substrate W from the processing block 7.

[0054] 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." In each figure, for reference, front, back, right, left, top, and bottom are indicated as appropriate.

[0055] 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 stores a plurality of substrates W. The carrier C is, for example, a Front Opening Unified Pod (FOUP), a Standard Mechanical Interface (SMIF), or an Open Cassette (OC).

[0056] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is disposed behind the carrier placement unit 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 is accessible to the carrier C placed on the carrier placement unit 4. The transport mechanism 5 includes a hand 5a and a hand drive unit 5b. The hand 5a supports the substrate W. The hand drive unit 5b is connected to the hand 5a. The hand drive unit 5b moves the hand 5a. The hand drive unit 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand drive unit 5b rotates the hand 5a, for example, in a horizontal plane.

[0057] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 and the transport mechanism 5 are capable of transferring the substrate W to each other. The transport mechanism 8 includes a hand 8a and a hand driver 8b. The hand 8a supports the substrate W. The hand driver 8b is connected to the hand 8a. The hand driver 8b moves the hand 8a. The hand driver 8b moves the hand 8a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 8b rotates the hand 8a, for example, in a horizontal plane.

[0058] The processing block 7 includes a plurality of processing units 11. The processing units 11 are disposed to the sides of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

[0059] The processing unit 11 includes a substrate holding part 13. The substrate holding part 13 holds a substrate W.

[0060] The transport mechanism 8 is accessible to each processing unit 11. The transport mechanism 8 can deliver the substrate W to the substrate holding portion 13. The transport mechanism 8 can take the substrate W from the substrate holding portion 13.

[0061] 2 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 controls the transport mechanisms 5 and 8 and the processing unit 11.

[0062] 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 that are stored in advance in the storage medium. The information held by the control unit 10 is, for example, transport information for controlling the transport mechanisms 5 and 8. The information held by the control unit 10 is, for example, processing information for controlling the processing unit 11. The processing information is also called a processing recipe.

[0063] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0064] The indexer unit 3 supplies the substrate W to the processing block 7. Specifically, the transport mechanism 5 delivers the substrate W from the carrier C to the transport mechanism 8 of the processing block 7.

[0065] The processing block 7 distributes the substrate W from the indexer section 3 to the processing units 11. Specifically, the transport mechanism 8 transports the substrate W from the transport mechanism 5 to the substrate holder 13 of each processing unit 11.

[0066] The processing unit 11 processes the substrate W held by the substrate holder 13. The processing unit 11 performs a drying process on the substrate W, for example.

[0067] After the processing unit 11 has processed the substrate W, the processing block 7 returns the substrate W from the processing unit 11 to the indexer unit 3. Specifically, the transport mechanism 8 transports the substrate W from the substrate holder 13 to the transport mechanism 5.

[0068] 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.

[0069] <1-2. Configuration of processing unit 11> 3 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.

[0070] The substrate holding portion 13 holds one substrate W. The substrate holding portion 13 holds the substrate W in a substantially horizontal position. The substrate holding portion 13 holds the peripheral portion of the substrate W or the lower surface of the substrate W.

[0071] The processing unit 11 includes a rotation drive unit 14. The rotation drive unit 14 is connected to the substrate holding unit 13. The rotation 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 about a rotation axis B. The rotation axis B passes through the center of the substrate W, for example, and extends in the vertical direction Z.

[0072] The processing unit 11 includes a first nozzle 15a, a second nozzle 15b, a third nozzle 15c, a fourth nozzle 15d, and a fifth nozzle 15e. In the following, when the first to fifth nozzles 15a-15e are not distinguished from each other, they are simply referred to as "nozzles 15". Each nozzle 15 ejects a liquid or a gas onto the substrate W. More specifically, each nozzle 15 ejects a liquid or a gas onto the upper surface W1 of the substrate W held by the substrate holder 13. Each nozzle 15 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.

[0073] The processing unit 11 includes a housing 16. The housing 16 has a substantially box-like shape. The housing 16 accommodates a substrate holder 13, a rotation driver 14, and a nozzle 15 therein. The substrate W is processed inside the housing 16.

[0074] The inside of the housing 16 is kept at room temperature. The inside of the housing 16 is kept at normal pressure. Therefore, the substrate W is processed in an environment of room temperature and normal pressure. Here, room temperature is, for example, a temperature in the range of 10°C or more and 35°C or less. Room temperature is, for example, a temperature in the range of 20°C or more and 30°C or less. Normal pressure includes standard atmospheric pressure (1 atmosphere, 1013 hPa). 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 an absolute vacuum.

[0075] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 16. The cup is disposed around the substrate holder 13. The cup receives liquid splashed from the substrate W held by the substrate holder 13.

[0076] The processing unit 11 includes pipes 17a, 17b, 17c, 17d, and 17e. The pipes 17a-17e are connected to the first to fifth nozzles 15a-15e, respectively. At least a portion of the pipe 17a may be provided outside the housing 16. The pipes 17b-17e may be arranged in the same manner as the pipe 17a.

[0077] The processing unit 11 includes valves 18a, 18b, 18c, 18d, and 18e. The valves 18a-18e are provided in the pipes 17a-17e, respectively. The valve 18a may be provided outside the housing 16. The valves 18b-18e may be arranged in the same manner as the valve 18a.

[0078] The substrate processing apparatus 1 includes a processing liquid generating unit 20. The processing liquid generating unit 20 is connected to a pipe 17a. The processing liquid generating unit 20 is connected in communication with a first nozzle 15a.

[0079] The processing liquid generating unit 20 generates a processing liquid. The processing liquid generating unit 20 sends the processing liquid to the first nozzle 15a. The first nozzle 15a ejects the processing liquid. The processing liquid generating unit 20 may supply the processing liquid to a plurality of processing units 11.

[0080] The first nozzle 15a is an example of a processing liquid supply unit in the present invention.

[0081] The pipe 17b is connected to a chemical liquid supply source 19b. The chemical liquid supply source 19b is connected in communication with the second nozzle 15b. The chemical liquid supply source 19b sends the chemical liquid to the second nozzle 15b. The second nozzle 15b ejects the chemical liquid.

[0082] The chemical liquid is, for example, an etching liquid, and contains, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0083] The pipe 17c is connected to a rinse liquid supply source 19c. The rinse liquid supply source 19c is connected to the third nozzle 15c. The rinse liquid supply source 19c sends the rinse liquid to the third nozzle 15c. The third nozzle 15c ejects the rinse liquid.

[0084] The rinse liquid is, for example, deionized water (DIW).

[0085] The pipe 17d is connected to a replacement liquid supply source 19d. The replacement liquid supply source 19d is connected to the fourth nozzle 15d. The replacement liquid supply source 19d sends the replacement liquid to the fourth nozzle 15d. The fourth nozzle 15d discharges the replacement liquid.

[0086] The replacement liquid is, for example, an organic solvent, or isopropyl alcohol (IPA).

[0087] The pipe 17e is connected to a gas supply source 19e. The gas supply source 19e is connected in communication with the fifth nozzle 15e. The gas supply source 19e sends gas to the fifth nozzle 15e. The fifth nozzle 15e ejects the gas. The fifth nozzle 15e blows out the gas.

[0088] The gas is, for example, a dry gas. The dry gas has a dew point lower than room temperature. The dew point is, for example, about -76°C. Therefore, the dry gas does not condense at room temperature. The gas is, for example, air. The gas is, for example, compressed air. The gas is, for example, an inert gas. The gas is, for example, nitrogen gas.

[0089] The fifth nozzle 15e is an example of a gas supply unit according to the present invention.

[0090] The chemical liquid supply source 19b may be a component of the substrate processing apparatus 1. For example, the chemical liquid supply source 19b may be a chemical liquid tank included in the substrate processing apparatus 1. Alternatively, the chemical liquid supply source 19b may not be a component of the substrate processing apparatus 1. For example, the chemical liquid supply source 19b may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the rinsing liquid supply source 19c, the replacement liquid supply source 19d, and the gas supply source 19e may or may not be components of the substrate processing apparatus 1.

[0091] Please refer to Figure 2. The control unit 10 controls the rotary drive unit 14 and the valves 18a-18e.

[0092] <1-3. Processing solution> The following describes the treatment liquid generated by the treatment liquid generating unit 20. The treatment liquid contains a sublimable substance, a solvent, and a surfactant. For example, the treatment liquid is composed of only a sublimable substance, a solvent, and a surfactant.

[0093] Here, the “sublimable substance” satisfies the following conditions E1 to E4. Condition E1: The sublimable substance has sublimability. Condition E2: The sublimable substance is a solid at room temperature. Condition E3: The sublimable substance is soluble in the solvent at room temperature. Condition E4: The sublimable substance has a vapor pressure of 0.01 Pa (absolute pressure) or more at room temperature.

[0094] Regarding condition E1, "sublimability" refers to the property of a single substance, compound, or mixture to undergo a phase transition from a solid to a gas or from a gas to a solid without passing through a liquid state.

[0095] With regard to condition E2, it is preferred that the sublimable material be capable of remaining solid over a temperature range defined by room temperature.

[0096] The solvent is a liquid at room temperature and dissolves the sublimable material.

[0097] For this reason, the sublimable substance in the treatment liquid is dissolved in a solvent, that is, the treatment liquid contains a solvent, a sublimable substance dissolved in the solvent, and a surfactant.

[0098] The surfactant is a liquid at room temperature.

[0099] Here, the volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. For example, it is preferable that the volume of the sublimable substance contained in the treatment liquid is 1% or more of the volume of the solvent contained in the treatment liquid and 10% or less of the volume of the solvent contained in the treatment liquid. In other words, it is preferable that the sublimable substance and the solvent in the treatment liquid satisfy the following relationship. (Sublimable material during processing):(Solvent during processing)=1:100~10:100 (volume ratio)

[0100] The volume of the surfactant contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. For example, the volume of the surfactant contained in the treatment liquid is preferably 0.01% or more of the volume of the solvent contained in the treatment liquid and 10% or less of the volume of the solvent contained in the treatment liquid. In other words, it is preferable that the surfactant and the solvent in the treatment liquid satisfy the following relationship. (Surfactant during treatment):(Solvent during treatment) = 0.01:100 to 10:100 (volume ratio)

[0101] The group of compounds selectable as a solvent and the group of compounds selectable as a surfactant may overlap each other. However, it is prohibited for the same compound to be selected as both a solvent and a surfactant at the same time. For example, methanol may be selected as a solvent and also as a surfactant. However, when the solvent contains methanol, the surfactant does not contain methanol. That is, when the solvent contains methanol, it is prohibited for the surfactant to contain methanol. For example, when the solvent does not contain methanol, the surfactant may contain methanol. That is, when the solvent does not contain methanol, it is permitted for the surfactant to contain methanol.

[0102] Here, the treatment liquid satisfies the following first condition F1 and second condition F2. Specifically, the surfactant and solvent contained in the treatment liquid satisfy the first condition F1 and the second condition F2. First condition F1: The octanol / water partition coefficient LogPow of the surfactant is -1 or more and 1 or less. Second condition F2: The vapor pressure Pc of the surfactant at room temperature is 0.9 times or more the vapor pressure Pb of the solvent at room temperature and 3 times or less the vapor pressure Pb of the solvent at room temperature.

[0103] Furthermore, it is preferable that the treatment liquid satisfies the following third condition F3. Specifically, it is preferable that the solvent and sublimable substance contained in the treatment liquid satisfy the third condition F3. Third condition F3: The vapor pressure Pb of the solvent at room temperature is higher than the vapor pressure Pa of the sublimable substance at room temperature.

[0104] Furthermore, it is preferable that the treatment liquid satisfies the following fourth condition F4. Specifically, it is preferable that the surfactant and sublimable substance contained in the treatment liquid satisfy the fourth condition F4. Fourth condition F4: The vapor pressure Pb of the surfactant at room temperature is higher than the vapor pressure Pa of the sublimable substance at room temperature.

