Substrate processing method

Abstract

The present invention provides a substrate processing method and a substrate processing apparatus that can properly dry substrates. [Solution] The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method is for processing a substrate. The substrate has a pattern formed on its surface. The substrate processing method comprises a hydrophilization step, a first supply step, a solidification film formation step, and a sublimation step. In the hydrophilization step, hydroxyl groups are formed on the surface of the substrate. In the first supply step, a drying aid is supplied to the substrate having hydroxyl groups. The drying aid contains a sublimable substance and a first solvent. The sublimable substance contains an organic compound containing an oxime group. In the solidification film formation step, the first solvent evaporates from the drying aid on the substrate. In the solidification film formation step, a solidification film is formed on the substrate. The solidification film contains a sublimable substance. In the sublimation step, the solidification film sublimes.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate 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.

Background Art

[0002] Patent Document 1 discloses a substrate processing method for processing a substrate. The substrate has a pattern formed on the surface thereof. The substrate processing method includes a cleaning step, a replacement step, a supply step, a coagulation step, and a sublimation step. In the cleaning step, a cleaning liquid and a rinse liquid are supplied to the substrate. The cleaning liquid is, for example, SC-1. The rinse liquid is, for example, deionized water. In the replacement step, a replacement liquid is supplied to the substrate. The replacement liquid is, for example, isopropyl alcohol. In the supply step, a drying aid liquid is supplied to the substrate. The drying aid liquid contains a sublimable substance. The sublimable substance contains a fluorocarbon compound. The drying aid liquid may further contain an organic solvent. In the coagulation step, the drying aid liquid coagulates on the substrate. In the coagulation step, a coagulation film is formed on the substrate. In the sublimation step, the coagulation film sublimates. In the sublimation step, the coagulation film is removed from the substrate.

[0003] The substrate processing method may further include a hydrophobization step. The hydrophobization step is performed after the replacement step and before the supply step. In the hydrophobization step, a water repellent is supplied to the substrate. In the hydrophobization step, the water repellent adheres to the substrate.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Even with conventional substrate processing methods, it was sometimes impossible to properly dry the substrate. For example, even with conventional substrate processing methods, the patterns formed on the substrate sometimes collapsed. For example, when the patterns were fine, conventional substrate processing methods sometimes could not sufficiently suppress the collapse of the patterns.

[0006] This invention has been made in view of these circumstances, and aims to provide a substrate processing method and a substrate processing apparatus that can properly dry a substrate. [Means for solving the problem]

[0007] To achieve this objective, the present invention has the following configuration. That is, the present invention is a substrate processing method for processing a substrate having a pattern formed on its surface, comprising: a hydrophilization step of forming hydroxyl groups on the surface of the substrate; a first supply step of supplying a drying auxiliary liquid containing a sublimable substance and a first solvent to the substrate having the hydroxyl groups; a solidification film formation step of evaporating the first solvent from the drying auxiliary 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 sublimable substance contains an organic compound containing an oxime group.

[0008] The substrate processing method is for processing a substrate. The substrate has a pattern formed on its surface. The substrate processing method comprises a hydrophilization step, a first supply step, a solidification film formation step, and a sublimation step. In the hydrophilization step, hydroxyl groups are formed on the surface of the substrate. In the first supply step, a drying aid is supplied to the substrate having hydroxyl groups. The drying aid contains a sublimable substance and a first solvent. In the solidification film formation step, the first solvent evaporates from the drying aid on the substrate. In the solidification film formation step, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. In the sublimation step, the solidified film sublimes. The substrate is dried by the sublimation of the solidified film.

[0009] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, in the first supply step, the drying aid is appropriately supplied to the substrate pattern. As a result, in the solidification film formation step, the solidification film is appropriately formed along the substrate pattern. The solidification film provides suitable support for the pattern. The solidification film effectively prevents the pattern from collapsing. With the pattern appropriately protected, the substrate is dried.

[0010] As described above, the substrate is properly dried according to this substrate processing method.

[0011] In the substrate processing method described above, it is preferable that an ammonia hydrogen peroxide mixture is supplied to the substrate in the hydrophilization step. In the hydrophilization step, hydroxyl groups are appropriately formed on the surface of the substrate.

[0012] In the above-described substrate processing method, it is preferable to further include an etching step, in which an etching solution is supplied to the substrate to remove the oxide film on the substrate, prior to the hydrophilization step. The etching step is performed before the hydrophilization step. In the etching step, an etching solution is supplied to the substrate. In the etching step, the oxide film on the substrate is removed. Therefore, in the hydrophilization step, hydroxyl groups are formed more appropriately on the surface of the substrate.

[0013] In the substrate processing method described above, it is preferable to further include a first rinsing step in which a first rinsing solution is supplied to the substrate after the etching step and before the hydrophilization step. The first rinsing step is performed after the etching step and before the hydrophilization step. In the first rinsing step, the first rinsing solution is supplied to the substrate. Therefore, in the first rinsing step, the etching solution is suitably removed from the substrate. Thus, in the hydrophilization step, hydroxyl groups are formed more appropriately on the surface of the substrate.

[0014] In the substrate processing method described above, it is preferable to further include a second rinsing step in which a second rinsing liquid is supplied to the substrate after the hydrophilization step and before the first supply step. The second rinsing step is performed after the hydrophilization step and before the first supply step. In the second rinsing step, the second rinsing liquid is supplied to the substrate. As a result, the substrate is properly cleaned in the second rinsing step. Therefore, in the first supply step, the drying aid liquid is supplied more appropriately to the patterns on the substrate.

[0015] In the substrate processing method described above, it is preferable to include a first replacement step in which a first replacement liquid is supplied to the substrate after the second rinsing step and before the first supply step. The first replacement step is performed after the second rinsing step and before the first supply step. In the first replacement step, the first replacement liquid is supplied to the substrate. As a result, the second rinsing liquid is removed from the substrate. Therefore, in the first supply step, the drying aid liquid is appropriately supplied to the patterns on the substrate.

[0016] In the substrate processing method described above, it is preferable that the substrate be cooled during the solidification film formation step. Therefore, the formation of the solidification film is further promoted during the solidification film formation step. As a result, the solidification film is formed more favorably along the pattern. Consequently, the substrate is dried more appropriately.

[0017] Furthermore, the present invention relates to a substrate processing method for processing a substrate having a pattern formed on its surface, comprising: a hydrophobicization step of attaching a water-repellent agent to the surface of the substrate; a second supply step of supplying a drying aid liquid containing a sublimable substance and a first solvent to the substrate to which the water-repellent agent has been attached; a solidification film formation step of evaporating the first solvent from the drying aid 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 sublimable substance contains an organic compound containing an oxime group.

[0018] The substrate processing method is for processing a substrate. The substrate has a pattern formed on its surface. The substrate processing method comprises a hydrophobicization step, a second supply step, a solidification film formation step, and a sublimation step. In the hydrophobicization step, a water-repellent agent is applied to the surface of the substrate. In the second supply step, a drying aid liquid is supplied to the substrate to which the water-repellent agent has been applied. The drying aid liquid contains a sublimable substance and a first solvent. In the solidification film formation step, the first solvent evaporates from the drying aid liquid on the substrate. In the solidification film formation step, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. In the sublimation step, the solidified film sublimes. The substrate is dried by the sublimation of the solidified film.

[0019] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, in the second supply step, the drying aid is appropriately supplied to the substrate pattern. As a result, in the solidification film formation step, the solidification film is appropriately formed along the substrate pattern. The solidification film provides suitable support for the pattern. The solidification film effectively prevents the pattern from collapsing. With the pattern appropriately protected, the substrate is dried.

[0020] As described above, the substrate is properly dried according to this substrate processing method.

[0021] In the substrate processing method described above, it is preferable that a mixed solution containing the water-repellent agent and the second solvent is supplied to the substrate in the hydrophobicization step. In the hydrophobicization step, the water-repellent agent contained in the mixed solution is suitably supplied to the substrate. Therefore, in the hydrophobicization step, the water-repellent agent contained in the mixed solution adheres suitably to the substrate.

[0022] In the substrate processing method described above, it is preferable to further include a hydrophilization step, which forms hydroxyl groups on the surface of the substrate, before the hydrophobicization step. The hydrophilization step is performed before the hydrophobicization step. In the hydrophilization step, hydroxyl groups are formed on the surface of the substrate. Therefore, in the hydrophobicization step, the surface of the substrate has hydroxyl groups. Thus, in the hydrophobicization step, the water repellent adheres more favorably to the surface of the substrate.

[0023] In the above-described substrate processing method, it is preferable to further include an etching step of supplying an etching solution to the substrate and removing the oxide film on the substrate before the hydrophilic treatment step. The etching step is executed before the hydrophilic treatment step. In the etching step, the etching solution is supplied to the substrate. In the etching step, the oxide film on the substrate is removed. Therefore, in the hydrophilic treatment step, hydroxy groups are appropriately formed on the surface of the substrate.

[0024] In the above-described substrate processing method, it is preferable to further include a first rinsing step of supplying a first rinsing solution to the substrate after the etching step and before the hydrophilic treatment step. The first rinsing step is executed after the etching step and before the hydrophilic treatment step. In the first rinsing step, the first rinsing solution is supplied to the substrate. Therefore, in the first rinsing step, the etching solution is preferably removed from the substrate. Therefore, in the hydrophilic treatment step, hydroxy groups are more appropriately formed on the surface of the substrate.

[0025] In the above-described substrate processing method, it is preferable to further include a second rinsing step of supplying a second rinsing solution to the substrate after the hydrophilic treatment step and before the hydrophobic treatment step. The second rinsing step is executed after the hydrophilic treatment step and before the hydrophobic treatment step. In the second rinsing step, the second rinsing solution is supplied to the substrate. Therefore, in the second rinsing step, the substrate is appropriately cleaned. Therefore, in the hydrophobic treatment step, the water repellent adheres to the substrate more preferably.

[0026] In the above-described substrate processing method, it is preferable to further include a second substitution step of supplying a second substitution solution to the substrate after the second rinsing step and before the hydrophobic treatment step. The second substitution step is executed after the second rinsing step and before the hydrophobic treatment step. In the second substitution step, the second substitution solution is supplied to the substrate. Therefore, in the second substitution step, the second rinsing solution is removed from the substrate. Therefore, in the hydrophobic treatment step, the water repellent adheres to the substrate more preferably.

[0027] In the above-described substrate processing method, it is preferable to further include a third replacement step of supplying a third replacement liquid to the substrate after the hydrophobization step and before the second supply step. The third replacement step is performed after the hydrophobization step and before the second supply step. In the third replacement step, the third replacement liquid is supplied to the substrate. Therefore, in the third replacement step, the substrate is appropriately cleaned. Thus, in the second supply step, the drying aid liquid is appropriately supplied to the pattern of the substrate.

[0028] In the above-described substrate processing method, it is preferable that the sublimable substance does not contain a fluorocarbon compound. In the first supply step, the drying aid liquid is more appropriately supplied to the pattern of the substrate. Also in the second supply step, the drying aid liquid is more appropriately supplied to the pattern of the substrate.

[0029] In the above-described substrate processing method, it is preferable that the sublimable substance contains at least one of cyclohexanone oxime and pinacolin oxime. In the first supply step, the drying aid liquid is more appropriately supplied to the pattern of the substrate. Also in the second supply step, the drying aid liquid is more appropriately supplied to the pattern of the substrate.

[0030] The present invention is a substrate processing apparatus including a substrate holding unit that holds a substrate, a hydrophilization unit that forms a hydroxy group on the surface of the substrate held by the substrate holding unit, and a first supply unit that supplies a drying aid liquid containing a sublimable substance and a first solvent to the substrate held by the substrate holding unit, wherein the sublimable substance includes an organic compound containing an oxime group.

[0031] The substrate processing apparatus comprises a substrate holding unit, a hydrophilization unit, and a first supply unit. The substrate holding unit holds the substrate. The hydrophilization unit forms hydroxyl groups on the substrate held by the substrate holding unit. The first supply unit supplies a drying aid liquid to the substrate held by the substrate holding unit. The drying aid liquid contains a sublimable substance and a first solvent. Therefore, when the first supply unit supplies the drying aid liquid to the substrate, the first solvent evaporates from the drying aid liquid on the substrate. A solidified film is formed on the substrate by the evaporation of the first solvent. The solidified film contains a sublimable substance. Therefore, the solidified film sublimes. The substrate is dried by the sublimation of the solidified film.

[0032] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, the drying aid is appropriately supplied to the pattern on the substrate. As a result, a solidified film is appropriately formed along the pattern on the substrate. The solidified film provides suitable support for the pattern. The solidified film effectively prevents the pattern from collapsing. With the pattern appropriately protected, the substrate is dried.

[0033] As described above, the substrate is properly dried using this substrate processing apparatus.

[0034] In the above-described substrate processing apparatus, it is preferable to include a cooling unit for cooling the substrate. Therefore, the substrate is suitably cooled. Consequently, the substrate is processed more appropriately.

[0035] The present invention relates to a substrate processing apparatus comprising: a substrate holding unit for holding a substrate; a hydrophobic unit for attaching a water-repellent agent to the surface of the substrate held by the substrate holding unit; and a first supply unit for supplying a drying aid liquid containing a sublimable substance and a first solvent to the substrate held by the substrate holding unit, wherein the sublimable substance contains an organic compound containing an oxime group.

[0036] The substrate processing apparatus comprises a substrate holding unit, a hydrophobicization unit, and a first supply unit. The substrate holding unit holds the substrate. The hydrophobicization unit applies a water-repellent agent to the surface of the substrate held by the substrate holding unit. The first supply unit supplies a drying aid liquid to the substrate held by the substrate holding unit. The drying aid liquid contains a sublimable substance and a first solvent. Therefore, when the first supply unit supplies the drying aid liquid to the substrate, the first solvent evaporates from the drying aid liquid on the substrate. Due to the evaporation of the first solvent, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. Therefore, the solidified film sublimes. Due to the sublimation of the solidified film, the substrate is dried.

[0037] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, the drying aid is appropriately supplied to the pattern on the substrate. As a result, a solidified film is appropriately formed along the pattern on the substrate. The solidified film provides suitable support for the pattern. The solidified film effectively prevents the pattern from collapsing. With the pattern appropriately protected, the substrate is dried.