[0105] FIG. 4-11 is a table showing examples of sublimable substances, solvents, and surfactants contained in the treatment liquids. No. 1-78 in FIG. 4-11 indicate the numbers of the treatment liquids. Each of the treatment liquids No. 1-78 satisfies the first condition F1 and the second condition F2. Each of the treatment liquids No. 1-78 in FIG. 4-11 further satisfies the third condition F3. Each of the treatment liquids No. 1-78 in FIG. 4-11 further satisfies the fourth condition F4.

[0106] Please refer to Figures 4 and 5. Figures 4 and 5 show treatment liquids No. 1-20. The sublimable substance is cyclohexanone oxime. The solvent and surfactant are one of the following a1)-a20). Here, treatment liquid No. 1 corresponds to a treatment liquid containing cyclohexanone oxime, a solvent and a surfactant as specified in a1). Similarly, treatment liquids No. 2-20 correspond to treatment liquids containing cyclohexanone oxime, a solvent and a surfactant as specified in a2)-a20), respectively.

[0107] a1) The solvent is methanol and the surfactant is acetone. a2) The solvent is ethanol and the surfactant is methanol. a3) The solvent is isopropyl alcohol (IPA) and the surfactant is methanol. a4) The solvent is isopropyl alcohol (IPA) and the surfactant is ethanol. a5) The solvent is isopropyl alcohol (IPA) and the surfactant is tert-butanol. a6) The solvent is tert-butanol and the surfactant is methanol. a7) The solvent is tert-butanol and the surfactant is ethanol. a8) The solvent is tert-butanol and the surfactant is isopropyl alcohol (IPA). a9) The solvent is 1-propanol and the surfactant is ethanol. a10) The solvent is 1-propanol and the surfactant is isopropyl alcohol (IPA). a11) The solvent is 1-propanol and the surfactant is tert-butanol. a12) The solvent is isobutanol and the surfactant is 1-propanol. a13) The solvent is 1-ethoxy-2-propanol (PGEE) and the surfactant is 1-propanol. a14) The solvent is 1-ethoxy-2-propanol (PGEE) and the surfactant is isobutanol. a15) The solvent is 1-butanol and the surfactant is 1-propanol. a16) The solvent is 1-butanol and the surfactant is isobutanol. a17) The solvent is 1-butanol and the surfactant is 1-ethoxy-2-propanol (PGEE). a18) The solvent is propylene glycol monomethyl ether acetate (PGMEA) and the surfactant is isobutanol. a19) The solvent is propylene glycol monomethyl ether acetate (PGMEA) and the surfactant is 1-ethoxy-2-propanol (PGEE). a20) The solvent is propylene glycol monomethyl ether acetate (PGMEA) and the surfactant is 1-butanol.

[0108] Figures 4 and 5 show the vapor pressure Pa of a sublimable substance at room temperature. Figures 4 and 5 show the vapor pressure Pb of a solvent at room temperature. Figures 4 and 5 show the vapor pressure Pc of a surfactant at room temperature. Figures 4 and 5 show the octanol / water partition coefficient LogPow of a surfactant. Figures 4 and 5 show the value G obtained by dividing the vapor pressure Pc by the vapor pressure Pb.

[0109] The vapor pressure Pa of cyclohexanone oxime is measured at 25°C. The vapor pressures Pb and Pc of PGEE are measured at 25°C. The vapor pressure Pb of solvents other than PGEE is measured at 20°C. The vapor pressure Pc of surfactants other than PGEE is measured at 20°C.

[0110] In the treatment solutions No. 1-20, the octanol / water partition coefficient LogPow of the surfactant is not less than -1 and not more than 1. That is, regardless of whether the surfactant is a1)-a20), the octanol / water partition coefficient LogPow of the surfactant is not less than -1 and not more than 1. Thus, each of the treatment solutions No. 1-20 satisfies the first condition F1.

[0111] In the treatment liquids No. 1-20, the value G is 0.9 or more and 3 or less. That is, regardless of whether the solvent and surfactant are a1)-a20), the vapor pressure Pc of the surfactant is 0.9 or more and 3 or less than the vapor pressure Pb of the solvent. Therefore, each of the treatment liquids No. 1-20 satisfies the second condition F2.

[0112] In the treatment solutions No. 1-20, the vapor pressure Pb of the solvent is higher than the vapor pressure Pa of cyclohexanone oxime. That is, regardless of whether the solvent is a1)-a20), the vapor pressure Pb of the solvent is higher than the vapor pressure Pa of cyclohexanone oxime. Therefore, each of the treatment solutions No. 1-20 satisfies the third condition F3.

[0113] In the treatment solutions No. 1-20, the vapor pressure Pc of the surfactant is higher than the vapor pressure Pa of cyclohexanone oxime. That is, regardless of whether the surfactant is a1)-a20), the vapor pressure Pb of the surfactant is higher than the vapor pressure Pa of cyclohexanone oxime. Therefore, each of the treatment solutions No. 1-20 satisfies the fourth condition F4.

[0114] Please refer to Figures 6 and 7. Figures 6 and 7 show the treatment liquids No. 21-40. The sublimable substance is camphor. The solvent and surfactant are any one of a1)-a20) above. Here, the treatment liquid No. 21 corresponds to a treatment liquid containing camphor, a solvent and a surfactant as specified in a1). Similarly, the treatment liquids No. 22-40 correspond to treatment liquids containing camphor, a solvent and a surfactant as specified in a2)-a20), respectively.

[0115] 6 and 7 show the vapor pressure Pa of camphor at room temperature. The temperature at which the vapor pressure Pa of camphor is measured is 25 degrees.

[0116] As described above, regardless of whether the surfactant is a1)-a20), the octanol / water partition coefficient LogPow of the surfactant is not less than -1 and not more than 1. Therefore, in the treatment solutions No. 21-40, the octanol / water partition coefficient LogPow of the surfactant is also not less than -1 and not more than 1. Therefore, each of the treatment solutions No. 21-40 satisfies the first condition F1.

[0117] As described above, regardless of whether the solvent and surfactant are a1)-a20), the vapor pressure Pc of the surfactant is 0.9 to 3 times the vapor pressure Pb of the solvent. Therefore, in the treatment liquids No. 21-40, the vapor pressure Pc of the surfactant is 0.9 to 3 times the vapor pressure Pb of the solvent. Therefore, each of the treatment liquids No. 21-40 satisfies the second condition F2.

[0118] In the treatment solutions No. 21-40, the vapor pressure Pb of the solvent is higher than the vapor pressure Pa of camphor. That is, regardless of whether the solvent is a1)-a20), the vapor pressure Pb of the solvent is higher than the vapor pressure Pa of camphor. Therefore, each of the treatment solutions No. 21-40 satisfies the third condition F3.

[0119] In the treatment solutions No. 21-40, the vapor pressure Pc of the surfactant is higher than the vapor pressure Pa of camphor. That is, regardless of whether the surfactant is a1)-a20), the vapor pressure Pb of the surfactant is higher than the vapor pressure Pa of camphor. Therefore, each of the treatment solutions No. 21-40 satisfies the fourth condition F4.

[0120] Please refer to Figures 8 and 9. Figures 8 and 9 show the treatment liquids No. 41-60. The sublimable substance is ε-caprolactam. The solvent and surfactant are any one of the above a1)-a20).

[0121] Here, the treatment solution No. 41 corresponds to a treatment solution containing ε-caprolactam, a solvent and a surfactant as specified in a1), and similarly, the treatment solutions No. 42-60 correspond to treatment solutions containing ε-caprolactam, a solvent and a surfactant as specified in a2)-a20), respectively.

[0122] 8 and 9 show the vapor pressure Pa of ε-caprolactam at room temperature. The vapor pressure Pa of ε-caprolactam is measured at 25 degrees.

[0123] As described above, regardless of whether the surfactant is a1)-a20), the octanol / water partition coefficient LogPow of the surfactant is not less than -1 and not more than 1. Therefore, in the treatment solutions No. 41-60, the octanol / water partition coefficient LogPow of the surfactant is not less than -1 and not more than 1. Therefore, each of the treatment solutions No. 41-60 satisfies the first condition F1.

[0124] As described above, regardless of whether the solvent and surfactant are a1)-a20), the vapor pressure Pc of the surfactant is 0.9 to 3 times the vapor pressure Pb of the solvent. Therefore, in the treatment liquids No. 41-60, the vapor pressure Pc of the surfactant is 0.9 to 3 times the vapor pressure Pb of the solvent. Therefore, each of the treatment liquids No. 41-60 satisfies the second condition F2.

[0125] In the treatment solutions No. 41-60, the vapor pressure Pb of the solvent is higher than the vapor pressure Pa of ε-caprolactam. That is, regardless of whether the solvent is a1)-a20), the vapor pressure Pb of the solvent is higher than the vapor pressure Pa of ε-caprolactam. Thus, each of the treatment solutions No. 41-60 satisfies the third condition F3.

[0126] In the treatment solutions No. 41-60, the vapor pressure Pc of the surfactant is higher than the vapor pressure Pa of ε-caprolactam. That is, regardless of whether the surfactant is a1)-a20), the vapor pressure Pb of the surfactant is higher than the vapor pressure Pa of ε-caprolactam. Thus, each of the treatment solutions No. 41-60 satisfies the fourth condition F4.

[0127] Please refer to FIG. 10. FIG. 10 shows the treatment liquids No. 61-69. The sublimable substance is, for example, at least one of cyclohexanone oxime, camphor, and ε-caprolactam. The solvent and surfactant are one of b1)-b9) below. Here, the treatment liquid No. 61 corresponds to a treatment liquid containing a sublimable substance, a solvent and a surfactant as specified in b1). Similarly, the treatment liquids No. 62-69 correspond to treatment liquids containing a sublimable substance, a solvent and a surfactant as specified in b2)-b9), respectively.

[0128] The solvent and surfactant are any one of the following b1)-b9). b1) The solvent is methanol and the surfactant is acetone. b2) The solvent is ethanol and the surfactant is methanol. b3) The solvent is isopropyl alcohol (IPA) and the surfactant is at least one of methanol, ethanol, and tert-butanol. b4) The solvent is tert-butanol, and the surfactant is at least one of methanol, ethanol, and isopropyl alcohol (IPA). b5) The solvent is 1-propanol, and the surfactant is at least one of ethanol, isopropyl alcohol (IPA), and tert-butanol. b6) The solvent is isobutanol and the surfactant is 1-propanol. b7) The solvent is 1-ethoxy-2-propanol (PGEE) and the surfactant is at least one of 1-propanol and isobutanol. b8) The solvent is 1-butanol and the surfactant is at least one of 1-propanol, isobutanol, and 1-ethoxy-2-propanol (PGEE). b9) The solvent is propylene glycol monomethyl ether acetate (PGMEA) and the surfactant is at least one of isobutanol, 1-ethoxy-2-propanol (PGEE) and 1-butanol.

[0129] Here, the expression "at least one of" will be explained. For example, the expression "M is at least one of Ma, Mb, and Mc" means any one of the following d1) to d7). d1) M is Ma. d2) M is Mb. d3) M is Mc. d4) M is Ma and Mb. d5) M is Ma and Mc. d6) M is Mb and Mc. d7) M is Ma, Mb, and Mc. M is, for example, a sublimable material, a solvent, or a surfactant. Ma, Mb, and Mc are the names of compounds.

[0130] b1) is the same as a1). Therefore, the treatment liquid No. 61 satisfies the first to fourth conditions F1-F4. For the same reason, the treatment liquids No. 62 and 66 each satisfy the first to fourth conditions F1-F4.

[0131] The solvent in b3) is the same as the solvent in a3)-a5). The surfactant in b3) is at least one of the surfactants in a3)-a5). Therefore, the treatment liquid No. 63 satisfies the first to fourth conditions F1-F4. For the same reason, the treatment liquids No. 64, 65, 67-69 each satisfy the first to fourth conditions F1-F4.

[0132] Please refer to FIG. 11. FIG. 11 shows the treatment liquids No. 70-78. The sublimable substance is, for example, at least one of cyclohexanone oxime, camphor, and ε-caprolactam. The solvent and surfactant are one of c1)-c9) below. Here, the treatment liquid No. 70 corresponds to a treatment liquid containing a sublimable substance, a solvent and a surfactant as specified in c1). Similarly, the treatment liquids No. 71-78 correspond to treatment liquids containing a sublimable substance, a solvent and a surfactant as specified in c2)-c9), respectively.

[0133] The solvent and surfactant are any one of the following c1)-c9). c1) The solvent is methanol and the surfactant is acetone. c2) The solvent is at least one of ethanol, isopropyl alcohol (IPA) and tert-butanol, and the surfactant is methanol. c3) The solvent is at least one of isopropyl alcohol (IPA), tert-butanol, and 1-propanol, and the surfactant is ethanol. c4) The solvent is at least one of isopropyl alcohol (IPA) and 1-propanol, and the surfactant is tert-butanol. c5) The solvent is at least one of tert-butanol and 1-propanol, and the surfactant is isopropyl alcohol (IPA). c6) The solvent is at least one of isobutanol, 1-ethoxy-2-propanol (PGEE) and 1-butanol, and the surfactant is 1-propanol. c7) The solvent is at least one of 1-ethoxy-2-propanol (PGEE), 1-butanol, and propylene glycol monomethyl ether acetate (PGMEA), and the surfactant is isobutanol. c8) The solvent is at least one of 1-butanol and propylene glycol monomethyl ether acetate (PGMEA), and the surfactant is 1-ethoxy-2-propanol (PGEE). c9) The solvent is propylene glycol monomethyl ether acetate (PGMEA) and the surfactant is 1-butanol.

[0134] c1) is the same as a1). Therefore, the treatment liquid No. 70 satisfies the first to fourth conditions F1 to F4. For the same reason, the treatment liquid No. 78 satisfies the first to fourth conditions F1 to F4, respectively.

[0135] The surfactant in c2) is the same as the surfactant in a2), a3), or a6). The solvent in c2) is at least one of the solvents in a2), a3), or a6). Therefore, the treatment liquid No. 71 satisfies the first to fourth conditions F1 to F4. For the same reason, the treatment liquids No. 72 to 77 each satisfy the first to fourth conditions F1 to F4.

[0136] <1-4. Configuration of treatment liquid generating unit 20> Please refer to Fig. 3. The treatment liquid generating unit 20 generates a treatment liquid containing a sublimable substance, a solvent, and a surfactant.

[0137] The processing liquid generation unit 20 includes a first tank 21. The first tank 21 is connected in communication with the first nozzle 15a. In the first embodiment, the processing liquid generation unit 20 generates the processing liquid in the first tank 21. The processing liquid is generated in a room temperature environment. The processing liquid is generated in a normal pressure environment. The processing liquid generation unit 20 stores the generated processing liquid in the first tank 21. The processing liquid is stored in a room temperature environment. The processing liquid is stored in a normal pressure environment.

[0138] The treatment liquid production unit 20 includes a sublimable substance supplying section 23, a solvent supplying section 25, and a surfactant supplying section 27. The sublimable substance supplying section 23 supplies a sublimable substance to the first tank 21. The solvent supplying section 25 supplies a solvent to the first tank 21. The surfactant supplying section 27 supplies a surfactant to the first tank 21. The sublimable substance, the solvent, and the surfactant are mixed in the first tank 21. As a result, a treatment liquid containing the sublimable substance, the solvent, and the surfactant is produced.

[0139] The sublimable substance supply unit 23 includes, for example, a pipe 23a and a valve 23b. The pipe 23a is connected to the first tank 21. The pipe 23a is further connected to a sublimable substance supply source 24. The valve 23b is provided on the pipe 23a. When the valve 23b is open, the pipe 23a supplies the sublimable substance from the sublimable substance supply source 24 to the first tank 21.

[0140] The solvent supply unit 25 includes, for example, a pipe 25a and a valve 25b. The pipe 25a is connected in communication with the first tank 21. The pipe 25a is further connected in communication with a solvent supply source 26. The valve 25b is provided on the pipe 25a. When the valve 25b is opened, the pipe 25a supplies the solvent from the solvent supply source 26 to the first tank 21.

[0141] The surfactant supply unit 27 includes, for example, a pipe 27a and a valve 27b. The pipe 27a is connected in communication with the first tank 21. The pipe 27a is further connected in communication with a surfactant supply source 28. The valve 27b is provided on the pipe 27a. When the valve 27b is opened, the pipe 27a supplies the surfactant from the surfactant supply source 28 to the first tank 21.

[0142] The processing liquid generation unit 20 includes at least one or more (e.g., two) first sensors 29. The first sensor 29 detects the amount of processing liquid stored in the first tank 21. The first sensor 29 is attached to, for example, the first tank 21. The first sensor 29 detects, for example, the height position of the liquid surface of the processing liquid stored in the first tank 21. The first sensor 29 is, for example, a liquid surface sensor.

[0143] The treatment liquid generation unit 20 further sends the treatment liquid to the first nozzle 15a. The treatment liquid generation unit 20 includes a liquid delivery section 31. The liquid delivery section 31 delivers the treatment liquid from the first tank 21 to the first nozzle 15a.

[0144] Specifically, the liquid delivery section 31 includes a pipe 32, a pump 33, a filter 34, and a joint 35. The pipe 32 is connected in communication with the first tank 21. The pipe 32 extends from the first tank 21 to the pipe 17a. The pump 33 is provided in the pipe 32. The pump 33 delivers the treatment liquid from the first tank 21 to the pipe 32. The filter 34 is provided in the pipe 32. The filter 34 filters the treatment liquid flowing through the pipe 32. The filter 34 removes foreign matter from the treatment liquid. The joint 35 is connected to the pipe 32. The joint 35 is further connected to the pipe 17a. The pipe 32 and the pipe 17a are connected to each other by the joint 35. Therefore, the pump 33 delivers the treatment liquid from the first tank 21 to the pipe 17a (first nozzle 15a).

[0145] Please refer to Fig. 2. The control unit 10 controls the treatment liquid generating unit 20. The control unit 10 is electrically connected to the treatment liquid generating unit 20 so as to be able to communicate with each other.

[0146] The control unit 10 controls the sublimable material supply unit 23, the solvent supply unit 25, and the surfactant supply unit 27. The control unit 10 controls the valves 23b, 25b, 27b, and the pump 33.

[0147] The control unit 10 acquires the detection result of the first sensor 29 .

[0148] The control unit 10 controls the liquid delivery unit 31. The control unit 10 controls the pump 33.

[0149] The control unit 10 has treatment liquid generation information for controlling the treatment liquid generating unit 20. The treatment liquid generation information is stored in advance in a storage medium of the control unit 10. The treatment liquid generation information specifies, for example, the compounding ratio of the sublimable material, the solvent, and the surfactant contained in the treatment liquid.

[0150] <1-5. Operational Example of Mixture Adjustment Unit 20 and Processing Unit 11> 12 is a flowchart showing the procedure of the substrate processing method. The substrate processing method includes step S1 and steps S11-S18. Step S1 is performed by the processing liquid generation unit 20. Steps S11-18 are substantially performed by the processing unit 11. Step S1 is performed in parallel with steps S11-18. The processing liquid generation unit 20 and the processing unit 11 operate according to the control of the control unit 10.

[0151] Step S1: Processing solution generation process The treatment liquid generation unit 20 generates a treatment liquid. Specifically, the sublimable substance supplying section 23 supplies a sublimable substance to the first tank 21. The solvent supplying section 25 supplies a solvent to the first tank 21. The surfactant supplying section 27 supplies a surfactant to the first tank 21. In this way, the treatment liquid is generated in the first tank 21. Then, the treatment liquid is stored in the first tank 21.

[0152] The first sensor 29 detects the amount of the treatment liquid stored in the first tank 21. The control unit 10 monitors the detection result of the first sensor 29.

[0153] The control unit 10 starts and stops the treatment liquid generation process based on the detection result of the first sensor 29. For example, when the amount of treatment liquid stored in the first tank 21 is smaller than a first threshold, the control unit 10 starts the treatment liquid generation process. As a result, the treatment liquid generation unit 20 starts generating the treatment liquid. As a result, the treatment liquid stored in the first tank 21 increases. For example, when the amount of treatment liquid stored in the first tank 21 is larger than a second threshold, the control unit 10 stops the treatment liquid generation process. The second threshold is larger than the first threshold. As a result, the treatment liquid generation unit 20 stops generating the treatment liquid. As a result, the increase in the treatment liquid stored in the first tank 21 stops. The first threshold and the second threshold are, for example, set in advance. The first threshold and the second threshold are, for example, specified in the treatment liquid generation information.

[0154] Step S11: Rotation start process The substrate holding unit 13 holds the substrate W. The substrate W is held by the substrate holding unit 13 in a substantially horizontal position. The rotation drive unit 14 rotates the substrate holding unit 13. The substrate W held by the substrate holding unit 13 starts to rotate. Steps S12-S17 are performed with the substrate W rotated.

[0155] Step S12: Chemical solution supply process The second nozzle 15b supplies the chemical liquid to the substrate W. Specifically, the valve 18b opens. The second nozzle 15b supplies the chemical liquid to the substrate W held by the substrate holding part 13. The second nozzle 15b ejects the chemical liquid onto the upper surface W1 of the substrate W. The chemical liquid is supplied to the upper surface W1 of the substrate W. Then, the valve 18b closes. The second nozzle 15b stops supplying the chemical liquid.

[0156] Step S13: Rinse liquid supply process The third nozzle 15c supplies the rinsing liquid to the substrate W. Specifically, the valve 18c opens. The third nozzle 15c supplies the rinsing liquid to the substrate W held by the substrate holder 13. The third nozzle 15c ejects the rinsing liquid onto the upper surface W1 of the substrate W. The rinsing liquid is supplied to the upper surface W1 of the substrate W. The rinsing liquid cleans the substrate W. The rinsing liquid removes the chemical liquid from the substrate W. Then, the valve 18c closes. The third nozzle 15c stops supplying the rinsing liquid.

[0157] Step S14: Replacement liquid supply process The fourth nozzle 15d supplies the replacement liquid to the substrate W. Specifically, the valve 18d opens. The fourth nozzle 15d supplies the replacement liquid to the substrate W held by the substrate holder 13. The fourth nozzle 15d ejects the replacement liquid onto the upper surface W1 of the substrate W. The replacement liquid is supplied to the upper surface W1 of the substrate W. As a result, the replacement liquid replaces the rinsing liquid on the substrate W. In other words, the replacement liquid removes the rinsing liquid from the substrate W. Then, the valve 18d closes. The fourth nozzle 15d stops supplying the replacement liquid.

[0158] Step S15: Processing liquid supply process The processing liquid generating unit 20 sends the processing liquid generated in the processing liquid generating step to the first nozzle 15a. Specifically, the pump 33 sends the processing liquid from the first tank 21 to the pipe 17a. The valve 18a opens. The first nozzle 15a supplies the processing liquid to the substrate W held by the substrate holder 13. The first nozzle 15a ejects the processing liquid onto the upper surface W1 of the substrate W. The processing liquid is supplied to the upper surface W1 of the substrate W. As a result, the processing liquid replaces the replacement liquid on the substrate W. In other words, the processing liquid removes the replacement liquid from the substrate W. Then, the pump 33 stops. The valve 18a closes. The first nozzle 15a stops supplying the processing liquid.

[0159] 13 is a diagram illustrating a substrate W in a processing liquid supplying step. The substrate W has a pattern R. The pattern R is formed on the surface of the substrate W. When the substrate W is held by the substrate holding part 13, the pattern R is located on the upper surface W1 of the substrate W. When the substrate W is held by the substrate holding part 13, the pattern R faces upward.