[0038] As described above, the substrate is properly dried using this substrate processing apparatus. [Effects of the Invention]

[0039] According to the substrate processing method and substrate processing apparatus of the present invention, the substrate is properly dried. [Brief explanation of the drawing]

[0040] [Figure 1] This is a schematic diagram showing a portion of the circuit board. [Figure 2] This is a plan view showing the inside of the substrate processing apparatus of the first embodiment. [Figure 3] This is a control block diagram of a substrate processing unit. [Figure 4] This diagram shows the configuration of the processing unit and the first supply source. [Figure 5] This is a flowchart showing the procedure for the substrate processing method of the first embodiment. [Figure 6] This diagram schematically shows the substrate in the first supply process. [Figure 7] This diagram schematically shows the substrate during the solidification film formation process. [Figure 8] This diagram schematically shows the substrate during the solidification film formation process. [Figure 9] This diagram schematically shows the substrate during the sublimation process. [Figure 10] This diagram schematically shows the substrate during the sublimation process. [Figure 11] This is a diagram illustrating the pattern protection mechanism. [Figure 12] This is a diagram illustrating the mechanism of pattern collapse. [Figure 13] This figure shows the configuration of the processing unit and the first supply source according to the second embodiment. [Figure 14] This is a flowchart showing the procedure for the substrate processing method of the second embodiment. [Figure 15] This figure shows the configuration of the processing unit and the first supply source in a modified embodiment. [Figure 16] This figure shows the configuration of the processing unit in a modified embodiment. [Figure 17] This figure schematically shows the substrate during the solidification film formation process of a modified embodiment. [Figure 18] This figure schematically shows the substrate during the solidification film formation process of a modified embodiment. [Modes for carrying out the invention]

[0041] The substrate processing method and substrate processing apparatus of the present invention will be described below with reference to the drawings.

[0042] <1. First Embodiment> <1-1. Circuit board> The substrate W is, for example, a semiconductor wafer, a substrate for liquid crystal displays, an organic electroluminescence (EL) substrate, a flat panel display (FPD) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, or a solar cell substrate. The substrate W has a thin, flat shape. The substrate W has a roughly circular shape in plan view.

[0043] Figure 1 is a schematic diagram showing a part of the substrate W. The substrate W has a surface WS. The surface WS includes a pattern WP. The pattern WP is formed on the surface WS.

[0044] For example, surface WS includes a first surface WS1. Although not shown in the illustration, surface WS further includes a second surface and a peripheral edge. The second surface is located on the opposite side of the first surface. The peripheral edge is located between the periphery of the first surface and the periphery of the second surface. The pattern WP is formed on the first surface WS1. The first surface WS1 is also called the pattern-forming surface.

[0045] The pattern WP has, for example, an uneven shape. The pattern WP is, for example, at least one of a line and space pattern, a hole pattern, and a dot pattern.

[0046] The pattern WP has, for example, multiple protrusions T. The protrusions T are part of the substrate W. The protrusions T are structural. The protrusions T have, for example, a column shape, a dot shape, a line shape, or a wall shape. The protrusions T project, for example, upward from the substrate W. The multiple protrusions T are, for example, arranged horizontally to one another.

[0047] A pattern WP has, for example, a plurality of recesses A. Recesses A are spaces. Recesses A are, for example, at least one of trenches, voids, pores, and holes. Holes are also called through holes or via holes. Recesses A are, for example, recessed downwards. Recesses A are, for example, open upwards.

[0048] The recess A is defined by at least one or more protrusions T. The recess A is in contact with at least one or more protrusions T. The recess A is located laterally to the protrusions T. For example, the recess A is located between two adjacent protrusions T. The two adjacent protrusions T are separated by the recess A.

[0049] More specifically, each convex portion T has a side T1. Side T1 is also called the side surface. Side T1 is in contact with the concave portion A.

[0050] The surface WS is composed of, for example, at least one of a silicon-containing film and a metal film. The protrusion T is also composed of, for example, at least one of a silicon-containing film and a metal film. The silicon-containing film includes, for example, at least one of single-crystal silicon films, polysilicon films, amorphous silicon films, SiO2 films, SiN films, BSG films, and TEOS films. Here, the BSG film is a boron-containing SiO2 film. The TEOS film is a SiO2 film formed by CVD using tetraethoxysilane (TEOS). The metal film includes, for example, at least one of Ti (titanium), W (tungsten), Cu (copper), and Al (aluminum). The metal film includes, for example, either a TiN film or a W film. The SiO2 film, BSG film, and TEOS film may be classified as oxide films. The SiN film and TiN film may be classified as nitride films.

[0051] For example, the protrusion T is composed of a single film. Alternatively, the protrusion T is composed of multiple films. These multiple films may be stacked on top of each other, for example.

[0052] <1-2. Overview of Substrate Processing Equipment> Figure 2 is a plan view showing the interior of the substrate processing apparatus 1 of the first embodiment. The substrate processing apparatus 1 processes the substrate W. The processing in the substrate processing apparatus 1 includes a drying process.

[0053] The substrate processing apparatus 1 comprises 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 the substrate W to the processing block 7. The processing block 7 performs processing on the substrate W. The indexer unit 3 retrieves the substrate W from the processing block 7.

[0054] In this specification, for convenience, the direction in which the indexer unit 3 and the processing block 7 are aligned is called the "front-to-back direction X". The front-to-back direction X is horizontal. Of the front-to-back direction X, the direction from the processing block 7 toward the indexer unit 3 is called "forward". The direction opposite to forward is called "backward". The horizontal direction perpendicular to the front-to-back direction X is called the "width direction Y". One direction of the "width direction Y" is appropriately called "right". The direction opposite to right is called "left". The direction perpendicular to the horizontal is called the "vertical direction Z". In each figure, front, back, right, left, up, and down are shown as appropriate for reference.

[0055] The indexer unit 3 comprises a plurality (for example, four) of carrier mounting units 4. Each carrier mounting unit 4 mounts one carrier C. The carrier C accommodates multiple substrates W. The carrier C is, for example, a FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), or OC (Open Cassette).

[0056] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is located behind the carrier mounting unit 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 has access to the carrier C which is placed on the carrier mounting 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 forward / backward 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 can transfer the substrate W to each other. The transport mechanism 8 includes a hand 8a and a hand drive unit 8b. The hand 8a supports the substrate W. The hand drive unit 8b is connected to the hand 8a. The hand drive unit 8b moves the hand 8a. The hand drive unit 8b moves the hand 8a, for example, in the forward / backward direction X, the width direction Y, and the vertical direction Z. The hand drive unit 8b rotates the hand 8a, for example, in a horizontal plane.

[0058] The processing block 7 comprises a plurality of processing units 11. Each processing unit 11 is positioned to the side of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

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

[0060] The transport mechanism 8 can access each processing unit 11. The transport mechanism 8 can transfer the substrate W to the substrate holding unit 13. The transport mechanism 8 can take the substrate W from the substrate holding unit 13.

[0061] Figure 3 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 can communicate with the transport mechanisms 5 and 8 and the processing unit 11. The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11.

[0062] The control unit 10 is implemented by a central processing unit (CPU) that executes various processes, RAM (Random-Access Memory) which serves as a workspace for calculations, and a storage medium such as a fixed disk. The control unit 10 has various types of information that are pre-stored in the storage medium. For example, the information held by the control unit 10 is transport condition information for controlling the transport mechanisms 5 and 8. For example, the information held by the control unit 10 is processing condition information for controlling the processing unit 11. Processing condition information is also called a processing recipe.

[0063] A brief explanation of the operation of the substrate processing device 1 will be given.

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

[0065] The transport mechanism 8 distributes the substrates W to the processing units 11. Specifically, the transport mechanism 8 transports the substrates W from the transport mechanism 5 to the substrate holding section 13 of each processing unit 11.

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

[0067] After the processing unit 11 has processed the substrate W, the transport mechanism 8 collects the substrate W from each processing unit 11. Specifically, the transport mechanism 8 takes the substrate W from each substrate holding unit 13. Then, the transport mechanism 8 passes the substrate W 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] <1-3. Configuration of Processing Unit 11> Figure 4 shows the configuration of the processing unit 11. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer type. That is, each processing unit 11 processes only one substrate W at a time.

[0070] The processing unit 11 includes a housing 12. The housing 12 has a roughly box-like shape. The substrate W is processed inside the housing 12.

[0071] The inside of the enclosure 12 is kept at room temperature. Therefore, the substrate W is processed in a room temperature environment. Here, room temperature includes ambient temperature. Room temperature is, for example, a temperature in the range of 5°C or higher and 35°C or lower. Room temperature is, for example, a temperature in the range of 10°C or higher and 30°C or lower. Room temperature is, for example, a temperature in the range of 20°C or higher and 25°C or lower.

[0072] The inside of the housing 12 is maintained at atmospheric pressure. Therefore, the substrate W is processed under an environment of atmospheric pressure. Here, atmospheric pressure includes standard atmospheric pressure (1 atmosphere, 101325 Pa). Atmospheric pressure is, for example, within the range of 0.7 atmospheres or more and 1.3 atmospheres or less. In this specification, pressure values ​​are given as absolute pressure relative to absolute vacuum.

[0073] The aforementioned substrate holder 13 is installed inside the housing 12. The substrate holder 13 holds one substrate W. The substrate holder 13 holds the substrate W in a substantially horizontal position.

[0074] The substrate holder 13 is located below the substrate W that it holds. The substrate holder 13 is in contact with at least one of the lower surface of the substrate W and the peripheral edge of the substrate W. The substrate holder 13 is not in contact with the upper surface of the substrate W.

[0075] The processing unit 11 includes a rotary drive unit 14. At least a portion of the rotary drive unit 14 is installed inside the housing 12. The rotary drive unit 14 is connected to the substrate holder 13. The rotary drive unit 14 rotates the substrate holder 13. The substrate W held by the substrate holder 13 rotates together with the substrate holder 13. The substrate W held by the substrate holder 13 rotates around the axis of rotation B. The axis of rotation B passes through the center of the substrate W and extends vertically in the direction Z.

[0076] The processing unit 11 includes a supply unit 15. The supply unit 15 supplies liquid or gas to the substrate W held by the substrate holding unit 13. Specifically, the supply unit 15 supplies liquid or gas to the upper surface of the substrate W held by the substrate holding unit 13.

[0077] The supply unit 15 comprises a first supply unit 15a, a second supply unit 15b, a third supply unit 15c, a fourth supply unit 15d, a fifth supply unit 15e, and a sixth supply unit 15f. The first supply unit 15a supplies drying auxiliary liquid g. The second supply unit 15b supplies etching solution. The third supply unit 15c supplies hydrophilic agent. The fourth supply unit 15d supplies rinsing solution. The fifth supply unit 15e supplies displacement solution. The sixth supply unit 15f supplies drying gas.

[0078] The liquids and gases supplied by the supply unit 15 will be described.

[0079] The drying aid liquid g supplied by the first supply unit 15a is used to dry the substrate W. The drying aid liquid g has the function of assisting in the drying of the substrate W.

[0080] The drying aid liquid g contains a sublimable substance. The sublimable substance has sublimation properties. "Sublimation" refers to the property of an element, compound, or mixture to undergo a phase transition from solid to gas, or from gas to solid, without passing through a liquid phase.

[0081] Sublimable substances include organic compounds containing an oxime group. An oxime group is also called a "C=N-OH group." Organic compounds containing an oxime group are also called oximes.

[0082] Sublimable substances include, for example, cyclohexanone oxime. Cyclohexanone oxime is represented by the following chemical formula (1). As shown in chemical formula (1), cyclohexanone oxime is an example of an organic compound containing an oxime group.

[0083] [ka]

[0084] Sublimable substances include, for example, pinacolin oxime. Sublimable substances include, for example, at least one of cyclohexanone oxime and pinacolin oxime. Pinacoline oxime is also an example of an organic compound containing an oxime group.

[0085] Sublimable substances do not contain carbon fluoride compounds. Cyclohexanone oxime is not a carbon fluoride compound. Pinacoline oxime is also not a carbon fluoride compound.

[0086] The drying aid solution g contains a first solvent. The first solvent is soluble in sublimable substances. The sublimable substance in the drying aid solution g is dissolved in the first solvent. That is, the drying aid solution g contains the first solvent and the sublimable substance dissolved in the first solvent. The sublimable substance corresponds to the solute in the drying aid solution g.

[0087] For example, the vapor pressure of the first solvent is preferably higher than the vapor pressure of the sublimable substance.

[0088] The first solvent is, for example, an organic solvent. The first solvent is, for example, an alcohol. The first solvent is, for example, isopropyl alcohol (IPA). Hereafter, isopropyl alcohol will be referred to as "IPA".

[0089] The drying aid g preferably does not contain water. The drying aid g consists, for example, only a sublimable substance and the first solvent. The drying aid g consists, for example, only cyclohexanone oxime and IPA. The drying aid g consists, for example, only pinacolin oxime and IPA.

[0090] The drying aid solution g is, for example, a mixture of a sublimable substance and a first solvent. The drying aid solution g is obtained, for example, by mixing a sublimable substance and a first solvent.

[0091] The initial amount Qb of the first solvent in the drying aid g is preferably greater than the initial amount Qa of the sublimable substance in the drying aid g. The initial amount Qa corresponds, for example, to the amount of sublimable substance used to produce the drying aid g. The initial amount Qb corresponds to the amount of the first solvent used to produce the drying aid g. The units of the initial amounts Qa and Qb are, for example, volume. The ratio of the initial amount Qa to the initial amount Qb is called the "mixing ratio R".

[0092] The etching solution supplied by the second supply unit 15b includes, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0093] The hydrophilic agent supplied by the third supply unit 15c forms hydroxyl groups on the surface WS. Hydroxyl groups are also called "-OH groups".

[0094] The hydrophilic agent is, for example, an ammonia hydrogen peroxide mixture. Hereafter, the ammonia hydrogen peroxide mixture will be referred to as "APM" as appropriate. APM is a liquid. APM is also called "SC-1".

[0095] The third supply section 15c is an example of a hydrophilic section in the present invention.

[0096] The rinse solution supplied by the fourth supply unit 15d contains water. The rinse solution is, for example, deionized water (DIW). The rinse solution consists of, for example, only deionized water (DIW).

[0097] The displacement fluid supplied by the fifth supply unit 15e is soluble in the rinse fluid and drying aid fluid g. The displacement fluid is compatible with the rinse fluid and drying aid fluid g.

[0098] The displacement solution includes, for example, an organic solvent. The displacement solution includes, for example, IPA.

[0099] The displacement solution preferably does not contain water. The displacement solution consists of, for example, only an organic solvent. The displacement solution consists of, for example, only IPA.

[0100] The dry gas supplied by the sixth supply unit 15f preferably has a dew point lower than room temperature. The dry gas is, for example, at least one of air and an inert gas. Air is, for example, compressed air. The inert gas is, for example, nitrogen gas.

[0101] The configuration of the supply unit 15 will be explained.

[0102] The first supply unit 15a is equipped with a nozzle 16a. Similarly, the second to sixth supply units 15b-15f are each equipped with nozzles 16b-16f. Nozzles 16a-16f are each installed inside the housing 12. Nozzle 16a discharges drying aid liquid g. Nozzle 16b discharges etching solution. Nozzle 16c discharges hydrophilic agent. Nozzle 16d discharges rinsing solution. Nozzle 16e discharges displacement solution. Nozzle 16f discharges drying gas.

[0103] The first supply unit 15a comprises a pipe 17a and a valve 18a. The pipe 17a is connected to a nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is open, the nozzle 16a discharges the drying aid liquid g. When the valve 18a is closed, the nozzle 16a does not discharge the drying aid liquid g. Similarly, the second to sixth supply units 15b-15f each comprise a pipe 17b-17f and a valve 18b-18f. The pipes 17b-17f are each connected to nozzles 16b-16f. The valves 18b-18f are each provided on the pipes 17b-17f. The valves 18b-18f control the discharge of etching solution, hydrophilic agent, rinse solution, displacement solution, and drying gas, respectively.

[0104] At least a portion of the piping 17a may be provided outside the housing 12. Piping 17b-17f may be arranged in the same manner as piping 17a. Valve 18a may be provided outside the housing 12. Valves 18b-18f may be arranged in the same manner as valve 18a.

[0105] The substrate processing apparatus 1 includes a first supply source 19a. The first supply source 19a communicates with the first supply unit 15a. The first supply source 19a is connected to the first supply unit 15a. The first supply source 19a is connected to, for example, piping 17a. The first supply source 19a is provided outside the housing 12. The first supply source 19a supplies drying aid liquid g to the first supply unit 15a. Similarly, the second to sixth supply units 15b-15f each communicate with the second to sixth supply sources 19b-19f. The second to sixth supply units 15b-15f each connect to the second to sixth supply sources 19b-19f. The second to sixth supply sources 19b-19f each connect to, for example, piping 17b-17f. The second to sixth supply sources 19b-19f each are provided outside the housing 12. The second supply source 19b supplies etching solution to the second supply unit 15b. The third supply source 19c supplies hydrophilic agent to the third supply unit 15c. The fourth supply source 19d supplies rinsing solution to the third supply unit 15c. The fifth supply source 19e supplies displacement solution to the fourth supply unit 15d. The sixth supply source 19f supplies drying gas to the fifth supply unit 15e.

[0106] The first supply source 19a may supply the drying aid liquid g to multiple processing units 11. Alternatively, the first supply source 19a may supply the drying aid liquid g to only one processing unit 11. The same applies to the second to sixth supply sources 19b-19f.

[0107] The second supply source 19b may be an element of the substrate processing apparatus 1. For example, the second supply source 19b may be a storage tank provided by the substrate processing apparatus 1. Alternatively, the second supply source 19b may not be an element of the substrate processing apparatus 1. For example, the second supply source 19b may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the third to sixth supply sources 19c-19f may each be an element of the substrate processing apparatus 1. Alternatively, the third to sixth supply sources 19c-19f may each not be an element of the substrate processing apparatus 1.

[0108] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12. The cup is positioned around the substrate holder 13. The cup catches any liquid splashed from the substrate W held by the substrate holder 13.

[0109] Refer to Figure 3. The control unit 10 controls the rotary drive unit 14. The control unit 10 controls the supply unit 15. The control unit 10 controls the first to sixth supply units 15a-15f. The control unit 10 controls the valves 18a-18f.

[0110] <1-4. Composition of the first supply source 19a> Refer to Figure 4. The first supply source 19a further generates a drying aid liquid g. An example configuration of the first supply source 19a is shown.

[0111] The first supply source 19a comprises a generation unit 21 and a pumping unit 31. The generation unit 21 generates a drying auxiliary liquid g. The pumping unit 31 sends the drying auxiliary liquid g to the first supply unit 15a.

[0112] The generation unit 21 comprises a tank 22 and supply units 23a and 23b. Supply unit 23a supplies the sublimable substance to the tank 22. Supply unit 23b supplies the first solvent to the tank 22. The sublimable substance and the first solvent are mixed in the tank 22. The sublimable substance and the first solvent become drying aid liquid g in the tank 22.

[0113] Tank 22 is installed under normal temperature conditions. Tank 22 is installed under normal pressure conditions. Therefore, the drying aid liquid g is produced under normal temperature conditions. The drying aid liquid g is produced under normal pressure conditions.

[0114] Furthermore, the generation unit 21 stores the drying aid liquid g. Specifically, the drying aid liquid g is stored in the tank 22. The drying aid liquid g is stored under normal temperature conditions. The drying aid liquid g is stored under normal pressure conditions.

[0115] The supply unit 23a comprises, for example, piping 24a and a valve 25a. Piping 24a communicates with the tank 22. Piping 24a is connected to the tank 22. Valve 25a is provided on piping 24a. When valve 25a is open, the supply unit 23a supplies sublimable material to the tank 22. When valve 25a is closed, the supply unit 23a does not supply sublimable material to the tank 22. Similarly, the supply unit 23b comprises piping 24b and a valve 25b. Piping 24b communicates with the tank 22. Piping 24b is connected to the tank 22. Valve 25b is provided on piping 24b. Valve 25b controls the supply of the first solvent to the tank 22.

[0116] Furthermore, valve 25a adjusts the amount of sublimable substance supplied to tank 22. Valve 25b adjusts the amount of first solvent supplied to tank 22. The amount of sublimable substance supplied to tank 22 corresponds to the initial amount Qa. The amount of first solvent supplied to tank 22 corresponds to the initial amount Qb. Therefore, valves 25a and 25b adjust the mixing ratio R of the drying aid liquid g.

[0117] Valves 25a and 25b may each include, for example, a flow control valve. Valves 25a and 25b may each include, for example, a flow control valve and an on / off valve.

[0118] The supply unit 23a communicates with the supply source 26a. The supply unit 23a is connected to the supply source 26a. For example, the supply source 26a is connected to the piping 24a. The supply source 26a delivers a sublimable substance to the supply unit 23a. Similarly, the supply unit 23b communicates with the supply source 26b. The supply unit 23b is connected to the supply source 26b. For example, the supply source 26b is connected to the piping 24b. The supply source 26b delivers the first solvent to the supply unit 23b. The supply sources 26a and 26b may each be elements of the substrate processing apparatus 1. Alternatively, the supply sources 26a and 26b may each not be elements of the substrate processing apparatus 1.

[0119] The pumping unit 31 communicates with the generating unit 21. Specifically, the pumping unit 31 includes a pipe 32 and a fitting 33. The pipe 32 communicates with the tank 22. The pipe 32 is connected to the tank 22. The fitting 33 is connected to the pipe 32.

[0120] The pumping unit 31 is further connected to the first supply unit 15a. Specifically, the fitting 33 is connected to the first supply unit 15a. The fitting 33 is connected to, for example, the piping 17a.

[0121] The tank 22 is connected to the first supply unit 15a via piping 32 and fittings 33. The tank 22 communicates with the first supply unit 15a. The tank 22 communicates with the nozzle 16a.

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

[0123] Refer to Figure 3. The control unit 10 can communicate with the first supply source 19a. The control unit 10 controls the first supply source 19a. The control unit 10 controls the generation unit 21. The control unit 10 controls the supply units 23a and 23b. The control unit 10 controls the valves 25a and 25b. The control unit 10 controls the pressure supply unit 31. The control unit 10 controls the pump 34.

[0124] The control unit 10 has production condition information for controlling the production unit 21. The production condition information includes, for example, targets for initial amounts Qa and Qb. The production condition information also includes, for example, targets for the mixing ratio R. The production condition information is pre-stored in the storage medium of the control unit 10.

[0125] <1-5. Example of operation of the first supply source 19a and processing unit 11> Figure 5 is a flowchart showing the procedure of the substrate processing method according to the first embodiment. The substrate processing method is for processing a substrate W. As described above, the substrate W has a pattern WP formed on its surface WS. The substrate processing method comprises steps S1 and S10-S19. Steps S10-S19 are performed in parallel with step S1. Steps S10-S19 are performed in this order.

[0126] Step S1 is performed by the first supply source 19a. Steps S10-S19 are substantially performed by the processing unit 11. The first supply source 19a and the processing unit 11 operate according to the control of the control unit 10.

[0127] Refer to Figure 4 as appropriate to explain each step S1, S10-S19.

[0128] Step S1: Production process During the production process, drying aid liquid g is generated.

[0129] The control unit 10 controls the generation unit 21 based on the generation condition information. The generation unit 21 generates the drying auxiliary liquid g. For example, the control unit 10 controls the supply units 23a and 23b based on targets for initial amounts Qa and Qb. For example, the control unit 10 controls the supply units 23a and 23b based on targets for the mixing ratio R. The supply unit 23a supplies the sublimable substance to the tank 22. The supply unit 23b supplies the first solvent to the tank 22. The drying auxiliary liquid g is generated in the tank 22. The drying auxiliary liquid g is stored in the tank 22.

[0130] Step S10: Rotation start process The substrate holder 13 holds the substrate W. The substrate W is held in a substantially horizontal position.

[0131] When the substrate W is held by the substrate holder 13, the first surface WS1 of the substrate W faces upward. When the substrate W is held by the substrate holder 13, the first surface WS1 of the substrate W is located on the top surface of the substrate W. When the substrate W is held by the substrate holder 13, the pattern WP faces upward. When the substrate W is held by the substrate holder 13, the pattern WP is located on the top surface of the substrate W.

[0132] The rotary drive unit 14 rotates the substrate holding unit 13. As a result, the substrate W held by the substrate holding unit 13 begins to rotate.

[0133] In steps S11-S18 described later, the substrate W continues to rotate, for example.

[0134] Step S11: Etching process In the etching process, an etching solution is supplied to the substrate W. In the etching process, the oxide film on the substrate W is removed.

[0135] The second supply unit 15b supplies etching solution to the substrate W held by the substrate holding unit 13. Specifically, the valve 18b opens. The nozzle 16b discharges the etching solution. The etching solution is supplied to the surface WS (specifically, the first surface WS1). The etching solution comes into contact with the surface WS (specifically, the first surface WS1). That is, the etching solution comes into contact with the pattern WP.

[0136] In the following explanation, "surface WS" specifically refers to the first surface WS1. In other words, in the following explanation, "surface WS" is synonymous with "surface WS (specifically the first surface WS1)."

[0137] The etching solution etches the substrate W. The etching solution etches the oxide film on the substrate W. The etching solution etches the oxide film located on the surface WS. The oxide film on the substrate W is removed. The oxide film on the substrate W is removed from the substrate W.

[0138] Subsequently, the second supply unit 15b stops supplying etching solution to the substrate W. Specifically, valve 18b closes, and nozzle 16b stops discharging the etching solution.

[0139] Step S12: First rinsing process Following the etching process, a first rinsing process is performed. In the first rinsing process, a rinsing solution is supplied to the substrate W. In this specification, the rinsing solution supplied to the substrate W in the first rinsing process is referred to as the "first rinsing solution".

[0140] The fourth supply unit 15d supplies the first rinsing liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18d opens. The nozzle 16d discharges the first rinsing liquid. The first rinsing liquid is supplied to the surface WS.

[0141] The first rinse solution cleans the substrate W. Specifically, the first rinse solution removes the etching solution from the substrate W. The etching solution on the substrate W is removed from the substrate W. The etching solution on the substrate W is replaced by the first rinse solution. The first rinse solution comes into contact with the surface WS.

[0142] Subsequently, the fourth supply unit 15d stops supplying the first rinsing liquid to the substrate W. Specifically, the valve 18d closes. The nozzle 16d stops discharging the first rinsing liquid.

[0143] Step S13: Hydrophilization process After the first rinsing step, a hydrophilization step is performed. In the hydrophilization step, a hydrophilic agent is supplied to the substrate W. In the hydrophilization step, for example, APM is supplied to the substrate W. In the hydrophilization step, hydroxyl groups are formed on the surface WS.

[0144] The third supply unit 15c supplies a hydrophilic agent to the substrate W held by the substrate holding unit 13. Specifically, the valve 18c opens. The nozzle 16c discharges the hydrophilic agent. The hydrophilic agent is supplied to the surface WS.

[0145] The hydrophilic agent removes the first rinse solution from the substrate W. The first rinse solution on the substrate W is removed from the substrate W. The first rinse solution on the substrate W is replaced by the hydrophilic agent. The hydrophilic agent comes into contact with the surface WS.

[0146] Hydrophilic agents form hydroxyl groups on the surface WS. Specifically, the hydroxyl groups terminate the surface WS of the substrate W. The hydroxyl groups terminate atoms located on the surface WS of the substrate W. The hydroxyl groups bond with atoms located on the surface WS of the substrate W. The hydroxyl groups bond with the bonds of atoms located on the surface WS of the substrate W. The atoms are, for example, silicon atoms. The hydroxyl groups and silicon atoms that bond to each other are also called silanol groups. The bonds are, for example, dangling bonds.

[0147] When the hydrophilic agent is APM, the APM forms an oxide film on the surface WS and forms hydroxyl groups on the oxide film.

[0148] The formation of hydroxyl groups on the surface WS makes the surface WS hydrophilic.

[0149] As described above, the third supply unit 15c forms hydroxyl groups on the surface WS of the substrate W held by the substrate holding unit 13.

[0150] Subsequently, the third supply unit 15c stops supplying the hydrophilic agent to the substrate W. Specifically, the valve 18c closes, and the nozzle 16c stops discharging the hydrophilic agent.