[0160] The pattern R may be formed, for example, before the processing unit 11 processes the substrate W. The pattern R may be formed, for example, by a chemical liquid supplying step (step S12).

[0161] The pattern R has a convex portion W2 and a concave portion A. The convex portion W2 is a part of the substrate W. The convex portion W2 is a structure. The convex portion W2 is composed of, for example, a silicon oxide film (SiO2), a silicon nitride film (SiN), or a polysilicon film. The convex portion W2 protrudes upward. The concave portion A is adjacent to the side of the convex portion W2. The concave portion A is a space. The concave portion A is open upward. The convex portion W2 corresponds to a wall that defines the concave portion A.

[0162] The processing liquid H is located on the upper surface W1 of the substrate W. The processing liquid H forms a film covering the upper surface W1 of the substrate W.

[0163] The processing liquid H has an upper surface H1. The upper surface H1 is located at a position higher than the entirety of the pattern R. The entirety of the pattern R is immersed in the processing liquid H. The upper surface H1 is located at a position higher than the entirety of the protruding portion W2. The entirety of the protruding portion W2 is immersed in the processing liquid H.

[0164] The recess A is filled with the treatment liquid H. The entire recess A is filled with the treatment liquid H only.

[0165] It should be noted that the substitute liquid has already been removed from the upper surface W1 of the substrate W by the processing liquid H. Therefore, the substitute liquid is no longer present on the upper surface W1 of the substrate W. The substitute liquid does not remain in the recess A.

[0166] The gas J is located above the processing liquid H. The gas J is in contact with the upper surface H1. The upper surface H1 corresponds to the gas-liquid interface between the processing liquid H and the gas J. The convex portion W2 is not in contact with the upper surface H1. Therefore, the processing liquid H does not form a meniscus with the convex portion W2. Therefore, the surface tension of the processing liquid H does not act on the convex portion W2.

[0167] The processing liquid supplying step may further adjust the height position of the upper surface H1 of the processing liquid H. The height position of the upper surface H1 corresponds to the film thickness of the processing liquid H. For example, the height position of the upper surface H1 may be adjusted while the first nozzle 15a is supplying the processing liquid H to the substrate W. For example, the height position of the upper surface H1 may be adjusted after the first nozzle 15a stops supplying the processing liquid H. For example, the height position of the upper surface H1 may be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface H1 may be adjusted by adjusting the rotation time of the substrate W.

[0168] Step S16: Solidified film formation process The solvent and surfactant each evaporate from the processing liquid H on the substrate W1. The solvent and surfactant each change from a liquid to a gas. The evaporation of the solvent and surfactant causes the solvent and surfactant to be removed from the substrate W. The evaporation of the solvent and surfactant causes the sublimable substance to precipitate on the substrate W. A solidified film is formed on the substrate W. The solidified film is formed on the upper surface W1 of the substrate W. The solidified film includes the precipitated sublimable substance. The solidified film does not include the solvent or the surfactant. The solidified film is a solid.

[0169] 14 is a diagram showing a substrate W in a solidified film forming process. As the solvent and surfactant evaporate from the processing liquid H, the sublimable substance precipitates to form a solidified film K. The solvent and surfactant contained in the processing liquid H leave the upper surface W1 of the substrate W, and the sublimable substance contained in the processing liquid H turns into a solidified film.

[0170] As described above, the treatment liquid satisfies the third condition F3. That is, the vapor pressure Pb of the solvent at room temperature is higher than the vapor pressure Pa of the sublimable substance at room temperature. Therefore, the solvent evaporates more easily than the sublimable substance. Therefore, the solidified film K is properly formed.

[0171] Furthermore, the treatment liquid satisfies the fourth condition F4 described above. That is, the vapor pressure Pc of the surfactant at room temperature is higher than the vapor pressure Pa of the sublimable substance at room temperature. Therefore, the surfactant evaporates more easily than the sublimable substance. Therefore, the solidified film K is formed more appropriately.

[0172] The processing liquid H gradually changes into a solidified film K. First, the upper part of the processing liquid H changes into the solidified film K. The solidified film K is formed above the upper surface H1 of the processing liquid H. The solidified film K covers the upper surface H1 of the processing liquid H. The height position of the upper surface H1 of the processing liquid H gradually decreases. The remaining processing liquid H is located below the solidified film K.

[0173] After the solidified film K covers the upper surface H1 of the processing liquid H, the upper surface H1 of the processing liquid H does not come into contact with the gas J. In other words, the processing liquid H does not come into contact with the gas J. As the upper surface H1 is covered with the solidified film K, the gas-liquid interface between the processing liquid H and the gas J disappears. The upper surface H1 comes into contact with the solidified film K. The gas J comes into contact with the solidified film K. Therefore, in the solidified film formation process, the processing liquid H decreases without exerting a significant force on the protruding portion W2. The solvent and surfactant each leave the substrate W without exerting a significant force on the protruding portion W2.

[0174] FIG. 15 is a diagram showing a schematic of the substrate W in the solidified film formation process. Eventually, the processing liquid H disappears from the substrate W. No liquid is present on the upper surface W1 of the substrate W. At the end of the solidified film formation process, no processing liquid H remains in the recess A. The recess A is filled with the solidified film K. The entire recess A is filled only with the solidified film K. No liquid is present in the recess A. The pattern R is in contact with the solidified film K. The pattern R is not in contact with the liquid. The protruding portion W2 is in contact with the solidified film K. The protruding portion W2 is not in contact with the liquid.

[0175] Step S17: Sublimation process In the sublimation process, the solidified film is sublimated. Specifically, the valve 18e opens. The fifth nozzle 15e supplies gas to the substrate W held by the substrate holding part 13. The fifth nozzle 15e blows out gas toward the upper surface W1 of the substrate W. The fifth nozzle 15e supplies gas to the solidified film on the substrate W. The solidified film sublimes. The solidified film changes from a solid to a gas without passing through a liquid state. The sublimation of the solidified film removes the solidified film from the substrate W. Then, the valve 18e closes. The fifth nozzle 15e stops supplying gas.

[0176] 16 is a diagram showing a substrate W in a sublimation step. As the solidified film K sublimes, the solidified film K gradually decreases, and gas J enters the recess A.

[0177] When the solidified film K sublimes, the solidified film K does not change into liquid. Therefore, in the sublimation process, no liquid is present on the upper surface W1 of the substrate W. No liquid is present in the recess A. The pattern R does not come into contact with the liquid. The protrusion W2 does not come into contact with the liquid. The solidified film K leaves the upper surface W1 of the substrate W without exerting a significant force on the protrusion W2.

[0178] 17 is a diagram showing a substrate W in a sublimation process. Finally, the solidified film K disappears from the upper surface W1 of the substrate W. The recess A is filled with gas J. The entire recess A is filled only with gas J. No liquid is present on the upper surface W1 of the substrate W. The substrate W is completely dried.

[0179] The above-mentioned processing liquid supplying step, solidified film forming step, and sublimation step correspond to examples of using the processing liquid. The processing liquid is used in an environment at room temperature. The processing liquid is used in an environment at normal pressure.

[0180] Step S18: Rotation stop process The rotation driver 14 stops the rotation of the substrate holder 13. The substrate W held by the substrate holder 13 stops rotating. The substrate W comes to rest. The processing unit 11 finishes the processing of the substrate W.

[0181] <1-6. Technical significance of the first condition F1 and the second condition F2> The technical significance of the first condition F1 and the second condition F2 will be explained using Experimental Examples 1 and 2 and Comparative Examples 1 to 3.

[0182] Experimental example 1 is performed under the following conditions. In experimental example 1, a series of processes including a chemical liquid supplying step, a rinsing liquid supplying step, a replacement liquid supplying step, a processing liquid supplying step, a solidified film forming step, and a sublimation step are performed on a substrate W. The chemical liquid supplying step uses hydrofluoric acid as the chemical liquid. The rinsing liquid supplying step uses deionized water (DIW) as the rinsing liquid. The replacement liquid supplying step uses isopropyl alcohol as the replacement liquid.

[0183] In the processing liquid supplying step, multiple types of processing liquids with different amounts of surfactant added are prepared. Specifically, first, a surfactant-free liquid is generated. The surfactant-free liquid contains a sublimable substance and a solvent, but does not contain a surfactant. The surfactant-free liquid is, for example, composed only of a sublimable substance and a solvent. The sublimable substance is cyclohexanone oxime. The solvent is isopropyl alcohol (IPA). The volume ratio of the sublimable substance to the solvent is as follows: sublimable substance:solvent=2.5:100 (volume ratio). Next, a surfactant is added to the surfactant-free liquid to generate a processing liquid. Specifically, multiple types of processing liquids are generated by changing the amount of surfactant added.

[0184] In this specification, the amount T of the surfactant to be added is defined based on the volume of the solvent. Specifically, the amount T of the surfactant to be added is defined as follows. Addition amount T = (volume of surfactant contained in treatment liquid) / (volume of solvent contained in treatment liquid) * 100 [vol%] 100 vol % corresponds to the volume of the solvent in the treatment liquid.

[0185] The surfactant is tert-butanol in Experimental Example 1. Therefore, in Experimental Example 1, the treatment liquid contains cyclohexanone oxime as a sublimable substance, isopropyl alcohol (IPA) as a solvent, and tert-butanol as a surfactant.

[0186] The treatment liquid of Experimental Example 1 corresponds to treatment liquid No. 5 shown in Fig. 4. In other words, the treatment liquid of Experimental Example 1 corresponds to a treatment liquid containing cyclohexanone oxime, and the solvent and surfactant specified in a5).

[0187] In the treatment liquid supplying step, one of the treatment liquids was used. Therefore, in Experimental Example 1, a series of treatments was performed on the substrates W for the number of types of treatment liquid. Then, a plurality of substrates W that had been subjected to a series of treatments for each type of treatment liquid were obtained.

[0188] On the other hand, in the processing liquid supplying step, a series of processing steps was carried out on the substrate W using a surfactant-free liquid instead of the processing liquid.

[0189] Experimental Example 2 is carried out under the following conditions: The surfactant is methanol. The rest is the same as Experimental Example 1.

[0190] The treatment liquid of Experimental Example 2 corresponds to treatment liquid No. 3 shown in Fig. 4. In other words, the treatment liquid of Experimental Example 2 corresponds to a treatment liquid containing cyclohexanone oxime, and the solvent and surfactant specified in a3).

[0191] Comparative Example 1 is carried out under the following conditions: The surfactant is cyclohexane. The rest is the same as in Experimental Example 1.

[0192] The treatment liquid of Comparative Example 1 satisfies the second, third and fourth conditions, but does not satisfy the first condition. When the surfactant is cyclohexane, the octanol / water partition coefficient of the surfactant is greater than 1. Specifically, the octanol / water partition coefficient of cyclohexane is about 3.

[0193] Comparative Example 2 was carried out under the following conditions: The surfactant was acetone. The rest was the same as in Experimental Example 1.

[0194] The treatment liquid of Comparative Example 2 satisfies the first, third and fourth conditions but does not satisfy the second condition. When the solvent is isopropyl alcohol (IPA) and the surfactant is acetone, the vapor pressure Pc of the surfactant at room temperature is more than three times the vapor pressure Pb of the solvent at room temperature. Specifically, the vapor pressure of isopropyl alcohol (IPA) at room temperature is 4.4 kPa. The vapor pressure of acetone at room temperature is 24 kPa. The vapor pressure of acetone at room temperature Pc is about five times the vapor pressure Pb of isopropyl alcohol (IPA) at room temperature.

[0195] Comparative Example 3 is carried out under the following conditions: The surfactant is 1-butanol. The rest is the same as in Experimental Example 1.