[0151] Step S14: Second rinsing process Following the hydrophilization step, a second rinsing step is performed. In the second rinsing step, a rinsing solution is supplied to the substrate W. In the second rinsing step, the rinsing solution is supplied to the substrate W having hydroxyl groups. In this specification, the rinsing solution supplied to the substrate W in the second rinsing step is referred to as the "second rinsing solution".

[0152] In the first embodiment, the second rinse solution is of the same type as the first rinse solution. For example, both the first and second rinse solutions are deionized water.

[0153] The fourth supply unit 15d supplies the second rinsing liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18d opens. The nozzle 16d discharges the second rinsing liquid. The second rinsing liquid is supplied to the surface WS.

[0154] The second rinse solution cleans the substrate W. Specifically, the second rinse solution removes the hydrophilic agent from the substrate W. The hydrophilic agent on the substrate W is removed from the substrate W. The hydrophilic agent on the substrate W is replaced by the second rinse solution. The second rinse solution comes into contact with the surface WS.

[0155] The hydroxyl groups formed on the surface WS of the substrate W are not removed by the second rinsing solution. Even after the second rinsing replacement step, the substrate W still has hydroxyl groups formed on its surface WS.

[0156] Subsequently, the fourth supply unit 15d stops supplying the second rinsing liquid to the substrate W. Specifically, the valve 18d closes. The nozzle 16d stops discharging the second rinsing liquid.

[0157] Step S15: First replacement process Following the second rinsing step, the first substitution step is performed. In the first substitution step, a substitution solution is supplied to the substrate W. In the first substitution step, the substitution solution is supplied to the substrate W having hydroxyl groups. In this specification, the substitution solution supplied to the substrate W in the first substitution step is referred to as the "first substitution solution".

[0158] The fifth supply unit 15e supplies the first replacement liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18e opens. The nozzle 16e discharges the first replacement liquid. The first replacement liquid is supplied to the surface WS.

[0159] The first replacement solution removes the second rinse solution from the substrate W. The second rinse solution on the substrate W is removed from the substrate W. The second rinse solution on the substrate W is replaced by the first replacement solution. The first replacement solution comes into contact with the surface WS.

[0160] The hydroxyl groups formed on the surface of the substrate W are not removed by the first substitution solution. Even after the first substitution step, the substrate W still has hydroxyl groups formed on its surface WS.

[0161] Subsequently, the fifth supply unit 15e stops supplying the first replacement fluid to the substrate W. Specifically, the valve 18e closes, and the nozzle 16e stops discharging the first replacement fluid.

[0162] Step S16: First supply process Following the first substitution step, the first supply step is performed. In the first supply step, a drying aid g is supplied to the substrate W. The drying aid g contains a sublimable substance and a first solvent. In the first supply step, the drying aid g is supplied to the substrate W having hydroxyl groups. The hydroxyl groups are located on the surface WS.

[0163] The pumping unit 31 supplies the drying aid liquid g to the first supply unit 15a. The first supply unit 15a supplies the drying aid liquid g to the substrate W held by the substrate holding unit 13. Specifically, the pump 34 pumps the drying aid liquid g from the tank 22 to the first supply unit 15a. The valve 18a opens. The nozzle 16a discharges the drying aid liquid g. The drying aid liquid g is supplied to the surface WS.

[0164] The drying aid g removes the first replacement liquid from the substrate W. The first replacement liquid on the substrate W is removed from the substrate W. The first replacement liquid on the substrate W is replaced by the drying aid g. The drying aid g comes into contact with the surface WS.

[0165] Subsequently, the pumping unit 31 stops supplying the drying aid liquid g to the first supply unit 15a. The first supply unit 15a stops supplying the drying aid liquid g to the substrate W. Specifically, the pump 34 stops. The valve 18a closes. The nozzle 16a stops discharging the drying aid liquid g.

[0166] Figure 6 is a schematic diagram showing the substrate W in the first supply process. The drying aid liquid g on the substrate W forms a liquid film G. The liquid film G is located on the substrate W. The liquid film G is in contact with the substrate W.

[0167] Specifically, the liquid film G is located on the surface WS. The liquid film G is in contact with the surface WS. The liquid film G covers the surface WS. That is, the liquid film G is in contact with the pattern WP. The liquid film G covers the pattern WP.

[0168] The entire pattern WP is immersed in the liquid film G. The entire convex portion T is immersed in the liquid film G. The recess A is filled with the liquid film G. The entire recess A is filled with only the liquid film G.

[0169] The liquid film G has an upper surface G1. The upper surface G1 is located higher than the entire pattern WP. The upper surface G1 does not intersect with the pattern WP. The upper surface G1 is located higher than the entire protrusion T. The upper surface G1 does not intersect with the protrusion T.

[0170] Furthermore, the first replacement solution has already been removed from the substrate W by the drying aid solution g. Therefore, in Figure 6, the first replacement solution is not present on the substrate W. In Figure 6, the first replacement solution is not present in the recess A.

[0171] Gas J is located above the liquid film G. Pattern WP does not come into contact with gas J. Pattern WP is not exposed to gas J. The protrusion T does not come into contact with gas J. The protrusion T is not exposed to gas J.

[0172] The gas J is in contact with the liquid film G. The gas J is in contact with the upper surface G1. The upper surface G1 corresponds to the gas-liquid interface between the liquid film G and the gas J. Therefore, pattern WP does not intersect with the gas-liquid interface between the liquid film G and the gas J. The convex portion T does not intersect with the gas-liquid interface between the liquid film G and the gas J. Therefore, the liquid film G does not exert a significant force on pattern WP. The liquid film G does not exert a significant force on convex portion T.

[0173] In the first supply process, the height position of the upper surface G1 may be further adjusted. For example, the height position of the upper surface G1 may be adjusted while the first supply unit 15a supplies the drying aid liquid g to the substrate W. For example, the height position of the upper surface G1 may be adjusted after the first supply unit 15a stops supplying the drying aid liquid g. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation time of the substrate W.

[0174] Step S17: Solidification film formation process Following the first supply process, a solidification film formation process is performed. In the solidification film formation process, the first solvent evaporates from the drying aid liquid g on the substrate W. In the solidification film formation process, a solidified film is formed on the substrate W. The solidified film contains a sublimable substance.

[0175] Figure 7 is a schematic diagram showing the substrate W in the solidification film formation process. As described above, the first solvent has a relatively high vapor pressure. Specifically, at room temperature, the first solvent has a higher vapor pressure than the sublimable substance. Therefore, the first solvent smoothly evaporates from the drying aid liquid g on the substrate W. The first solvent smoothly changes from liquid to gas.

[0176] The first solvent evaporates from the drying aid liquid g on the substrate W, causing it to leave the drying aid liquid g on the substrate W. As the first solvent evaporates from the drying aid liquid g on the substrate W, the amount of the first solvent contained in the liquid film G decreases. As the amount of the first solvent contained in the liquid film G decreases, the concentration of the sublimable substance in the liquid film G increases.

[0177] Eventually, the sublimable substance in the liquid film G begins to precipitate on the substrate W. That is, the sublimable substance changes from a solute in the drying aid liquid g to a solid-phase sublimable substance. The solid-phase sublimable substance constitutes the solidified film K. The solidified film K does not contain the first solvent. The solidified film K is solid. The solidified film K is formed on the substrate W. The solidified film K is located on the substrate W. Specifically, the solidified film K is formed on the surface WS. The solidified film K is located on the surface WS.

[0178] Due to the evaporation of the first solvent and the precipitation of sublimable substances, the liquid film G gradually decreases. Due to the precipitation of sublimable substances, the liquid film G gradually transforms into a solidified film K.

[0179] First, the upper part of the liquid film G is transformed into the solidified film K. The solidified film K is located above the liquid film G. The solidified film K covers the upper surface G1 of the liquid film G.

[0180] When the solidified film K completely covers the upper surface G1, the solidified film K separates the liquid film G from the gas J. The liquid film G is in contact with the solidified film K. The upper surface G1 of the liquid film G is in contact with the solidified film K. The liquid film G is not in contact with the gas J. The upper surface G1 is not in contact with the gas J. The gas-liquid interface between the liquid film G and the gas J disappears.

[0181] Therefore, pattern WP does not intersect with the gas-liquid interface. The convex portion T does not intersect with the gas-liquid interface. Therefore, the liquid film G does not exert a significant force on pattern WP. The liquid film G does not exert a significant force on convex portion T.

[0182] The solidified film K is in contact with the gas J. The solidified film K has an upper surface K1. The upper surface K1 is in contact with the gas J.

[0183] The liquid film G decreases further. The liquid film G decreases without the liquid film G exerting a significant force on the protrusion T. The first solvent leaves the substrate W without the first solvent exerting a significant force on the protrusion T. The height position of the upper surface G1 decreases further. The solidified film K increases further.

[0184] Furthermore, the solidified film K may form before the completion of the first supply process. The period during which the solidified film formation process is performed may overlap with the period during which the first supply process is performed.

[0185] Figure 8 schematically shows the substrate W during the solidification film formation process. For example, Figure 8 schematically shows the substrate W at the end of the solidification film formation process. Only the solidified film K is present on the substrate W. At the end of the solidification film formation process, the entire liquid film G disappears from the substrate W. The liquid film G does not remain in the recess A. The entire first solvent disappears from the substrate W. The first solvent also does not remain in the recess A.

[0186] The surface WS is in contact with the solidified film K. The pattern WP is in contact with the solidified film K. The protrusion T is in contact with the solidified film K. The side T1 of the protrusion T is in contact with the solidified film K. The recess A is filled with the solidified film K. The entire recess A is filled with the solidified film K alone.

[0187] The solidification film K supports the pattern WP. The solidification film K protects the pattern WP. For example, the solidification film K prevents the pattern WP from collapsing.

[0188] The solidification film K supports the protrusion T. The solidification film K protects the protrusion T. For example, the solidification film K prevents the protrusion T from collapsing. For example, the solidification film K prevents the protrusion T from tilting. For example, the solidification film K prevents two adjacent protrusions T from coming into contact.

[0189] Step S18: Sublimation process After the solidification film formation process, a sublimation process is performed. In the sublimation process, the solidification film K sublimes.

[0190] The sixth supply unit 15f supplies drying gas to the substrate W held by the substrate holding unit 13. Specifically, the valve 18f opens. The nozzle 16f discharges the drying gas. The nozzle 16f blows out the drying gas. The drying gas is supplied to the surface WS. The drying gas is supplied to the solidification film K. The solidification film K is exposed to the drying gas. As a result, the solidification film K sublimes. The solidification film K changes into a gas without passing through a liquid state. Due to the sublimation of the solidification film K, the solidification film K is removed from the substrate W.

[0191] Subsequently, the sixth supply unit 15f stops supplying drying gas to the solidified film K. Specifically, valve 18f closes, and nozzle 16f stops blowing out the drying gas.

[0192] Figure 9 is a schematic diagram showing the substrate W during the sublimation process. As the solidified film K sublimes, the solidified film K gradually decreases. As the solidified film K sublimes, the solidified film K gradually becomes thinner. As the solidified film K sublimes, the height of the upper surface K1 gradually decreases.

[0193] Furthermore, sublimable materials possess sublimation properties. Therefore, the sublimation of the solidified film K may begin before the liquid film G disappears from the substrate W. Part of the period during which the sublimation process is performed may overlap with part of the period during which the solidified film formation process is performed.

[0194] Pattern WP begins to be exposed to gas J. The convex portion T begins to be exposed to gas J.

[0195] When the solidified film K sublimes, the solidified film K does not change into a liquid. The solidified film K does not exert a significant force on the pattern WP. The solidified film K does not exert a significant force on the protrusions T. The solidified film K leaves the substrate W without exerting a significant force on the pattern WP. The solidified film K leaves the substrate W without exerting a significant force on the protrusions T.

[0196] In the sublimation process, no liquid exists on the substrate W. In the sublimation process, no liquid exists on the surface WS. In the sublimation process, no liquid exists on the pattern WP. In the sublimation process, no liquid exists in the recess A. Therefore, in the sublimation process, no gas-liquid interface intersects with the pattern WP. In the sublimation process, no gas-liquid interface intersects with the convex portion T. Therefore, in the sublimation process, the pattern WP is not subjected to surface tension. In the sublimation process, the convex portion T is not subjected to surface tension.

[0197] Figure 10 is a schematic diagram of the substrate W during the sublimation process. Figure 10 schematically shows, for example, the substrate W at the end of the sublimation process. At the end of the sublimation process, the entire solidified film K disappears from the substrate W. No liquid remains on the substrate W. The surface WS is exposed to the gas J. The entire pattern WP is exposed to the gas J. The entire protrusion T is exposed to the gas J. The entire recess A is filled only with gas J. The substrate W is dried.

[0198] The processes in the first supply step, solidification film formation step, and sublimation step described above are examples of drying processes. The processes in the first supply step, solidification film formation step, and sublimation step described above correspond to examples of using drying aid liquid g. Drying aid liquid g is used in an environment at room temperature. Drying aid liquid g is used in an environment at normal pressure.

[0199] Step S19: Rotation stop process The rotary drive unit 14 stops the rotation of the substrate holder 13. The substrate W held by the substrate holder 13 stops rotating. The substrate W becomes stationary. The processing unit 11 finishes processing the substrate W.

[0200] <1-6. Technical significance of the hydrophilization process> The technical significance of the hydrophilization step will be explained by Example 1 and Comparative Example 1. In Example 1, the substrate W is treated by a substrate treatment method that includes a hydrophilization step. In Comparative Example 1, the substrate W is treated by a substrate treatment method that does not include a hydrophilization step.

[0201] The conditions for Example 1 are described below. In Example 1, the substrate W is treated in an etching step, a first rinsing step, a hydrophilization step, a second rinsing step, a first substitution step, a first supply step, a solidification film formation step, and a sublimation step. The etching solution is hydrofluoric acid (HF). The first rinsing solution is deionized water (DIW). The hydrophilic agent is APM. The second rinsing solution is deionized water (DIW). The first substitution solution is IPA. The sublimable substance in the drying aid g is cyclohexanone oxime. The first solvent in the drying aid g is IPA.

[0202] The conditions for Comparative Example 1 are described below. In Comparative Example 1, the substrate W is processed in the etching step, the first rinsing step, the first substitution step, the first supply step, the solidification film formation step, and the sublimation step. In Comparative Example 1, the substrate W is not processed in the hydrophilization step and the second rinsing step. Therefore, in Comparative Example 1, the hydrophilic agent and the second rinsing solution are not supplied to the substrate W. Except for the fact that the substrate W is not processed in the hydrophilization step and the second rinsing step, the conditions for Comparative Example 1 are the same as those for Example 1.

[0203] Each substrate W processed in Example 1 and Comparative Example 1 was evaluated by its collapse rate. The collapse rate is the probability that a pattern WP on the substrate W will collapse. The collapse rate is, for example, the ratio of the number of collapsed protrusions T to the total number of protrusions T.

[0204] The collapse rate of the substrate W treated in Example 1 was lower than that of the substrate W treated in Comparative Example 1.

[0205] Therefore, in Example 1, the substrate W was dried more appropriately than in Comparative Example 1. In Example 1, the pattern WP was protected more appropriately than in Comparative Example 1. In Example 1, the collapse of the pattern WP was prevented more appropriately than in Comparative Example 1. In Example 1, the substrate W was dried with the pattern WP suitably protected.

[0206] <1-7. Mechanism for protecting Pattern WP> The inventors investigated the mechanism for protecting the pattern WP in the substrate processing method of the first embodiment. The inventors investigated the mechanism for protecting the pattern WP in Example 1. The mechanism assumed by the inventors will be described below.

[0207] In the first supply process, when the drying aid liquid g is supplied to the substrate W, the substrate W has hydroxyl groups. Hydroxyl groups are polar. Sublimable substances are organic compounds containing oxime groups. Oxime groups are also polar. Hydroxyl groups and oxime groups form hydrogen bonds with each other. Hydroxyl groups and oxime groups attract each other through hydrogen bonds. Therefore, hydroxyl groups and sublimable substances attract each other through hydrogen bonds. Hydrogen bonds are a type of intermolecular force.

[0208] The intermolecular forces acting between the hydroxyl group and the sublimable substance are greater than the intermolecular forces acting between the hydroxyl group and the first solvent.

[0209] Figure 11 illustrates the mechanism of protection of the pattern WP in the substrate processing method of the first embodiment. The hydroxyl group is located on the surface WS. Therefore, the sublimable substance in the drying aid g is attracted to the surface WS. The sublimable substance in the drying aid g is attracted to the surface WS preferentially over the first solvent. The sublimable substance in the drying aid g removes the first solvent from the interface between the surface WS and the drying aid g. The sublimable substance in the drying aid g occupies the interface between the surface WS and the drying aid g.

[0210] The surface WS includes side T1 of the convex portion T. Therefore, the hydroxyl group is also located on side T1. Thus, the sublimable substance in the drying aid g is attracted to side T1. The sublimable substance in the drying aid g is attracted to side T1 preferentially over the first solvent.

[0211] The interface between side T1 and drying aid g is called "interface L". The sublimable substance in drying aid g displaces the first solvent from interface L. The sublimable substance in drying aid g occupies interface L.

[0212] The portion of interface L occupied by the sublimable substance is called "first region L1". Figure 11 clearly shows first region L1 in black. Figure 11 clearly shows first region L1 with a thick black line. First region L1 extends over the entire interface L. That is, the entire interface L is occupied by the sublimable substance in the drying aid g. First region L1 covers the entire side T1. That is, the entire side T1 is covered by the sublimable substance in the drying aid g.

[0213] In the solidification film formation process, the sublimable substance in the drying aid liquid g transforms into a solidified film K. As described above, the sublimable substance in the drying aid liquid g occupies the interface between the surface WS and the drying aid liquid g. In other words, the first solvent is not present at the interface between the surface WS and the drying aid liquid g. Therefore, the first solvent does not prevent the formation of the solidified film K at the interface between the surface WS and the drying aid liquid g. The first solvent does not prevent the formation of the solidified film K at a position in contact with the surface WS. Thus, the solidified film K is suitably formed on the surface WS. The solidified film K is suitably formed at a position in contact with the surface WS.

[0214] Furthermore, the sublimable substance in the drying aid liquid g occupies the entire interface L. In other words, the first solvent is not present at interface L. Therefore, the first solvent does not prevent the formation of the solidified film K at interface L. The first solvent does not prevent the formation of the solidified film K at a position in contact with side T1. Thus, the solidified film K is preferably formed on side T1. The solidified film K is preferably formed at a position in contact with side T1.

[0215] Since the solidified film K is formed in contact with side T1, the solidified film K grows appropriately in recess A. Therefore, the drying aid liquid g smoothly leaves recess A. The first solvent smoothly leaves recess A. Thus, at the end of the solidified film formation process, the drying aid liquid g does not remain in recess A. At the end of the solidified film formation process, the first solvent does not remain in recess A.

[0216] As a result, at the end of the solidification film formation process, the solidified film K is in contact with the entire side T1. The solidified film K is in surface contact with the entire side T1. Therefore, the solidified film K suitably supports the protrusion T. That is, the solidified film K suitably supports the pattern WP. Thus, the solidified film K suitably protects the pattern WP. The solidified film K suitably prevents the collapse of the pattern WP.

[0217] The mechanism for protecting the pattern WP in the substrate processing method of the first embodiment is summarized below. In the first supply step, the drying aid liquid g is appropriately supplied to the pattern WP. Specifically, the sublimable substance in the drying aid liquid g is attracted to the interface L by hydrogen bonding between the hydroxyl group and the sublimable substance. The sublimable substance in the drying aid liquid g enters the recess A appropriately. Therefore, in the solidification film formation step, the solidification film K is formed along the pattern WP. Thus, the pattern WP is protected.

[0218] <1-8. Mechanism of collapse in Pattern WP> The inventors investigated the mechanism of collapse of Pattern WP in Comparative Example 1. The mechanism assumed by the inventors is described below.

[0219] The substrate processing method of Comparative Example 1 does not include a hydrophilization step. Therefore, in Comparative Example 1, when the drying aid liquid g is supplied to the substrate W, the substrate W does not have hydroxyl groups.

[0220] Specifically, in the etching process, the substrate W is etched, and the surface WS of the substrate W is terminated with hydrogen. For example, hydrogen atoms bond with atoms located on the surface WS (e.g., silicon atoms). In the first rinsing process, the hydrogen on the surface WS is not removed. In the first substitution process, the hydrogen on the surface WS is also not removed. Therefore, in the comparative example, when the drying aid liquid g is supplied to the substrate W, the substrate W contains hydrogen.

[0221] Hydrogen atoms on substrate W bond with atoms located on surface WS. Therefore, hydrogen atoms on substrate W are nonpolar. Consequently, hydrogen atoms on substrate W and oxime groups do not form hydrogen bonds with each other. In other words, hydrogen atoms on substrate W and oxime groups do not attract each other. Therefore, hydrogen atoms on substrate W and sublimable materials do not attract each other.

[0222] Figure 12 illustrates the mechanism of collapse of pattern WP. The sublimable material is not attracted to the surface WS. The sublimable material does not occupy the interface between the surface WS and the drying aid g. The sublimable material does not displace the first solvent from the interface between the surface WS and the drying aid g. Therefore, not only the sublimable material but also the first solvent is present at the interface between the surface WS and the drying aid g.

[0223] In particular, when the initial amount Qb is greater than the initial amount Qa, the first solvent is present in greater quantities than the sublimable substance at the interface between the surface WS and the drying aid liquid g.

[0224] The sublimable substance does not occupy interface L. The sublimable substance does not displace the first solvent from interface L. Therefore, not only the sublimable substance but also the first solvent is present at interface L.

[0225] The portion of interface L not occupied by the sublimable substance is called the "second region L2". The second region L2 contains, for example, the first solvent. As shown in Figure 12, interface L contains multiple first regions L1 and multiple second regions L2. The first region L1 is divided by the second region L2. The size of each first region L1 is small. The area of ​​each first region L1 is small. The first region L1 does not extend over the entire interface L. That is, the entire interface L is not occupied by the sublimable substance in the drying aid g. The first solvent is present in at least a portion of interface L. The first region L1 does not cover the entire side T1. That is, the entire side T1 is not covered by the sublimable substance in the drying aid g.

[0226] In the solidification film formation process, the sublimable substance in the drying aid liquid g is transformed into a solidified film K. As described above, the sublimable substance in the drying aid liquid g does not occupy the interface between the surface WS and the drying aid liquid g. In other words, the first solvent is present at the interface between the surface WS and the drying aid liquid g. For this reason, the first solvent prevents the solidified film K from forming at the interface between the surface WS and the drying aid liquid g. The first solvent prevents the solidified film K from forming at a position in contact with the surface WS. Therefore, the solidified film K is not suitably formed on the surface WS. The solidified film K is not suitably formed at a position in contact with the surface WS.

[0227] Furthermore, the sublimable substance in the drying aid liquid g does not occupy the entire interface L. In other words, the first solvent is present at interface L (for example, in the second region L2). Therefore, the first solvent prevents the formation of the solidified film K at interface L. The first solvent prevents the formation of the solidified film K at a position in contact with side T1. In particular, the solidified film K is unlikely to form in the second region L2. Therefore, the solidified film K is not preferably formed on side T1. The solidified film K is not preferably formed at a position in contact with side T1.

[0228] Since the solidified film K is not formed in contact with side T1, the solidified film K does not grow properly in recess A. Therefore, the drying aid liquid g does not smoothly leave recess A. The first solvent does not smoothly leave recess A. Therefore, at the end of the solidified film formation process, the drying aid liquid g may remain in recess A. At the end of the solidified film formation process, the first solvent may remain in recess A.

[0229] As a result, at the end of the solidification film formation process, the solidified film K does not come into contact with the entire side T1. The solidified film K comes into contact with only a portion of the side T1. Therefore, the solidified film K does not adequately support the protrusion T. In other words, the solidified film K does not adequately support the pattern WP. Consequently, the solidified film K does not adequately protect the pattern WP. The solidified film K does not adequately prevent the collapse of the pattern WP.

[0230] The mechanism of pattern WP collapse is summarized below. The drying aid liquid g is not properly supplied to pattern WP. Specifically, the sublimable material in the drying aid liquid g is not attracted to the interface L. The sublimable material in the drying aid liquid g does not properly enter the recess A. Therefore, the solidified film K is not formed along pattern WP. Thus, pattern WP is not protected.

[0231] <1-9. Effects of the First Embodiment> The substrate processing method of the first embodiment is for processing a substrate W. The substrate W has a pattern WP formed on its surface WS. The substrate processing method comprises a hydrophilization step, a first supply step, a solidification film formation step, and a sublimation step. In the hydrophilization step, hydroxyl groups are formed on the surface WS. In the first supply step, a drying aid liquid g is supplied to the substrate W having hydroxyl groups. The drying aid liquid g contains a sublimable substance and a first solvent. In the solidification film formation step, the first solvent evaporates from the drying aid liquid g on the substrate W. In the solidification film formation step, a solidification film K is formed on the substrate. The solidification film K contains a sublimable substance. In the sublimation step, the solidification film K sublimes. The substrate is dried by the sublimation of the solidification film K.

[0232] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, in the first feeding step, the drying aid liquid g is appropriately supplied to pattern WP.

[0233] According to the mechanism assumed by the present inventors, in the first supply step, the hydroxyl group is located on the surface WS. In the first supply step, the hydroxyl group is located on the pattern WP. The sublimable substance contains an oxime group. Therefore, the sublimable substance and the hydroxyl group attract each other through interaction (specifically, hydrogen bonding). Thus, in the first supply step, the sublimable substance in the drying aid g is attracted to the surface WS. In the first supply step, the sublimable substance in the drying aid g is attracted to the pattern WP. Therefore, in the first supply step, the drying aid g is appropriately supplied to the pattern WP.

[0234] As a result, in the solidification film formation process, the solidification film K is properly formed along the pattern WP. This is because the solidification film K contains a sublimable substance. The solidification film K provides suitable support for the pattern WP. The solidification film K effectively prevents the collapse of the pattern WP. With the pattern WP suitably protected, the substrate W is dried.

[0235] As described above, according to the substrate processing method of the first embodiment, the substrate W is properly dried.

[0236] According to the mechanism envisioned by the present inventors, in the first supply step, the sublimable material is attracted to the pattern WP by intermolecular forces. Therefore, even when the pattern WP is fine, the drying aid liquid g is appropriately supplied to the pattern WP. Even when the size of the recess A is minute, the drying aid liquid g is appropriately supplied to the recess A. Even when the distance between two adjacent protrusions T is minute, the drying aid liquid g is appropriately supplied to the recess A. Thus, the finer the pattern WP becomes, the more significantly the usefulness of appropriately supplying the drying aid liquid g to the recess A increases.

[0237] As described above, in the first supply step, the substrate W has hydroxyl groups. Therefore, in the first supply step, the surface WS is hydrophilic. In the first supply step, the pattern WP is hydrophilic. If the pattern WP comes into contact with the gas-liquid interface, surface tension acts on the pattern WP. When the pattern WP is hydrophilic, the surface tension acting on the pattern WP is even greater. Therefore, the presence of hydroxyl groups in the substrate W in the first supply step may hinder the protection of the pattern WP. In other words, the first supply step may have a problem that hinders the protection of the pattern WP. Therefore, to a person skilled in the art, it may seem difficult to adopt the first supply step. However, the substrate processing method of the first embodiment deliberately adopts the first supply step. The reason is that the inventors have found that a combination of the first supply step and a specific sublimable substance produces a remarkable effect. Here, the specific sublimable substance is a sublimable substance containing an organic compound containing an oxime group. The remarkable effect is that the drying aid liquid g is appropriately supplied to the pattern WP.

[0238] Furthermore, the substrate processing method of the first embodiment does not include a step of applying a water-repellent agent to the surface WS of the substrate W. The substrate processing method of the first embodiment does not include a step of making the substrate W hydrophobic. Therefore, the number of steps included in the substrate processing method of the first embodiment is suitably reduced. Thus, the time required to carry out the substrate processing method of the first embodiment is suitably shortened. Furthermore, the substrate processing method of the first embodiment does not use a water-repellent agent. Therefore, the cost required to carry out the substrate processing method of the first embodiment is effectively reduced.

[0239] In the hydrophilization process, APM is supplied to the substrate W. Therefore, in the hydrophilization process, hydroxyl groups are appropriately formed on the surface WS.