[0196] The treatment liquid of Comparative Example 3 satisfies the first, third and fourth conditions but does not satisfy the second condition. When the solvent is isopropyl alcohol (IPA) and the surfactant is 1-butanol, the vapor pressure Pc of the surfactant at room temperature is less than 0.9 times the vapor pressure Pb of the solvent at room temperature. Specifically, the vapor pressure of isopropyl alcohol (IPA) at room temperature is 4.4 kPa. The vapor pressure of 1-butanol at room temperature is 0.7 kPa. Therefore, the vapor pressure of 1-butanol at room temperature is about 0.2 times the vapor pressure of isopropyl alcohol (IPA) at room temperature.

[0197] Each substrate W processed in Experimental Examples 1 and 2 and Comparative Examples 1-3 is evaluated according to the following evaluation criteria. An observer observes measurement points on the substrate W. The measurement points are minute areas at any position on the substrate W. The measurement points are magnified 50,000 times by a scanning electron microscope. At each measurement point, the observer counts the number N of convex portions W2 and the number n of collapsed convex portions W2. Here, the number n is equal to or less than the number N. The observer calculates the collapse rate at each measurement point. Furthermore, an average collapse rate is calculated for each substrate W.

[0198] The collapse rate is determined by the numbers N and n as follows: Collapse rate at each measurement point = n / N*100 (%) The average collapse rate (%) is the sum of the collapse rates at each measurement point divided by the number of measurement points.

[0199] Furthermore, the collapse index is calculated using the following formula. Collapse index = (average collapse rate) / (average collapse rate when using a solution without surfactant)

[0200] A collapse index of less than 1 means that the collapse rate has been improved compared to the collapse rate when a liquid without surfactant was used. In other words, when the collapse index is less than 1, it can be said that the collapse rate of pattern R has been suppressed. A collapse index of greater than 1 means that the collapse rate has worsened compared to the collapse rate when a liquid without surfactant was used. In other words, when the collapse index is greater than 1, it can be said that the collapse rate of pattern R has increased.

[0201] Fig. 18 is a table showing the evaluation of each substrate W processed in Experimental Examples 1 and 2 and Comparative Examples 1 to 3. Specifically, Fig. 18 shows the relationship between the amount T of surfactant added and the collapse index.

[0202] In Experimental Example 1, when the additive amount T is between 0.01 vol% and 10 vol%, the collapse index is substantially less than 1. Therefore, in Experimental Example 1, the collapse rate of pattern R was suppressed. When the additive amount T is in the range of 0.01 vol% to 0.1 vol%, the collapse index decreases as the additive amount T increases. When the additive amount T is in the range of 0.1 vol% to 10 vol%, the collapse index increases as the additive amount T increases. When the additive amount T is 0.1 vol%, the collapse index is 0.47. 0.47 is the minimum value of the collapse index in Experimental Example 1.

[0203] In Experimental Example 2, when the additive amount T is between 0.01 vol% and 10 vol%, the collapse index is less than 1. Therefore, in Experimental Example 2, the collapse rate of pattern R was suppressed. When the additive amount T is in the range of 0.01 vol% to 1.0 vol%, the collapse index decreases as the additive amount T increases. When the additive amount T is in the range of 1.0 vol% to 10 vol%, the collapse index increases as the additive amount T increases. When the additive amount T is 1.0 vol%, the collapse index is 0.31. 0.31 is the minimum value of the collapse index in Experimental Example 2.

[0204] In Comparative Example 1, the collapse index is significantly large in more than half of the range of the additive amount T from 0.05 vol% to 10 vol%. Therefore, the collapse rate of pattern R deteriorates in Comparative Example 1. In Comparative Example 1, when the additive amount T is from 0.05 vol% to 10 vol%, the collapse index repeatedly fluctuates between values ​​less than 1 and values ​​significantly greater than 1.

[0205] In Comparative Example 2, the collapse index is greater than 1 in most cases where the additive amount T is between 0.01 vol% and 10 vol%. Therefore, in Comparative Example 2, the collapse rate of pattern R worsened. When the additive amount T is in the range of 0.01 vol% to 0.1 vol%, the collapse index repeatedly fluctuates between values ​​less than 1 and values ​​greater than 1. When the additive amount T is in the range of 5 vol% to 10 vol%, the collapse index is significantly large.

[0206] In Comparative Example 3, when the additive amount T was from 0.50 vol % to 10 vol %, the collapse index was significantly greater than 1. Therefore, in Comparative Example 3, the collapse rate of pattern R was deteriorated.

[0207] <1-7. Relationship between the first condition F1 and drying of the substrate W> As shown in Comparative Example 1, when the octanol / water partition coefficient LOGPow of the surfactant is greater than 1, the collapse rate of pattern R increases. The present inventors speculate that this phenomenon is caused by an excessively large liquid film of the treatment liquid at the end of the treatment liquid supplying step. The mechanism assumed in the case of Comparative Example 1 will be described below.

[0208] Fig. 19 is a diagram showing a substrate W in a processing liquid supplying step. Fig. 20 is a diagram showing a substrate W in a solidified film forming step. Fig. 21 is a diagram showing a substrate W in a sublimation step. Figs. 19-21 show the case of Comparative Example 1. Figs. 19-21 show the case where the octanol / water distribution coefficient of the surfactant is greater than 1.

[0209] Refer to FIG. 19. When the octanol / water distribution coefficient of the surfactant is greater than 1, the processing liquid H has strong hydrophobicity. The convex portion W2 is hydrophobic. Therefore, the affinity between the processing liquid H and the substrate W is excessively high. Therefore, in the processing liquid supplying step, the film thickness of the processing liquid H formed on the substrate W tends to be excessively large. For example, the film thickness of the processing liquid H tends to be excessively large compared to the height of the pattern R. For example, the film thickness of the processing liquid H tends to be excessively large compared to the height of the convex portion W2.

[0210] Furthermore, there is a high affinity between the processing liquid H and the substrate W. For this reason, it is difficult to thin the film thickness of the processing liquid H in the processing liquid supplying step. It is difficult to adjust the film thickness of the processing liquid H in the processing liquid supplying step.

[0211] Refer to Fig. 20. As a result, in the solidified film forming step, the thickness of the solidified film K formed on the substrate W tends to be excessively large. For example, the thickness of the solidified film K tends to be excessively large compared to the height of the pattern R. For example, the thickness of the solidified film K tends to be excessively large compared to the height of the protrusion W2.

[0212] Refer to Fig. 21. As a result, in the sublimation process, when the solidified film K is sublimated, the protrusions W2 (pattern R) collapse. For example, two adjacent protrusions W2 stick together.

[0213] On the other hand, it is considered that the collapse rate of pattern R is also high when the octanol / water partition coefficient of the surfactant is smaller than -1. The present inventors speculate that this phenomenon is caused by the replacement liquid remaining in the recess A at the end of the processing liquid supplying step. The mechanism assumed when the octanol / water partition coefficient of the surfactant is smaller than -1 will be described below.

[0214] Fig. 22 is a diagram showing a substrate W in a processing liquid supplying step. Fig. 23 is a diagram showing a substrate W in a solidified film forming step. Fig. 24 is a diagram showing a substrate W in a sublimation step. Figs. 22-24 show a case where the octanol / water distribution coefficient of the surfactant is smaller than -1.

[0215] Please refer to FIG. 22. When the octanol / water distribution coefficient of the surfactant is smaller than -1, the processing liquid H has strong hydrophilicity. As described above, the convex portion W2 is hydrophobic. Therefore, the affinity between the processing liquid H and the substrate W is excessively low. Therefore, for example, the processing liquid H has difficulty sufficiently entering the concave portion A. For example, the processing liquid H cannot sufficiently remove the replacement liquid L from the substrate W. As a result, when the processing liquid supplying process is completed, the replacement liquid L remains in the concave portion A as a liquid. Even when the processing liquid supplying process is completed, the concave portion A is not entirely filled with only the processing liquid H.

[0216] 23. As a result, in the solidified film forming process, the recess A is not entirely filled with only the solidified film K. In other words, the solidified film K is not formed in the entire recess A. Even at the end of the solidified film forming process, the replacement liquid L exists in the recess A as a liquid.

[0217] Refer to FIG. 24. In the sublimation process, the solidified film K sublimes. Even after the solidified film K sublimes, the replacement liquid L remains in the recess A. The replacement liquid L has an upper surface L1. After the solidified film K sublimes, the upper surface L1 comes into contact with the gas J. The upper surface L1 becomes a gas-liquid interface between the replacement liquid L and the gas J. The upper surface L1 comes into contact with the protrusion W2. Therefore, the replacement liquid L forms a meniscus with respect to the protrusion W2. Therefore, the surface tension of the replacement liquid L acts on the protrusion W2. The replacement liquid L exerts a significant force on the protrusion W2. As a result, the protrusion W2 (pattern R) collapses.

[0218] As described above, even if the octanol / water partition coefficient of the surfactant is greater than 1 or smaller than -1, the collapse of the pattern R is not suppressed. Rather, the collapse of the pattern R is aggravated. Therefore, when the processing liquid H does not satisfy the first condition F1, the substrate W cannot be appropriately dried.

[0219] In contrast, as described above, in Experimental Examples 1 and 2, the processing liquid H satisfies the first condition F1. Therefore, the processing liquid H has an appropriate affinity for the substrate W. Therefore, the collapse rate of the pattern R is suitably suppressed in Experimental Examples 1 and 2. That is, in Experimental Examples 1 and 2, the substrate W can be appropriately dried while protecting the pattern R.

[0220] More specifically, when the octanol / water partition coefficient of the surfactant is -1 or more and 1 or less, the surfactant has amphipathicity. That is, the surfactant has both hydrophobicity and hydrophilicity. Therefore, the surfactant has affinity for the substrate W and affinity for the sublimable substance. For example, the affinity between the surfactant and the substrate W is higher than the affinity between the sublimable substance and the substrate W. For example, the affinity between the surfactant and the sublimable substance is higher than the affinity between the sublimable substance and the substrate W. Therefore, the affinity between the sublimable substance and the substrate W is improved via the surfactant. As a result, the processing liquid H has a moderate affinity for the substrate W.

[0221] <1-8. Relationship between the second condition F2 and drying of the substrate W> As shown in Comparative Example 2, when the vapor pressure Pc of the surfactant at room temperature is greater than three times the vapor pressure Pb of the solvent at room temperature, the collapse rate of the pattern R increases. The present inventors speculate that this phenomenon is caused by the replacement liquid remaining in the recess A at the end of the processing liquid supply step. Hereinafter, a mechanism assumed when the vapor pressure Pc of the surfactant at room temperature is greater than three times the vapor pressure Pb of the solvent at room temperature will be described.

[0222] For convenience, refer to FIG. 22. The surfactant has an excessively large vapor pressure. Therefore, the surfactant starts to evaporate immediately after the processing liquid is supplied to the substrate W in the processing liquid supplying process. The surfactant may not remain in the processing liquid until the processing liquid is in sufficient contact with the substrate W. The surfactant may evaporate before the processing liquid is in sufficient contact with the substrate W. The affinity between the processing liquid and the substrate may be significantly reduced before the processing liquid is in sufficient contact with the substrate W. Therefore, the processing liquid H cannot sufficiently remove the substitute liquid from the substrate W. When the processing liquid supplying process is completed, the substitute liquid L remains in the recess A as a liquid. Even when the processing liquid supplying process is completed, the recess A is not entirely filled with only the processing liquid H.

[0223] For convenience, reference will be made to Fig. 23. As a result, in the solidified film forming step, the recess A is not entirely filled with only the solidified film K. Even at the end of the solidified film forming step, the substitute liquid L is present in the recess A as a liquid.

[0224] For convenience, refer to FIG. 24. Even after the solidified film K is sublimated, the replacement liquid L remains in the recess A. The upper surface L1 becomes a gas-liquid interface between the replacement liquid L and the gas J. The upper surface L1 contacts the protrusion W2. Therefore, the surface tension of the replacement liquid L acts on the protrusion W2. As a result, the protrusion W2 (pattern R) collapses.