[0240] The substrate processing method of the first embodiment includes an etching step. The etching step is performed before the hydrophilization step. In the etching step, an etching solution is supplied to the substrate W. In the etching step, the oxide film on the substrate W is removed. Therefore, in the hydrophilization step, hydroxyl groups are formed more appropriately on the surface WS. For example, in the hydrophilization step, hydroxyl groups are formed uniformly over the entire surface WS.

[0241] The substrate processing method of the first embodiment includes a first rinsing step. The first rinsing step is performed after the etching step and before the hydrophilization step. In the first rinsing step, a first rinsing solution is supplied to the substrate W. Therefore, in the first rinsing step, the etching solution is suitably removed from the substrate W. Thus, in the hydrophilization step, hydroxyl groups are formed more appropriately on the surface WS.

[0242] The substrate processing method of the first embodiment includes a second rinsing step. The second rinsing step is performed after the hydrophilization step and before the first supply step. In the second rinsing step, a second rinsing liquid is supplied to the substrate W. As a result, the substrate W is properly cleaned in the second rinsing step. For example, in the second rinsing step, the hydrophilic agent is suitably removed from the substrate W. Therefore, in the first supply step, the drying aid liquid g is supplied to the pattern WP more appropriately.

[0243] The substrate processing method of the first embodiment includes a first replacement step. The first replacement step is performed after the second rinsing step and before the first supply step. In the first replacement step, the first replacement liquid is supplied to the substrate. As a result, the second rinsing liquid is suitably removed from the substrate. Therefore, in the first supply step, the drying aid liquid g is supplied to the pattern WP more appropriately.

[0244] The sublimable material does not contain fluorocarbon compounds. Therefore, in the first supply step, the drying aid liquid g is supplied more appropriately to pattern WP.

[0245] The sublimable substance includes, for example, at least one of cyclohexanone oxime and pinacolin oxime. Therefore, in the first supply step, the drying aid liquid g is supplied to pattern WP more appropriately.

[0246] The substrate processing apparatus 1 of the first embodiment comprises a substrate holding unit 13, a third supply unit 15c, and a first supply unit 15a. The substrate holding unit 13 holds the substrate W. The third supply unit 15c forms hydroxyl groups on the substrate W held by the substrate holding unit 13. The first supply unit 15a supplies a drying aid liquid g to the substrate W held by the substrate holding unit 13. The drying aid liquid g contains a sublimable substance and a first solvent. Therefore, when the first supply unit 15a supplies the drying aid liquid g to the substrate W, the first solvent evaporates from the drying aid liquid g on the substrate W. By the evaporation of the first solvent, a solidified film K is formed on the substrate W. The solidified film K contains a sublimable substance. Therefore, the solidified film K sublimes. By the sublimation of the solidified film K, the substrate W is dried.

[0247] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, the drying aid liquid g is appropriately supplied to the pattern WP. As a result, the solidified film K is appropriately formed along the pattern WP. The solidified film K suitably supports the pattern WP. The solidified film K appropriately prevents the collapse of the pattern WP. With the pattern WP suitably protected, the substrate W is dried.

[0248] As described above, according to the substrate processing apparatus 1 of the first embodiment, the substrate W is properly dried.

[0249] <2. Second Embodiment> The second embodiment will be described with reference to the drawings. Note that components identical to those in the first embodiment will be denoted by the same reference numerals, and detailed explanations will be omitted.

[0250] <2-1. Configuration of Processing Unit 11> The second embodiment of the substrate processing apparatus 1 is substantially the same as that of the first embodiment. The configuration of the processing unit 11 of the second embodiment will be described below.

[0251] Figure 13 shows the configuration of the processing unit 11 and the first supply source 19a according to the second embodiment.

[0252] The supply unit 15 includes the 1st to 6th supply units 15a-15f, as well as the 7th supply unit 15g. The 7th supply unit 15g supplies a water repellent. The 7th supply unit 15g supplies, for example, a mixed liquid containing a water repellent. The mixed liquid is a liquid.

[0253] The water repellent supplied by the 7th supply unit 15g includes, for example, at least one of a silicone-based water repellent and a metal-based water repellent. A silicone-based water repellent makes silicone water-repellent. A silicone-based water repellent makes compounds containing silicone water-repellent. A silicone-based water repellent makes films containing silicone water-repellent. A silicone-based water repellent is also called a silane-based water repellent. A metal-based water repellent makes metal water-repellent. A metal-based water repellent makes compounds containing metal water-repellent. A metal-based water repellent makes metal films water-repellent.

[0254] Silicone-based water repellents are, for example, silane coupling agents. Silane coupling agents include, for example, hexamethyldisilazane (HMDS), tetramethylsilane (TMS), fluorinated alkylchlorosilane, alkyldisilazane, and at least one non-chloro water repellent. Non-chloro water repellents include, for example, dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethylaminotrimethylsilane, N-(trimethylsilyl)dimethylamine, and at least one organosilane compound. Alternatively, the silicone-based water repellent comprises at least one of the following: 3-aminopropyltriethoxysilane (APTES), benzyltrichlorosilane, 11-cyanoundecyltrichlorosilane, 11-iodoundecyltrichlorosilane, 11-bromoundecyltrichlorosilane, 11-chloroundecyltrichlorosilane, N-undecyltrichlorosilane, and 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS).

[0255] A metal-based water repellent includes, for example, an amine having a hydrophobic group and at least one organosilicon compound.

[0256] The mixture supplied by the 7th supply unit 15 g contains a second solvent in addition to the water repellent. The second solvent is, for example, soluble in the water repellent. The second solvent dilutes the water repellent. The second solvent includes, for example, an organic solvent. The second solvent includes, for example, IPA and at least one of propylene glycol monomethyl ether acetate (PGMEA).

[0257] The mixture preferably does not contain water. The mixture consists of, for example, only a water repellent and a second solvent. For example, the mixture consists of only hexamethyldisilazane and propylene glycol monomethyl ether acetate. Hereinafter, hexamethyldisilazane will be referred to as "HMDS". Propylene glycol monomethyl ether acetate will be referred to as "PGMEA".

[0258] Furthermore, the drying aid liquid g supplied by the first supply unit 15a does not contain a water repellent. The rinsing liquid supplied by the fourth supply unit 15d does not contain a water repellent. The replacement liquid supplied by the fifth supply unit 15e does not contain a water repellent. The replacement liquid is soluble in the mixed liquid. The replacement liquid is compatible with the mixed liquid.

[0259] The seventh supply unit 15g comprises a nozzle 16g, piping 17g, and a valve 18g. The nozzle 16g is installed inside the housing 12. The nozzle 16g discharges the mixed liquid. The piping 17g is connected to the nozzle 16g. At least a portion of the piping 17g may be provided outside the housing 12. The valve 18g is provided on the piping 17g. The valve 18g may be provided outside the housing 12. The valve 18g controls the discharge of the mixed liquid.

[0260] The seventh supply unit 15g communicates with the seventh supply source 19g. The seventh supply unit 15g is connected to the seventh supply source 19g. The seventh supply source 19g is connected, for example, to piping 17g. The seventh supply source 19g is provided outside the housing 12. The seventh supply source 19g sends the mixed liquid to the seventh supply unit 15g. The seventh supply source 19g may be an element of the substrate processing apparatus 1. The seventh supply source 19g may not be an element of the substrate processing apparatus 1.

[0261] The seventh supply section 15g is an example of a hydrophobic section in the present invention.

[0262] Although not shown in the diagram, the control unit 10 controls the seventh supply unit 15g. The control unit 10 also controls the valve 18g.

[0263] <2-2. Example of operation of the first supply source 19a and processing unit 11> Figure 14 is a flowchart showing the procedure of the substrate processing method of the second embodiment. The substrate processing method of the second embodiment has steps S21-S24 in place of steps S15 and S16 of the first embodiment. Specifically, the substrate processing method of the second embodiment comprises steps S1 and steps S10-S14, S17-S19, and S21-S24. Steps S21-S24 are executed after steps S10-S14. Steps S21-S24 are executed in this order. Steps S21-S24 are substantially executed by the processing unit 11. Steps S16-S19 are executed after steps S21-S24.

[0264] The operations in steps S1, S10-S14, and S16-S19 are substantially the same between the first and second embodiments. Therefore, the explanation of the operations in steps S1, S10-S14, and S16-S19 will be omitted. The operations in steps S21-S24 will now be explained.

[0265] Step S21: Second replacement process Following the second rinsing step, a second substitution step is performed. In the second substitution step, a substitution solution is supplied to the substrate W. In the second substitution step, the substitution solution is supplied to the substrate W having hydroxyl groups. In this specification, the substitution solution supplied to the substrate W in the second substitution step is referred to as the "second substitution solution".

[0266] The fifth supply unit 15e supplies the second replacement liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18e opens. The nozzle 16e discharges the second replacement liquid. The second replacement liquid is supplied to the surface WS (specifically, the first surface WS1).

[0267] In the following explanation, "surface WS" specifically refers to the first surface WS1. In other words, in the following explanation, "surface WS" is synonymous with "surface WS (specifically the first surface WS1)."

[0268] The second replacement liquid removes the second rinse liquid on the substrate W. The second rinse liquid on the substrate W is removed from the substrate W. The second rinse liquid on the substrate W is replaced with the second replacement liquid. The second replacement liquid contacts the surface WS.

[0269] The hydroxyl groups formed on the surface of the substrate W are not removed by the second replacement liquid. Even after the second replacement step, the substrate W has hydroxyl groups formed on the surface WS.

[0270] Thereafter, the fifth supply unit 15e stops supplying the second replacement liquid to the substrate W. Specifically, the valve 18e closes. The nozzle 16e stops discharging the second replacement liquid.

[0271] Step S22: Hydrophobicization process After the second replacement step, a hydrophobicization process is performed. In the hydrophobicization process, the substrate W has hydroxyl groups. In the hydrophobicization process, a water repellent is supplied to the substrate W. In the hydrophobicization process, for example, a mixed liquid is supplied to the substrate W. The mixed liquid contains a water repellent and a second solvent. In the hydrophobicization replacement process, the water repellent adheres to the surface WS of the substrate W.

[0272] The seventh supply unit 15g supplies the mixed liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18g opens. The nozzle16g discharges the mixed liquid. The mixed liquid is supplied to the surface WS.

[0273] The mixed liquid removes the second replacement liquid on the substrate W. The second replacement liquid on the substrate W is removed from the substrate W. The second replacement liquid on the substrate W is replaced with the mixed liquid. The mixed liquid contacts the surface WS.

[0274] The water repellent contained in the mixed liquid adheres to the surface WS. For example, the water repellent adheres to the surface WS by at least one of chemisorption and physisorption. When the water repellent adheres to the surface WS by chemisorption, the water repellent, for example, forms a chemical bond with the surface WS. When the water repellent adheres to the surface WS by physisorption, the water repellent does not necessarily form a chemical bond with the surface WS.

[0275] For example, a water-repellent agent forms a water-repellent film on the surface WS. The water-repellent film adheres to the surface WS. The water-repellent film adheres to the surface WS by at least one of chemiadsorption and physiadsorption. When the water-repellent film adheres to the surface WS by chemiadsorption, the water-repellent film chemically bonds with the surface WS, for example. When the water-repellent film adheres to the surface WS by physiadsorption, the water-repellent film does not need to chemically bond with the surface WS.

[0276] At least a portion of the water-repellent agent contained in the mixture adheres to the surface WS. For example, only a portion of the water-repellent agent contained in the mixture may adhere to the surface WS. For example, the other portion of the water-repellent agent contained in the mixture may not adhere to the surface WS. Here, the water-repellent agent contained in the mixture that does not adhere to the surface is specifically referred to as the "unreacted portion of the water-repellent agent."

[0277] The entire molecule of the water repellent may adhere to the surface WS. Only a portion of the molecule of the water repellent may adhere to the surface WS. The portion of the molecule of the water repellent corresponds to, for example, a hydrophobic group. For example, the molecule of the water repellent may have a hydrophobic group, and only the hydrophobic group may adhere to the surface WS.

[0278] When the water repellent is HMDS, HMDS reacts with the hydroxyl groups formed on the surface WS. The hydroxyl groups on the surface WS are converted into trimethylsiloxy groups (-OSi(CH3)3). Here, the trimethylsiloxy group corresponds to a hydrophobic group. The trimethylsiloxy group contains a portion of one HMDS molecule.

[0279] When the water-repellent agent adheres to the surface WS, the surface WS becomes hydrophobic.

[0280] As described above, the seventh supply unit 15g applies a water-repellent agent to the surface WS of the substrate W held by the substrate holding unit 13.

[0281] Subsequently, the seventh supply unit 15g stops supplying the mixed liquid to the substrate W. Specifically, valve 18g closes, and nozzle 16g stops discharging the mixed liquid.

[0282] Step S23: Third replacement step Following the hydrophobicization step, a third substitution step is performed. In the third substitution step, a substitution solution is supplied to the substrate W. In the third substitution step, the substitution solution is supplied to the substrate W to which the water repellent is attached. In this specification, the substitution solution supplied to the substrate W in the third substitution step is referred to as the "third substitution solution".

[0283] In the second embodiment, the third replacement solution is of the same type as the second replacement solution. For example, both the second and third replacement solutions are IPA.

[0284] The fifth supply unit 15e supplies the third replacement liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18e opens. The nozzle 16e discharges the third replacement liquid. The third replacement liquid is supplied to the surface WS.

[0285] The third replacement liquid removes the mixture from the substrate W. The third replacement liquid removes, for example, unreacted water repellent. The mixture on the substrate W is removed from the substrate W. The unreacted water repellent is removed from the substrate W. The mixture on the substrate W is replaced by the third replacement liquid. The third replacement liquid comes into contact with the surface WS.

[0286] The water-repellent agent adhering to the surface WS of the substrate W is not removed by the third displacement solution. Even after the third displacement step, the substrate W still has the water-repellent agent adhering to its surface WS.

[0287] Subsequently, the fifth supply unit 15e stops supplying the third replacement fluid to the substrate W. Specifically, the valve 18e closes, and the nozzle 16e stops discharging the third replacement fluid.

[0288] Step S24: Second supply process The second supply process is similar to the first supply process of the first embodiment. Therefore, the second supply process will be briefly described.