[0225] As shown in Comparative Example 3, when the vapor pressure Pc of the surfactant at room temperature is smaller than 0.9 times the vapor pressure Pb of the solvent at room temperature, the collapse rate of the pattern R increases. The inventors presume that this phenomenon is caused by the processing liquid remaining in the recess A at the end of the solidified film formation process. The mechanism assumed when the vapor pressure Pc of the surfactant at room temperature is smaller than 0.9 times the vapor pressure of the solvent Pb at room temperature will be described below.

[0226] Fig. 25 is a diagram showing a substrate W in a solidified film forming step. Fig. 26 is a diagram showing a substrate W in a sublimation step. Figs. 25-26 show the case of Comparative Example 3. Figs. 25-26 show the case where the vapor pressure Pc of the surfactant is excessively low.

[0227] It is assumed that at the end of the processing liquid supplying step, no replacement liquid remains in the recess A. In this case, at the end of the processing liquid supplying step, the recess A is entirely filled with only the processing liquid H (see FIG. 13).

[0228] Refer to FIG. 25. In the solidified film forming process, the solvent evaporates from the processing liquid H. However, the surfactant contained in the processing liquid H does not evaporate easily because the vapor pressure Pc of the surfactant is excessively low. Even after all the solvent contained in the processing liquid H has evaporated, the processing liquid H containing the surfactant remains in the recess A. As a result, at the end of the solidified film forming process, the processing liquid H remains in the recess A. The solidified film K is not formed in the entire recess A.

[0229] Please refer to FIG. 26. In the sublimation process, the solidified film K sublimes. Even after the solidified film K sublimes, the processing liquid H remains in the recess A. After the solidified film K sublimes, the upper surface H1 of the processing liquid H comes into contact with the gas J. After the solidified film K sublimes, the upper surface H1 becomes a gas-liquid interface between the processing liquid H and the gas J. The upper surface H1 comes into contact with the protruding portion W2. Therefore, the processing liquid H forms a meniscus with respect to the protruding portion W2. Therefore, the surface tension of the processing liquid H acts on the protruding portion W2. Therefore, the processing liquid H exerts a significant force on the protruding portion W2. As a result, the protruding portion W2 (pattern R) collapses.

[0230] As described above, when the vapor pressure Pc of the surfactant at room temperature is greater than three times the vapor pressure Pb of the solvent at room temperature, the collapse of pattern R is not suppressed. In fact, the collapse of pattern R becomes worse. When the vapor pressure Pc of the surfactant at room temperature is less than 0.9 times the vapor pressure Pb of the solvent at room temperature, the collapse of pattern R is not suppressed. In fact, the collapse of pattern R becomes worse. Therefore, when the processing liquid H does not satisfy the second condition F2, the substrate W cannot be properly dried.

[0231] In contrast, as described above, in Experimental Examples 1 and 2, the processing liquid H satisfies the second condition F2. Therefore, the surfactant has an appropriate vapor pressure Pc. Therefore, in Experimental Examples 1 and 2, the collapse rate of the pattern R is suitably suppressed. That is, in Experimental Examples 1 and 2, the substrate W can be appropriately dried while protecting the pattern R.

[0232] <1-9. Relationship between the amount of surfactant added T and drying of the substrate W> In Experimental Example 1, the collapse index is substantially less than 1 even in the range of 0.1 vol% to 10 vol%. However, in Experimental Example 1, the collapse index increases as the additive amount T increases in the range of 0.1 vol% to 10 vol%. In Experimental Example 2, the collapse index is less than 1 even in the range of 1.0 vol% to 10 vol%. However, in Experimental Example 2, the collapse index increases as the additive amount T increases in the range of 1.0 vol% to 10 vol%. The present inventors presume that this phenomenon is caused by the fact that the liquid film of the treatment liquid is somewhat large at the end of the treatment liquid supplying step. The mechanism assumed when the additive amount T increases will be described below.

[0233] As the additive amount T increases, the affinity between the processing liquid and the substrate W increases. Therefore, as the additive amount T increases, the film thickness of the processing liquid H formed in the processing liquid supplying process increases. As the additive amount T increases, the film thickness of the processing liquid H is less likely to become thin. As a result, as the additive amount T increases, the film thickness of the solidified film K formed in the solidified film forming process increases. Then, in the sublimation process, when the solidified film sublimes, the convex portion W2 (pattern R) becomes somewhat more likely to collapse.

[0234] Therefore, it is preferable to appropriately select the amount T of the surfactant to be added. This makes it possible to more effectively prevent the pattern R from collapsing.

[0235] For example, the amount T of the surfactant added is preferably 10 vol % or less of the volume of the solvent contained in the treatment liquid. In other words, the volume of the surfactant contained in the treatment liquid is preferably 10% or less of the volume of the solvent contained in the treatment liquid.

[0236] On the other hand, in Experimental Examples 1 and 2, even when the amount of surfactant added T was 0.01 vol%, the collapse of pattern R was sufficiently suppressed. For example, in Experimental Example 1, when the amount of surfactant added T was 0.01 vol%, the collapse index was 0.68. For example, in Experimental Example 2, when the amount of surfactant added T was 0.01 vol%, the collapse index was 0.72.

[0237] Therefore, for example, the amount T of the surfactant added is preferably 0.01 vol% or more of the volume of the solvent contained in the treatment liquid. In other words, the volume of the surfactant contained in the treatment liquid is preferably 0.01% or more of the volume of the solvent contained in the treatment liquid.

[0238] <1-10. Effects of the First Embodiment> The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. The processing liquid supplying step supplies a processing liquid to the substrate W. The processing liquid includes a sublimable substance, a solvent, and a surfactant. The solidified film forming step evaporates the solvent and the surfactant from the processing liquid on the substrate W. The solidified film forming step forms a solidified film on the substrate W. The solidified film includes a sublimable substance. The sublimation step sublimes the solidified film.

[0239] The processing liquid satisfies the first condition F1. Specifically, the octanol / water partition coefficient of the surfactant is equal to or greater than -1 and equal to or less than 1. Therefore, the processing liquid has an appropriate affinity for the substrate W. Thus, the surfactant improves the affinity between the sublimable substance and the substrate. Therefore, the processing liquid supplying process can appropriately supply the processing liquid to the substrate W. For example, in the processing liquid supplying process, the processing liquid is in sufficient contact with the upper surface W1 of the substrate W. In other words, in the processing liquid supplying process, the processing liquid is sufficiently compatible with the upper surface W1 of the substrate W. Even if the substrate W has a pattern R, the processing liquid is in sufficient contact with the pattern R.

[0240] The treatment liquid satisfies the second condition F2. Specifically, the vapor pressure of the surfactant at room temperature is 0.9 to 3 times the vapor pressure of the solvent at room temperature.

[0241] The vapor pressure of the surfactant at room temperature is three times or less than the vapor pressure of the solvent at room temperature. Therefore, the vapor pressure of the surfactant at room temperature is not excessively high. Therefore, the processing liquid supplying step can more appropriately supply the processing liquid to the substrate W. For example, in the processing liquid supplying step, the surfactant does not evaporate but remains in the processing liquid, and the processing liquid is sufficiently in contact with the substrate W. Therefore, in the processing liquid supplying step, the processing liquid is sufficiently and reliably in contact with the substrate W. For example, in the processing liquid supplying step, the processing liquid can sufficiently remove the substitute liquid from above the substrate W. For example, the processing liquid can suitably prevent the substitute liquid from remaining in the recess A at the end of the processing liquid supplying step.

[0242] Furthermore, the vapor pressure of the surfactant at room temperature is 0.9 times or more the vapor pressure of the solvent at room temperature. Therefore, the vapor pressure of the surfactant at room temperature is not excessively low. Therefore, in the solidified film formation process, the surfactant evaporates appropriately. Since the surfactant evaporates appropriately, the sublimable substance precipitates appropriately. Therefore, the solidified film formation process can properly form a solidified film on the substrate W. For example, at the end of the solidified film formation process, the processing liquid is preferably prevented from remaining in the recess A. As a result, the pattern R can be preferably protected even in the sublimation process.

[0243] In summary, since the processing liquid satisfies the first condition F1 and the second condition F2, the processing liquid supplying step can appropriately supply the processing liquid to the substrate W. Since the processing liquid satisfies the second condition, the solidified film forming step can appropriately form a solidified film on the substrate W. Therefore, according to the above-described substrate processing method, the substrate W can be appropriately dried.

[0244] The processing liquid satisfies the third condition F3. Specifically, the vapor pressure of the solvent at room temperature is higher than the vapor pressure of the sublimable substance at room temperature. Therefore, the solvent evaporates more easily than the sublimable substance. Thus, the evaporation of the solvent allows the sublimable substance to precipitate more appropriately. Therefore, the solidified film forming process can more appropriately form a solidified film on the substrate W.

[0245] The processing liquid satisfies the fourth condition F4. Specifically, the vapor pressure of the surfactant at room temperature is higher than the vapor pressure of the sublimable substance at room temperature. Therefore, the surfactant evaporates more easily than the sublimable substance. Thus, the evaporation of the surfactant allows the sublimable substance to precipitate more appropriately. Therefore, the solidified film forming step can form a solidified film on the substrate W more appropriately.

[0246] The processing liquid is used to dry the substrate and contains a sublimable material, a solvent, and a surfactant.

[0247] The processing liquid satisfies the first condition F1. Therefore, the processing liquid has an appropriate affinity for the substrate W. Therefore, for example, when the processing liquid is supplied to the substrate W, the processing liquid comes into contact with the substrate W sufficiently.

[0248] The processing liquid satisfies the second condition F2. Therefore, the vapor pressure of the surfactant at room temperature is not excessively high. Therefore, for example, when the processing liquid is supplied to a substrate, the processing liquid contacts the substrate sufficiently and reliably. Furthermore, the vapor pressure of the surfactant at room temperature is not excessively low. Therefore, the surfactant evaporates appropriately. Since the surfactant evaporates appropriately, the sublimable substance precipitates appropriately and the solidified film is formed appropriately.

[0249] As described above, the processing liquid satisfies the first condition F1 and the second condition F2. Therefore, the processing liquid can appropriately dry the substrate W.

[0250] The treatment liquid satisfies the third condition F3. Therefore, the solvent evaporates more easily than the sublimable substance. Therefore, as the solvent evaporates, the sublimable substance precipitates more appropriately and the solidified film is formed more appropriately.

[0251] The treatment liquid satisfies the fourth condition F4. Therefore, the surfactant evaporates more easily than the sublimable substance. Therefore, when the surfactant evaporates, the sublimable substance precipitates more appropriately, and the solidified film is formed more appropriately.

[0252] For example, the sublimable substance is any one of cyclohexanone oxime, camphor, and ε-caprolactam. The solvent and surfactant are any one of a1)-a20) above. When the sublimable substance, the solvent, and the surfactant are specified in this way, the treatment liquid satisfies the first condition F1 and the second condition F2 suitably. Therefore, the substrate treatment method can properly dry the substrate W. By using the treatment liquid, the substrate W can be properly dried.

[0253] When the sublimable substance, the solvent, and the surfactant are specified in this way, the processing liquid further satisfies the third condition F3. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0254] When the sublimable substance, the solvent, and the surfactant are specified in this way, the processing liquid further satisfies the fourth condition F4. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0255] For example, the sublimable substance is at least one of cyclohexanone oxime, camphor, and ε-caprolactam. The solvent and surfactant are any one of b1)-b9) above. When the sublimable substance, the solvent, and the surfactant are specified in this way, the treatment liquid satisfies the first condition F1 and the second condition F2 suitably. Therefore, the substrate treatment method can properly dry the substrate W. By using the treatment liquid, the substrate W can be properly dried.