[0289] After the third replacement step, the second supply step is executed. In the second supply step, the drying aid liquid g is supplied to the substrate W. In the second supply step, the drying aid liquid g is supplied to the substrate W to which the water repellent is attached. The water repellent is located on the surface WS.

[0290] The pressure feeding unit 31 supplies the drying aid liquid g to the first supply portion 15a. The first supply portion 15a supplies the drying aid liquid g to the substrate W held by the substrate holding portion 13.

[0291] The drying aid liquid g removes the third replacement liquid on the substrate W. The third replacement liquid on the substrate W is removed from the substrate W. The third replacement liquid on the substrate W is replaced with the drying aid liquid g. The drying aid liquid g contacts the surface WS.

[0292] Thereafter, the pressure feeding unit 31 stops the supply of the drying aid liquid g to the first supply portion 15a. The first supply portion 15a stops the supply of the drying aid liquid g to the substrate W.

[0293] <2-3. Technical significance of the hydrophobization process> The technical significance of the hydrophobization process will be explained by comparing Example 2 with Comparative Example 1. In Example 2, the substrate W is processed by a substrate processing method including a hydrophobization process. Comparative Example 1 was described in "1-6. Technical significance of the hydrophilicization process" of the first embodiment. The substrate processing method of Comparative Example 1 does not include a hydrophobization process.

[0294] The conditions of Example 2 will be described. In Example 2, the substrate W is processed in an etching step, a first rinse step, a hydrophilicization step, a second rinse step, a second replacement step, a hydrophobization step, a third replacement step, a second supply step, a solid film formation step, and a sublimation step. The etching solution is hydrofluoric acid (HF). The first rinse solution is deionized water (DIW). The hydrophilic agent is APM. The second rinse solution is deionized water (DIW). The second replacement solution is IPA. The water repellent of the mixed solution is HMDS. The second solvent of the mixed solution is PGMEA. The third replacement solution is IPA. The sublimable substance of the drying aid liquid g is cyclohexanone oxime. The first solvent of the drying aid liquid g is IPA.

[0295] Each substrate W processed in Example 2 and Comparative Example 1 was evaluated by its collapse rate.

[0296] The collapse rate of the substrate W treated in Example 2 was lower than that of the substrate W treated in Comparative Example 1. The collapse rate of the substrate W treated in Example 2 was about the same as that of the substrate W treated in Example 1.

[0297] Therefore, in Example 2, the substrate W was dried more appropriately than in Comparative Example 2. In Example 2, the pattern WP was protected more appropriately than in Comparative Example 1. In Example 2, the collapse of the pattern WP was prevented more appropriately than in Comparative Example 1. In Example 2, the substrate W was dried with the pattern WP suitably protected. In Example 2, the substrate W was dried to the same extent as in Example 1.

[0298] <2-4. Mechanism for protecting Pattern WP> The inventors investigated the mechanism for protecting the pattern WP in the substrate processing method of the second embodiment. The inventors also investigated the mechanism for protecting the pattern WP in Example 2. The mechanisms assumed by the inventors are described below.

[0299] In the second supply process, when the drying aid liquid g is supplied to the substrate W, the substrate W contains a water repellent. The molecular weight of the water repellent is relatively large. The size of one molecule of the water repellent is relatively large. For example, the molecular weight of the water repellent is larger than the molecular weight of a hydrogen atom. For example, the water repellent contains a carbon chain. For example, the water repellent is a chain compound. For example, the water repellent is a straight-chain compound. For example, the water repellent is a branched compound. Therefore, the van der Waals forces acting between the water repellent and the sublimable substance are large. The water repellent and the sublimable substance attract each other by van der Waals forces. Van der Waals forces are a type of intermolecular force.

[0300] The intermolecular forces acting between the water repellent and the sublimable substance are greater than the intermolecular forces acting between the water repellent and the first solvent.

[0301] For convenience, refer to Figure 11. The water-repellent agent is located on the surface WS. Therefore, the sublimable substance in the drying aid g is attracted to the surface WS. The sublimable substance in the drying aid g is attracted to the surface WS preferentially over the first solvent. The sublimable substance in the drying aid g removes the first solvent from the interface between the surface WS and the drying aid g. The sublimable substance in the drying aid g occupies the interface between the surface WS and the drying aid g.

[0302] The water-repellent agent is also located on side T1 of the protrusion T. Therefore, the sublimable substance in the drying aid liquid g is attracted to side T1. The sublimable substance is attracted to side T1 preferentially over the first solvent. The sublimable substance removes the first solvent from the interface L between side T1 and the drying aid liquid g. The sublimable substance occupies the entire interface L. As described above, the first region L1 is the portion of interface L occupied by the sublimable substance. The first region L1 extends over the entire interface L. The first region L1 covers the entire side T1.

[0303] In the solidification film formation process, the sublimable substance in the drying aid liquid g transforms into a solidified film K. As described above, the sublimable substance in the drying aid liquid g occupies the interface between the surface WS and the drying aid liquid g. In other words, the first solvent is not present at the interface between the surface WS and the drying aid liquid g. Therefore, the first solvent does not prevent the formation of the solidified film K at the interface between the surface WS and the drying aid liquid g. The first solvent does not prevent the formation of the solidified film K at a position in contact with the surface WS. Thus, the solidified film K is suitably formed on the surface WS. The solidified film K is suitably formed at a position in contact with the surface WS.

[0304] Furthermore, the sublimable substance in the drying aid liquid g occupies the entire interface L. In other words, the first solvent is not present at interface L. Therefore, the first solvent does not prevent the formation of the solidified film K at interface L. The first solvent does not prevent the formation of the solidified film K at a position in contact with side T1. Thus, the solidified film K is preferably formed on side T1. The solidified film K is preferably formed at a position in contact with side T1.

[0305] Since the solidified film K is formed in contact with side T1, the solidified film K grows appropriately in recess A. Therefore, the drying aid liquid g smoothly leaves recess A. The first solvent smoothly leaves recess A. Thus, at the end of the solidified film formation process, the drying aid liquid g does not remain in recess A. At the end of the solidified film formation process, the first solvent does not remain in recess A.

[0306] As a result, at the end of the solidification film formation process, the solidified film K is in contact with the entire side T1. The solidified film K is in surface contact with the entire side T1. Therefore, the solidified film K suitably supports the protrusion T. That is, the solidified film K suitably supports the pattern WP. Thus, the solidified film K suitably protects the pattern WP. The solidified film K suitably prevents the collapse of the pattern WP.

[0307] The mechanism for protecting the pattern WP in the substrate processing method of the second embodiment is summarized below. In the second supply step, the drying auxiliary liquid g is appropriately supplied to the pattern WP. Specifically, the sublimable substance in the drying auxiliary liquid g is attracted to the interface L by van der Waals forces between the water repellent and the sublimable substance. The sublimable substance in the drying auxiliary liquid g enters the recess A appropriately. Therefore, in the solidification film formation step, the solidification film K is formed along the pattern WP. Thus, the pattern WP is protected.

[0308] <2-5. Effects of the Second Embodiment> The substrate processing method of the second embodiment is for processing a substrate W. The substrate W has a pattern WP formed on its surface WS. The substrate processing method comprises a hydrophobicization step, a second supply step, a solidification film formation step, and a sublimation step. In the hydrophobicization step, a water-repellent agent is attached to the surface WS. In the second supply step, a drying auxiliary liquid g is supplied to the substrate W to which the water-repellent agent is attached. The drying auxiliary liquid g contains a sublimable substance and a first solvent. In the solidification film formation step, the first solvent evaporates from the drying auxiliary liquid g on the substrate W. In the solidification film formation step, a solidification film K is formed on the substrate W. The solidification film K contains a sublimable substance. In the sublimation step, the solidification film K sublimes. The substrate is dried by the sublimation of the solidification film K.

[0309] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, in the second feeding step, the drying aid liquid g is appropriately supplied to pattern WP.

[0310] According to the mechanism assumed by the present inventors, in the second supply step, the water repellent is located on the surface WS. In the second supply step, the water repellent is located on the pattern WP. Therefore, the sublimable substance and the water repellent attract each other through interaction (specifically, van der Waals forces). Thus, in the second supply step, the sublimable substance in the drying aid liquid g is attracted to the surface WS. In the second supply step, the sublimable substance in the drying aid liquid g is attracted to the pattern WP. Therefore, in the second supply step, the drying aid liquid g is appropriately supplied to the pattern WP.

[0311] As a result, in the solidification film formation process, the solidification film K is properly formed along the pattern WP. This is because the solidification film K contains a sublimable substance. The solidification film K provides suitable support for the pattern WP. The solidification film K effectively prevents the collapse of the pattern WP. With the pattern WP suitably protected, the substrate W is dried.

[0312] As described above, according to the substrate processing method of the second embodiment, the substrate W is properly dried.

[0313] In the second supply process, the substrate W contains a water-repellent agent. Therefore, in the second supply process, the surface WS is hydrophobic. In the second supply process, the pattern WP is also hydrophobic. If the pattern WP were to come into contact with the gas-liquid interface, surface tension would act on the pattern WP. However, if the pattern WP is hydrophobic, the surface tension acting on the pattern WP is even smaller. Therefore, even if the pattern WP were to come into contact with the gas-liquid interface from the second supply process to the sublimation process, the surface tension acting on the pattern WP would be suppressed, and the collapse of the pattern WP would be suppressed.

[0314] In the hydrophobicization process, a mixed solution is supplied to the substrate W. The mixed solution contains a water-repellent agent and a second solvent. Therefore, in the hydrophobicization process, the water-repellent agent contained in the mixed solution is suitably supplied to the substrate W. Thus, in the hydrophobicization process, the water-repellent agent contained in the mixed solution adheres suitably to the substrate W.

[0315] The substrate processing method of the second embodiment includes a hydrophilization step. The hydrophilization step is performed before the hydrophobicization step. In the hydrophilization step, hydroxyl groups are formed on the surface WS. Therefore, in the hydrophobicization step, the surface WS has hydroxyl groups. Thus, in the hydrophobicization step, the water repellent adheres more favorably to the surface of the substrate. For example, in the hydrophobicization step, the water repellent reacts favorably with the hydroxyl groups on the surface WS. For example, in the hydrophobicization step, the water repellent adheres uniformly to the entire surface WS.

[0316] The substrate processing method of the second embodiment includes an etching step. The etching step is performed before the hydrophilization step. In the etching step, an etching solution is supplied to the substrate W. In the etching step, the oxide film on the substrate W is removed. Thus, in the hydrophilization step, hydroxyl groups are appropriately formed on the surface WS. For example, in the hydrophilization step, hydroxyl groups are formed uniformly over the entire surface WS.

[0317] The substrate processing method of the second embodiment includes a first rinsing step. The first rinsing step is performed after the etching step and before the hydrophilization step. In the first rinsing step, a first rinsing solution is supplied to the substrate W. Therefore, in the first rinsing step, the etching solution is suitably removed from the substrate W. Thus, in the hydrophilization step, hydroxyl groups are formed more appropriately on the surface WS.

[0318] The substrate processing method of the second embodiment includes a second rinsing step. The second rinsing step is performed after the hydrophilization step and before the hydrophobicization step. In the second rinsing step, a second rinsing solution is supplied to the substrate W. As a result, the substrate W is properly cleaned in the second rinsing step. For example, in the second rinsing step, the hydrophilic agent is suitably removed from the substrate W. Therefore, in the hydrophobicization step, the water-repellent agent adheres more suitably to the substrate W.

[0319] The substrate processing method of the second embodiment includes a second substitution step. The second substitution step is performed after the second rinsing step and before the hydrophobicization step. In the second substitution step, the second substitution solution is supplied to the substrate W. As a result, the second rinsing solution is removed from the substrate W. Therefore, in the hydrophobicization step, the water repellent adheres more favorably to the substrate W.

[0320] The substrate processing method of the second embodiment includes a third substitution step. The third substitution step is performed after the hydrophobicization step and before the second supply step. In the third substitution step, the third substitution liquid is supplied to the substrate W. Therefore, in the third substitution step, the substrate W is properly cleaned. For example, in the third substitution step, any unreacted water repellent is suitably removed from the substrate W. For example, in the third substitution step, the mixed liquid is suitably removed from the substrate W. Therefore, in the second supply step, the drying aid liquid g is supplied to the pattern WP more appropriately.

[0321] The sublimable material does not contain fluorocarbon compounds. Therefore, in the second supply step, the drying aid liquid g is supplied more appropriately to pattern WP.

[0322] The sublimable substance includes, for example, at least one of cyclohexanone oxime and pinacolin oxime. Therefore, in the second feeding step, the drying aid liquid g is supplied to pattern WP more appropriately.

[0323] The substrate processing apparatus 1 of the second embodiment comprises a substrate holding unit 13, a seventh supply unit 15g, and a first supply unit 15a. The substrate holding unit 13 holds the substrate W. The seventh supply unit 15g applies a water-repellent agent to the surface WS of the substrate W held by the substrate holding unit 13. The first supply unit 15a supplies a drying aid liquid g to the substrate W held by the substrate holding unit 13. The drying aid liquid g contains a sublimable substance and a first solvent. Therefore, when the first supply unit 15a supplies the drying aid liquid g to the substrate W, the first solvent evaporates from the drying aid liquid g on the substrate W. Due to the evaporation of the first solvent, a solidified film K is formed on the substrate W. The solidified film K contains a sublimable substance. Therefore, the solidified film K sublimes. Due to the sublimation of the solidified film K, the substrate W is dried.

[0324] Here, the sublimable substance includes an organic compound containing an oxime group. Therefore, the drying aid liquid g is appropriately supplied to the pattern WP. As a result, the solidified film K is appropriately formed along the pattern WP. The solidified film K suitably supports the pattern WP. The solidified film K appropriately prevents the collapse of the pattern WP. With the pattern WP suitably protected, the substrate W is dried.

[0325] As described above, according to the substrate processing apparatus 1 of the second embodiment, the substrate W is properly dried.

[0326] <3. Modified Embodiments> The present invention is not limited to the first and second embodiments, and can be modified and implemented as described below.

[0327] (1) In the first and second embodiments, cyclohexanone oxime and pinacolin oxime were given as examples of organic compounds containing an oxime group. However, the organic compounds containing an oxime group may be compounds other than cyclohexanone oxime and pinacolin oxime. The sublimable substance may also include organic compounds containing an oxime group other than cyclohexanone oxime and pinacolin oxime.