[0256] When the sublimable substance, the solvent, and the surfactant are specified in this way, the processing liquid further satisfies the third condition F3. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0257] When the sublimable substance, the solvent, and the surfactant are specified in this way, the processing liquid further satisfies the fourth condition F4. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0258] The sublimable substance is at least one of cyclohexanone oxime, camphor, and ε-caprolactam. The solvent and surfactant are any one of c1)-c9) below. When the sublimable substance, the solvent, and the surfactant are specified in this way, the treatment liquid satisfies the first condition F1 and the second condition F2 suitably. Therefore, the substrate treatment method can properly dry the substrate W. By using the treatment liquid, the substrate W can be properly dried.

[0259] When the sublimable substance, the solvent, and the surfactant are specified in this way, the processing liquid further satisfies the third condition F3. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0260] When the sublimable substance, the solvent, and the surfactant are specified in this way, the processing liquid further satisfies the fourth condition F4. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0261] The volume of the sublimable substance contained in the processing liquid is smaller than the volume of the solvent contained in the processing liquid. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0262] The volume of the sublimable substance contained in the processing liquid is 1% or more of the volume of the solvent contained in the processing liquid and 10% or less of the volume of the solvent contained in the processing liquid. Therefore, the processing liquid contains an appropriate amount of sublimable substance. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0263] The volume of the surfactant contained in the processing liquid is smaller than the volume of the solvent contained in the processing liquid. Therefore, the substrate processing method can more appropriately dry the substrate W. By using the processing liquid, the substrate W can be more appropriately dried.

[0264] The volume of the surfactant contained in the processing liquid is 0.01% or more and 10% or less of the volume of the solvent contained in the processing liquid. In other words, assuming that the volume of the solvent in the processing liquid is 100 vol%, the amount T of surfactant added is 0.01 vol% or more and 10 vol% or less. Therefore, the processing liquid contains an appropriate amount of surfactant. Therefore, the processing liquid has an appropriate affinity for the substrate W. Therefore, the substrate processing method can dry the substrate W more appropriately. By using the processing liquid, the substrate W can be dried more appropriately.

[0265] The substrate W has a pattern R. The pattern R is formed on a surface of the substrate W. Even when the substrate W has the pattern R, the substrate processing method can properly dry the substrate W while protecting the pattern R. For example, the substrate processing method can properly dry the substrate W while preventing the pattern R from collapsing.

[0266] The substrate processing apparatus 1 includes a substrate holding part 13, a processing liquid generating unit 20, and a first nozzle 15a. The substrate holding part 13 holds a substrate W. The processing liquid generating unit 20 generates a processing liquid. The first nozzle 15a supplies the processing liquid to the substrate W held by the substrate holding part 13.

[0267] Here, the processing liquid generated by the processing liquid generating unit 20 satisfies the first condition F1 and the second condition F2. Therefore, the substrate processing apparatus 1 can suitably perform the above-mentioned substrate processing method. That is, the substrate processing apparatus 1 can appropriately dry the substrate W.

[0268] The processing liquid generated by the processing liquid generating unit 20 further satisfies the third condition F3. Therefore, the substrate processing apparatus 1 can dry the substrate W more appropriately.

[0269] The processing liquid generated by the processing liquid generating unit 20 further satisfies the fourth condition F4. Therefore, the substrate processing apparatus 1 can dry the substrate W more appropriately.

[0270] The treatment liquid generation unit 20 includes a first tank 21. Therefore, the treatment liquid generation unit 20 can suitably generate the treatment liquid in the first tank 21.

[0271] Furthermore, the treatment liquid production unit 20 can suitably store the treatment liquid in the first tank 21.

[0272] The substrate W held by the substrate holding part 13 has a pattern R on the substrate W. The pattern R is formed on the surface of the substrate W. Even when the substrate W has the pattern R, the substrate processing apparatus 1 can properly dry the substrate W while protecting the pattern R.

[0273] The substrate processing apparatus 1 includes a fifth nozzle 15e. The fifth nozzle 15e supplies gas to the substrate W held by the substrate holding part 13. Therefore, the substrate processing apparatus 1 can dry the substrate W efficiently.

[0274] <2. Second embodiment> A substrate processing apparatus 1 according to a second embodiment will be described with reference to the drawings. Note that the same components as those in the first embodiment are denoted by the same reference numerals and detailed description thereof will be omitted.

[0275] The second embodiment is substantially the same as the first embodiment in terms of the outline of the substrate processing apparatus 1 and the configuration of the processing unit 11. The configuration of the processing liquid generation unit 20 of the second embodiment will be described below.

[0276] 27 is a diagram showing the configuration of the processing unit and the processing liquid generation unit 20 of the second embodiment. The processing liquid generation unit 20 includes a first tank 41, a second tank 42, and a third tank 43. The first tank 41 stores a sublimable substance. For example, the first tank 41 may store a solvent together with the sublimable substance. The second tank 42 stores a solvent. For example, the second tank 42 stores only the solvent. The third tank 43 stores a surfactant. For example, the third tank 43 stores only the surfactant.

[0277] The treatment liquid generation unit 20 includes a mixer 44. The mixer 44 is connected in communication with the first to third tanks 41-43. The mixer 44 is further connected in communication with the first nozzle 15a. In the second embodiment, the treatment liquid generation unit 20 generates the treatment liquid in the mixer 44. In the second embodiment, the treatment liquid is also generated in a room temperature environment. The treatment liquid is generated in a normal pressure environment.

[0278] The treatment liquid generated in the mixing section 44 satisfies the first condition F1 and the second condition F2 described above. Furthermore, the treatment liquid preferably satisfies the third condition F3. The treatment liquid preferably satisfies the fourth condition F4. The treatment liquid is, for example, any one of the treatment liquids No. 1-78 shown in FIG. 4-11.

[0279] The mixing section 44 includes pipes 45a, 45b, and 45c, and a joint 46. The pipe 45a communicates and connects the first tank 41 to the joint 46. The pipe 45b communicates and connects the second tank 42 to the joint 46. The pipe 45c communicates and connects the third tank 43 to the joint 46. The joint 46 is further connected to the pipe 17a. The pipes 17a, 45a, 45b, and 45c communicate with each other via the joint 46.

[0280] The mixing section 44 includes valves 47a, 47b, and 47c. The valves 47a, 47b, and 47c are provided in the pipes 45a, 45b, and 45c, respectively. The valve 47a adjusts the flow rate of the sublimable material flowing through the pipe 45a. The valve 47b adjusts the flow rate of the solvent flowing through the pipe 45b. The valve 47c adjusts the flow rate of the surfactant flowing through the pipe 45c. The valve 47a may include, for example, a flow rate control valve. The valve 47a may include, for example, a flow rate control valve and an on-off valve.

[0281] The mixer 44 includes pumps 48a, 48b, and 48c. The pumps 48a, 48b, and 48c are provided on the pipes 45a, 45b, and 45c, respectively. The pump 48a flows the sublimable substance from the first tank 41 to the pipe 45a. The pump 48b flows the solvent from the second tank 42 to the pipe 45b. The pump 48c flows the surfactant from the third tank 43 to the pipe 45c.

[0282] The mixer 44 includes filters 49a, 49b, and 49c. The filters 49a, 49b, and 49c are provided on the pipes 45a, 45b, and 45c, respectively. The filter 49a filters the sublimable material flowing through the pipe 45a. The filter 49b filters the solvent flowing through the pipe 45b. The filter 49c filters the surfactant flowing through the pipe 45c.

[0283] Although not shown in the figure, the control unit 10 controls the mixer 44. The control unit 10 controls the valves 47a, 47b, and 47c and the pumps 48a, 48b, and 48c.

[0284] <2-2. Operational Example of Processing Liquid Generation Unit 20 and Processing Unit 11> Please refer to FIG. 4. The substrate processing method of the second embodiment includes step S1 and steps S11-S18, similarly to the first embodiment. The operations of steps S11-S14 and S16-S18 are substantially common between the first and second embodiments. Therefore, the description of the operations of steps S11-S14 and S16-S18 will be omitted. The operations of steps S1 and S15 will be described.

[0285] Steps S1 and S15: Processing solution generating step and processing solution supplying step The processing liquid generating unit 20 generates the processing liquid in the mixer 44. The first nozzle 15a supplies the processing liquid generated by the processing liquid generating unit 20 to the substrate W.

[0286] Specifically, pump 48a sends the sublimable material from the first tank 41 to joint 46 via pipe 45a. Valve 47a adjusts the amount of sublimable material supplied to joint 46. Pump 48b sends the solvent from the second tank 42 to joint 46 via pipe 45b. Valve 47b adjusts the amount of solvent supplied to joint 46. Pump 48c sends the surfactant from the third tank 43 to joint 46 via pipe 45c. Valve 47c adjusts the amount of surfactant supplied to joint 46. The sublimable material, solvent, and surfactant join at joint 46. Joint 46 produces a treatment liquid.

[0287] The valve 18a opens. The processing liquid flows from the joint 46 through the pipe 17a to the first nozzle 15a. The first nozzle 15a supplies the processing liquid to the substrate W held by the substrate holder 13. The first nozzle 15a ejects the processing liquid onto the upper surface W1 of the substrate W. The processing liquid is supplied to the upper surface W1 of the substrate W. As a result, the processing liquid replaces the replacement liquid on the substrate W. The pump 33 then stops. The valve 18a closes. The first nozzle 15a stops supplying the processing liquid.

[0288] 2-3. Effects of the Second Embodiment The second embodiment also has the same effects as the first embodiment. For example, the processing liquid satisfies the first condition F1 and the second condition F2. Therefore, the substrate processing method can appropriately dry the substrate W. The processing liquid can appropriately dry the substrate W.

[0289] The treatment liquid generation unit 20 includes a mixer 44. Therefore, the treatment liquid generation unit 20 can suitably generate the treatment liquid in the mixer 44.

[0290] The mixing section 44 corresponds to a flow path communicating with the first nozzle 15a. Therefore, the treatment liquid generating unit 20 generates the treatment liquid in the flow path communicating with the first nozzle 15a. Therefore, when the first nozzle 15a uses the treatment liquid, the treatment liquid generating unit 20 can generate the treatment liquid suitably. After the treatment liquid generating unit 20 generates the treatment liquid, the first nozzle 15a can use the treatment liquid promptly.

[0291] The present invention is not limited to the embodiments, and can be modified as follows.

[0292] (1) In the first and second embodiments, the treatment liquid No. 1-78 shown in Fig. 4-11 is exemplified. However, the present invention is not limited to this. In other words, the treatment liquid may be a treatment liquid other than the treatment liquid No. 1-78.

[0293] (2) In the first and second embodiments, the sublimable substance contained in the treatment liquid is, for example, at least one of cyclohexanone oxime, camphor, and ε-caprolactam. However, this is not limited thereto. In other words, the sublimable substance may contain a substance other than cyclohexanone oxime, camphor, and ε-caprolactam.

[0294] (3) In the first and second embodiments, the solvent and surfactant contained in the treatment liquid are, for example, any one of a1)-a20), b1)-b9), and c1)-c9). However, this is not limited thereto. In other words, the solvent and surfactant contained in the treatment liquid may contain a substance other than the substances specified in a1)-a20), b1)-b9), and c1)-c9).

[0295] (4) In the first and second embodiments, the chemical liquid supplying step, the rinse liquid supplying step, and the replacement liquid supplying step are provided. However, this is not limited to this. For example, at least one of the chemical liquid supplying step, the rinse liquid supplying step, and the replacement liquid supplying step may be omitted. For example, all of the chemical liquid supplying step, the rinse liquid supplying step, and the replacement liquid supplying step may be omitted.

[0296] (5) In the first and second embodiments, when the processing liquid supplying process was performed, a liquid (e.g., a substitute liquid) was present on the substrate W. That is, in the processing liquid supplying process, the processing liquid 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 process is performed, a liquid (e.g., a substitute liquid) does not have to be present on the substrate W. For example, in the processing liquid supplying process, the processing liquid may be supplied to the substrate W in a dried state.

[0297] (6) In the first and second embodiments, the processing liquid supplying step removes the replacement liquid from the substrate W by using the processing liquid. However, this is not limited to this. For example, the processing liquid supplying step may clean the substrate W by using the processing liquid. For example, the processing liquid supplying step may remove foreign matter adhering to the substrate W by using the processing liquid. For example, the processing liquid supplying step may dissolve foreign matter adhering to the substrate W by using the processing liquid. The foreign matter is, for example, resist residue.

[0298] (7) In the first and second embodiments, the solidified film forming process does not supply a gas to the substrate W. However, this is not limited to this. The solidified film forming process may supply a gas to the substrate W. The solidified film forming process may supply a gas to the processing liquid on the substrate W. This allows the solidified film to be efficiently formed on the substrate W in the solidified film forming process.

[0299] (8) In the first embodiment, the sublimable substance supplying section 23 may supply the sublimable substance in a liquid state to the first tank 21. For example, the sublimable substance supplying section 23 may supply the sublimable substance together with a solvent to the first tank 21. Alternatively, the sublimable substance supplying section 23 may supply the sublimable substance in a solid state to the first tank 21. For example, the sublimable substance supplying section 23 may supply a powdered sublimable substance to the first tank 21. The sublimable substance supplying section 23 may include a feeder that sends the solid sublimable substance to the first tank 21. Similarly, in the second embodiment, the first tank 41 may store a sublimable substance in a liquid state, or may store a sublimable substance in a solid state. When the first tank 41 stores a sublimable substance in a solid state, the mixing section 44 may include a feeder that sends the solid sublimable substance from the first tank 41 to the joint 46.

[0300] (9) In the second embodiment, the first tank 41 stores a sublimable material, the second tank 42 stores a solvent, and the third tank 43 stores a surfactant. However, this is not limited to this. For example, any one of the first to third tanks 41-43 may store any two of the sublimable material, the solvent, and the surfactant.

[0301] For example, the first tank 41 may store a solvent in addition to the sublimable material. For example, the first tank 41 may store a surfactant-free liquid. The mixer 44 may add a surfactant stored in the third tank 43 to the sublimable material and the solvent stored in the first tank 41. In this modified embodiment, the second tank 42 may be omitted.

[0302] For example, the first tank 41 may store a surfactant in addition to the sublimable substance. The mixer 44 may add the sublimable substance and the surfactant stored in the first tank 41 to the solvent stored in the second tank 42. In this modified embodiment, the third tank 43 may be omitted.

[0303] For example, the second tank 42 may store a surfactant in addition to the solvent. The mixer 44 may add the sublimable material stored in the first tank 41 to the solvent and surfactant stored in the second tank 42. In this modified embodiment, the third tank 43 may be omitted.

[0304] (10) In the first embodiment, the substrate processing apparatus 1 includes the first sensor 29. However, this is not limited to this. The first sensor 29 may be omitted.

[0305] (11) The first to fourth embodiments and each of the modified embodiments described above in (1) to (10) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment. [Explanation of symbols]

[0306] 1 ... Substrate processing equipment 10 ... Control section 11 … Processing unit 13... Board holding part 14 … Rotation drive unit 15a ... First nozzle (processing liquid supply unit) 15e … 5th nozzle (gas supply section) 16 … Chassis 20 … Processing liquid generation unit 21 … 1st tank 23 … Sublimable substance supply section 25 … Solvent supply section 27 … Surfactant Supply Section 31 ... Liquid delivery section 41 … 1st tank 42 … 2nd tank 43 … 3rd tank 44 … Mixing section F1: First condition F2 : Second condition F3: Third condition F4: Fourth condition LOGPow: Octanol / water partition coefficient of a surfactant H: Processing solution J... gas K: Solidified film L… Substitution liquid Pa … Vapor pressure of a sublimable substance at room temperature Pb: Vapor pressure of the solvent at room temperature Pc: Vapor pressure of the surfactant at room temperature T … Amount of surfactant added (ratio of the volume of surfactant contained in the treatment liquid to the volume of solvent contained in the treatment liquid) W … Substrate W1: Top surface of the board R...Pattern W2 … Convex part A … Recess S1: Processing solution generation process S15: Processing liquid supply process S16 … Solidified film formation process S17 … Sublimation process

Claims

1. A substrate processing method for processing a substrate, comprising the steps of: a treatment liquid supplying step of supplying a treatment liquid containing a sublimable material, a solvent, and a surfactant to the substrate; a solidified film forming step of evaporating the solvent and the surfactant 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 volume of the surfactant contained in the treatment liquid is 0.01% or more and 10% or less of a volume of the solvent contained in the treatment liquid; The surfactant has an octanol / water partition coefficient of -1 or more and 1 or less; The vapor pressure of the surfactant at room temperature is 0.9 times or more and 3 times or less than the vapor pressure of the solvent at room temperature. (However, this does not include the case where the sublimable substance is camphor, the solvent is isopropyl alcohol, and the surfactant is tert-butanol.) A method for processing a substrate.

2. 2. The substrate processing method according to claim 1, The vapor pressure of the solvent at room temperature is higher than the vapor pressure of the sublimable material at room temperature. A method for processing a substrate.

3. 3. The substrate processing method according to claim 1, further comprising the steps of: The vapor pressure of the surfactant at room temperature is higher than the vapor pressure of the sublimable material at room temperature. A method for processing a substrate.

4. 4. A substrate processing method according to claim 1, further comprising the steps of: the sublimable substance is any one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following a1) to a20). a1) The solvent is methanol and the surfactant is acetone. a2) The solvent is ethanol and the surfactant is methanol. a3) The solvent is isopropyl alcohol and the surfactant is methanol. a4) The solvent is isopropyl alcohol and the surfactant is ethanol. a5) The solvent is isopropyl alcohol and the surfactant is tert-butanol. a6) The solvent is tert-butanol, and the surfactant is methanol. a7) The solvent is tert-butanol, and the surfactant is ethanol. a8) The solvent is tert-butanol, and the surfactant is isopropyl alcohol. a9) The solvent is 1-propanol and the surfactant is ethanol. a10) The solvent is 1-propanol and the surfactant is isopropyl alcohol. a11) The solvent is 1-propanol, and the surfactant is tert-butanol. a12) The solvent is isobutanol and the surfactant is 1-propanol. a13) The solvent is 1-ethoxy-2-propanol, and the surfactant is 1-propanol. a14) The solvent is 1-ethoxy-2-propanol, and the surfactant is isobutanol. a15) The solvent is 1-butanol, and the surfactant is 1-propanol. a16) The solvent is 1-butanol and the surfactant is isobutanol. a17) The solvent is 1-butanol, and the surfactant is 1-ethoxy-2-propanol. a18) The solvent is propylene glycol monomethyl ether acetate and the surfactant is isobutanol. a19) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-ethoxy-2-propanol. a20) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-butanol. A method for processing a substrate.

5. 5. A substrate processing method according to claim 1, further comprising the steps of: The substrate has a pattern formed on a surface of the substrate. A method for processing a substrate.

6. A processing liquid used for drying a substrate, comprising: A sublimable material; A solvent; A surfactant, Including, a volume of the surfactant contained in the treatment liquid is 0.01% or more and 10% or less of a volume of the solvent contained in the treatment liquid; The surfactant has an octanol / water partition coefficient of -1 or more and 1 or less; The vapor pressure of the surfactant at room temperature is 0.9 times or more and 3 times or less than the vapor pressure of the solvent at room temperature. (However, this does not include the case where the sublimable substance is camphor, the solvent is isopropyl alcohol, and the surfactant is tert-butanol.) Processing liquid.

7. The treatment liquid according to claim 6, The vapor pressure of the solvent at room temperature is higher than the vapor pressure of the sublimable material at room temperature. Processing liquid.

8. The treatment liquid according to claim 6 or 7, The vapor pressure of the surfactant at room temperature is higher than the vapor pressure of the sublimable material at room temperature. Processing liquid.

9. 9. The treatment liquid according to claim 6, the sublimable substance is any one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following a1) to a20). a1) The solvent is methanol and the surfactant is acetone. a2) The solvent is ethanol and the surfactant is methanol. a3) The solvent is isopropyl alcohol and the surfactant is methanol. a4) The solvent is isopropyl alcohol and the surfactant is ethanol. a5) The solvent is isopropyl alcohol and the surfactant is tert-butanol. a6) The solvent is tert-butanol, and the surfactant is methanol. a7) The solvent is tert-butanol, and the surfactant is ethanol. a8) The solvent is tert-butanol, and the surfactant is isopropyl alcohol. a9) The solvent is 1-propanol and the surfactant is ethanol. a10) The solvent is 1-propanol and the surfactant is isopropyl alcohol. a11) The solvent is 1-propanol, and the surfactant is tert-butanol. a12) The solvent is isobutanol and the surfactant is 1-propanol. a13) The solvent is 1-ethoxy-2-propanol, and the surfactant is 1-propanol. a14) The solvent is 1-ethoxy-2-propanol, and the surfactant is isobutanol. a15) The solvent is 1-butanol, and the surfactant is 1-propanol. a16) The solvent is 1-butanol and the surfactant is isobutanol. a17) The solvent is 1-butanol, and the surfactant is 1-ethoxy-2-propanol. a18) The solvent is propylene glycol monomethyl ether acetate and the surfactant is isobutanol. a19) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-ethoxy-2-propanol. a20) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-butanol. Processing liquid.

10. 9. The treatment liquid according to claim 6, the sublimable substance is at least one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following b1) to b9). b1) The solvent is methanol and the surfactant is acetone. b2) The solvent is ethanol and the surfactant is methanol. b3) The solvent is isopropyl alcohol, and the surfactant is at least one of methanol, ethanol, and tert-butanol. b4) The solvent is tert-butanol, and the surfactant is at least one of methanol, ethanol, and isopropyl alcohol. b5) The solvent is 1-propanol, and the surfactant is at least one of ethanol, isopropyl alcohol, and tert-butanol. b6) The solvent is isobutanol and the surfactant is 1-propanol. b7) The solvent is 1-ethoxy-2-propanol, and the surfactant is at least one of 1-propanol and isobutanol. b8) The solvent is 1-butanol, and the surfactant is at least one of 1-propanol, isobutanol, and 1-ethoxy-2-propanol. b9) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is at least one of isobutanol, 1-ethoxy-2-propanol, and 1-butanol. Processing liquid.

11. 9. The treatment liquid according to claim 6, the sublimable substance is at least one of cyclohexanone oxime, camphor, and ε-caprolactam; The solvent and the surfactant are any one of the following c1) to c9). c1) The solvent is methanol and the surfactant is acetone. c2) The solvent is at least one of ethanol, isopropyl alcohol, and tert-butanol, and the surfactant is methanol. c3) The solvent is at least one of isopropyl alcohol, tert-butanol, and 1-propanol, and the surfactant is ethanol. c4) The solvent is at least one of isopropyl alcohol and 1-propanol, and the surfactant is tert-butanol. c5) The solvent is at least one of tert-butanol and 1-propanol, and the surfactant is isopropyl alcohol. c6) The solvent is at least one of isobutanol, 1-ethoxy-2-propanol, and 1-butanol, and the surfactant is 1-propanol. c7) The solvent is at least one of 1-ethoxy-2-propanol, 1-butanol, and propylene glycol monomethyl ether acetate, and the surfactant is isobutanol. c8) The solvent is at least one of 1-butanol and propylene glycol monomethyl ether acetate, and the surfactant is 1-ethoxy-2-propanol. c9) The solvent is propylene glycol monomethyl ether acetate, and the surfactant is 1-butanol. Processing liquid.

12. 12. The treatment liquid according to claim 6, The volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. Processing liquid.

13. 13. The treatment liquid according to claim 6, The volume of the sublimable substance contained in the treatment liquid is 1% or more and 10% or less of the volume of the solvent contained in the treatment liquid. Processing liquid.

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