[0328] (2) In the hydrophilization process of the first and second embodiments, APM was used as an example of a hydrophilic agent. However, it is not limited to this. For example, ozonated water may be used as the hydrophilic agent. Hydroxyl groups can also be suitably formed on the surface WS by this modified embodiment.

[0329] The configuration of the third supply unit 15c is modified as appropriate when the hydrophilic agent is changed.

[0330] (3) In the hydrophilization process of the first and second embodiments, a hydrophilic agent was supplied to the substrate W. However, it is not limited to this. For example, in the hydrophilization process, at least one of UV treatment, plasma treatment, and ozone baking may be performed on the substrate W. Here, in UV treatment, ultraviolet light is irradiated onto the substrate W. In plasma treatment, plasma of the treatment gas is supplied to the substrate W. In ozone baking, ozone gas is supplied to the substrate W while the substrate W is heated. Hydroxyl groups can be suitably formed on the surface WS by this modified embodiment as well.

[0331] The configuration of the processing unit 11 is modified as appropriate in accordance with the changes to the hydrophilization process. For example, the processing unit 11 may include an irradiation unit that irradiates the substrate W with ultraviolet light. For example, the processing unit 11 may include a plasma generation unit that generates plasma. For example, the processing unit 11 may include a heating unit that heats the substrate W. For example, the processing unit 11 may include a gas supply unit that supplies ozone gas to the substrate W.

[0332] (4) In the hydrophobicization step of the second embodiment, a liquid water repellent was supplied to the substrate W. In the hydrophobicization step of the second embodiment, a mixed solution was supplied to the substrate W. However, it is not limited to this. For example, a gas of the water repellent may be supplied to the substrate W. For example, a vapor of the water repellent may be supplied to the substrate W. Here, the vapor of the water repellent may be supplied to the substrate W together with the vapor of the second solvent. For example, a vapor of the mixed solution may be supplied to the substrate W. For example, a mist of the water repellent may be supplied to the substrate W.

[0333] The composition of the 15g supply unit of the 7th supply unit will be changed as appropriate in accordance with the change in the water-repellent agent.

[0334] (5) In the first and second embodiments, the composition of the second rinse solution was the same as the composition of the first rinse solution. However, it is not limited to this. The composition of the second rinse solution may be different from the composition of the first rinse solution.

[0335] (6) In the second embodiment, the composition of the third replacement solution was the same as the composition of the second replacement solution. However, it is not limited to this. The composition of the third replacement solution may be different from the composition of the second replacement solution.

[0336] (7) In the first and second embodiments, the first supply source 19a generated the drying aid liquid g in the tank 22. However, it is not limited to this. For example, the first supply source 19a may generate the drying aid liquid g in a flow path communicating with the first supply unit 15a.

[0337] Figure 15 shows the configuration of the processing unit 11 and the first supply source 19a in a modified embodiment. Note that components identical to those in the embodiment are denoted by the same reference numerals, and detailed explanations are omitted.

[0338] The first supply source 19a comprises a first tank 41 and a second tank 42. The first tank 41 stores a sublimable substance M. For example, the first tank 41 may store a solvent together with the sublimable substance M. The second tank 42 stores a first solvent N. For example, the second tank 42 stores only the first solvent N.

[0339] The first supply source 19a includes a mixing unit 44. The mixing unit 44 communicates with the first tank 41 and the second tank 42. The mixing unit 44 generates a drying aid liquid g. The mixing unit 44 is further connected to the first supply unit 15a. The mixing unit 44 supplies the drying aid liquid g to the first supply unit 15a.

[0340] Specifically, the mixing section 44 includes pipes 45a and 45b and a fitting 46. Pipe 45a communicates with the first tank 41. Pipe 45a is connected to the first tank 41, for example. Pipe 45b communicates with the second tank 42. Pipe 45b is connected to the second tank 42, for example. The fitting 46 communicates with pipes 45a and 45b. The fitting 46 is connected to pipes 45a and 45b, for example.

[0341] The fitting 46 communicates with the first supply unit 15a. The fitting 46 is connected to the first supply unit 15a. The fitting 46 is connected to, for example, the piping 17a.

[0342] The mixing section 44 is equipped with pumps 47a and 47b. Pumps 47a and 47b are provided in piping 45a and 45b, respectively. Pump 47a sends the sublimable substance M from the first tank 41 to the joint 46 through piping 45a. Pump 47b sends the first solvent N from the second tank 42 to the joint 46 through piping 45b.

[0343] The mixing section 44 is equipped with filters 48a and 48b. Filters 48a and 48b are provided in piping 45a and 45b, respectively. The sublimable substance M passes through filter 48a. Filter 48a filters out the sublimable substance M. The first solvent N passes through filter 48b. Filter 48b filters out the first solvent N.

[0344] The mixing section 44 includes valves 49a and 49b. Valves 49a and 49b are provided in pipes 45a and 45b, respectively. Valve 49a adjusts the flow rate of the sublimable substance M flowing through pipe 45a. Valve 49b adjusts the flow rate of the first solvent N flowing through pipe 45b. Valves 49a and 49b may each include, for example, a flow control valve. Valves 49a and 49b may each include, for example, a flow control valve and an on / off valve.

[0345] An example of the operation of the first supply source 19a in a modified embodiment will be described. In the first or second supply step, the first supply source 19a generates a drying auxiliary liquid g and sends the drying auxiliary liquid g to the first supply unit 15a. Specifically, valves 49a and 49b are opened. Pump 47a pumps the sublimable substance M from the first tank 41 to the fitting 46. Pump 47b pumps the first solvent N from the second tank 42 to the fitting 46. Valve 49a adjusts the flow rate of the sublimable substance M flowing into the fitting 46. Valve 49b adjusts the flow rate of the first solvent N flowing into the fitting 46. The sublimable substance M and the first solvent N are mixed in the fitting 46. The sublimable substance M and solvent N become the drying auxiliary liquid g in the fitting 46. That is, the drying auxiliary liquid g is generated in the fitting 46. The mixing ratio R of the drying aid liquid g is adjusted by valves 49a and 49b. The drying aid liquid g flows from the fitting 46 to the first supply unit 15a. The nozzle 16a discharges the drying aid liquid g.

[0346] The joint 46 corresponds to the "flow path communicating with the first supply section 15a" as described above.

[0347] According to this modified embodiment, it is not necessary to store the drying aid liquid g before it is supplied to the first supply unit 15a. Therefore, the mixing ratio R of the drying aid liquid g can be controlled with high precision. As a result, the substrate W is dried more appropriately.

[0348] Furthermore, the first supply source 19a does not include a tank 22. Therefore, the structure of the first supply source 19a is preferably simplified. The first supply source 19a is preferably miniaturized.

[0349] (8) In the solidification film formation step of the first embodiment, the substrate W was not cooled. In the sublimation step of the first embodiment, the substrate W was not cooled. However, this is not limited to the above. For example, in the solidification film formation step, the substrate W may be cooled. For example, in the sublimation step, the substrate W may be cooled. For example, in both the solidification film formation step and the sublimation step, the substrate W may be cooled. The modified embodiments will be described in detail below.

[0350] (8-1) Configuration of the modified embodiment This modified embodiment will be described with reference to the drawings. Note that components identical to those in the first embodiment are denoted by the same reference numerals, and detailed explanations will be omitted. The general overview of the substrate processing apparatus 1 and the configuration of the first supply source 19a are substantially the same in this modified embodiment as in the first embodiment. The configuration of the processing unit 11 in this modified embodiment will now be described.

[0351] Figure 16 shows the configuration of the processing unit 11 in a modified embodiment. Figure 16 also shows a simplified illustration of the first supply source 19a.

[0352] The substrate W has a surface WS. Surface WS includes a first surface WS1 and a second surface WS2. The second surface WS2 is located on the opposite side of the first surface. A pattern WP is formed on the first surface WS1. Pattern WP includes a protrusion T. Figure 16 omits the illustration of pattern WP and protrusion T.

[0353] The substrate W is described as it is held by the substrate holder 13. When the substrate W is held by the substrate holder 13, the substrate W is in a nearly horizontal position. The first surface WS1 faces upward. The first surface WS1 is located on the top surface of the substrate W. The pattern WP faces upward. The pattern WP is located on the top surface of the substrate W. The second surface WS2 faces downward. The second surface WS2 is located on the bottom surface of the substrate W. The bottom surface of the substrate W is also called the back side of the substrate W.

[0354] An example of the configuration of the substrate holding portion 13 will be described. The substrate holding portion 13 includes a support member 13a. The support member 13a has a plate shape. The support member 13a extends in the horizontal direction. Although not shown in the figures, the support member 13a has approximately the same size as the substrate W in a plan view. The support member 13a has an annular shape in a plan view. The support member 13a forms an opening. In a plan view, the opening of the support member 13a is located in the center of the support member 13a.

[0355] The substrate holder 13 comprises a plurality of retaining pins 13b. Each retaining pin 13b is supported by a support member 13a. Each retaining pin 13b is positioned on the periphery of the support member 13a. Each retaining pin 13b extends upward from the support member 13a. Each retaining pin 13b holds the substrate W. When the substrate W is held by the retaining pins 13b, the support member 13a is positioned below the substrate W.

[0356] An example configuration of the rotary drive unit 14 will be described. The rotary drive unit 14 comprises a shaft portion 14a and a motor 14b. The shaft portion 14a is connected to a support member 13a. The shaft portion 14a extends downward from the support member 13a. The shaft portion 14a extends along the rotation axis B. The shaft portion 14a is a so-called hollow shaft. The shaft portion 14a has a cylindrical shape. The shaft portion 14a forms a hollow portion. The hollow portion of the shaft portion 14a is located inside the shaft portion 14a. The hollow portion of the shaft portion 14a is connected to an opening in the support member 13a. The motor 14b is connected to the shaft portion 14a. The motor 14b rotates the shaft portion 14a around the rotation axis B.

[0357] The processing unit 11 includes a cooling unit 51. The cooling unit 51 cools the substrate W. The cooling unit 51 cools the substrate W held by the substrate holding unit 13.

[0358] The cooling unit 51 cools the second surface WS2 of the substrate W. The cooling unit 51 directly cools the second surface WS2. The cooling unit 51 does not directly cool the first surface WS1.

[0359] The cooling unit 51 cools the substrate W to a first cooling temperature. The first cooling temperature is, for example, lower than the ambient temperature around the substrate W. The first cooling temperature is, for example, lower than the ambient temperature above the substrate W. The first cooling temperature is, for example, lower than room temperature. When the housing 12 houses the substrate W, the room temperature is the temperature of the gas J inside the housing 12. The room temperature is, for example, 24 degrees. The first cooling temperature is, for example, 10 degrees or less.

[0360] The first cooling temperature is, for example, higher than 0 degrees. The first cooling temperature is, for example, higher than 0 degrees and 10 degrees or less.

[0361] The cooling unit 51 includes a coolant supply unit 55. The coolant supply unit 55 supplies coolant to the substrate W, for example. The coolant has, for example, a first cooling temperature. The coolant has, for example, a second cooling temperature. The second cooling temperature is lower than the first cooling temperature. For example, the second cooling temperature is slightly lower than the first cooling temperature. The coolant is, for example, water. The coolant is, for example, deionized water (DIW).

[0362] The coolant supply unit 55 supplies coolant to the second surface WS2, for example. The coolant supply unit 55 does not supply coolant to the first surface WS1, for example.

[0363] An example configuration of the coolant supply unit 55 will be described. The coolant supply unit 55 has a nozzle 56, piping 57, and a valve 58. The nozzle 56 discharges coolant. Piping 57 is connected to the nozzle 56. The valve 58 is provided on the piping 57. When the valve 58 is open, the nozzle 56 discharges coolant. When the valve 58 is closed, the nozzle 56 does not discharge coolant.

[0364] The nozzle 56 is installed inside the housing 12. The nozzle 56 is positioned below the substrate W held by the substrate holding portion 13, for example. The nozzle 56 is positioned at the opening of the support member 13a, for example. The nozzle 56 discharges coolant upward, for example. The nozzle 56 discharges coolant toward the second surface WS2. The nozzle 56 discharges coolant toward the center of the second surface WS2. Part of the piping 57 is provided inside the housing 12, for example. Part of the piping 57 is positioned in the hollow part of the shaft portion 14a, for example. Another part of the piping 57 is provided outside the housing 12, for example. The valve 58 is provided outside the housing 12, for example.

[0365] The coolant supply unit 55 communicates with the coolant supply source 59. The coolant supply source 59 is connected to the coolant supply unit 55. The coolant supply source 59 is connected, for example, to piping 57. The coolant supply source 59 is provided outside the housing 12. The coolant supply source 59 supplies coolant to the coolant supply unit 55. The coolant supply source 59 may further adjust the temperature of the coolant. The coolant supply source 59 may adjust the temperature of the coolant to, for example, a first cooling temperature. The coolant supply source 59 may adjust the temperature of the coolant to, for example, a second cooling temperature. The coolant supply source 59 may supply coolant to a plurality of processing units 11. Alternatively, the coolant supply source 59 may supply coolant to only one processing unit 11. The coolant supply source 59 may be an element of the substrate processing apparatus 1. Alternatively, the coolant supply source 59 may not be an element of the substrate processing apparatus 1.

[0366] The dry gas supplied by the sixth supply unit 15f preferably has a dew point lower than the first cooling temperature. The dry gas preferably has a dew point lower than the second cooling temperature. The dry gas is, for example, at least one of air and an inert gas. Air is, for example, compressed air. The inert gas is, for example, nitrogen gas.

[0367] (8-2) Example of operation of a modified embodiment The substrate processing method of this modified embodiment comprises steps S1, S11-S19 described in the first embodiment. For convenience, please refer to Figure 5. The operations of steps S1-S16 and S19 are substantially the same between the first embodiment and this modified embodiment. Therefore, the explanation of the operations of steps S1-S16 and S19 will be omitted. The operations of steps S17 and S18 will be explained.

[0368] Step S17: Solidification film formation process Figure 17 schematically shows the substrate W in the solidification film formation process of a modified embodiment. In the solidification film formation process, the first solvent evaporates from the drying aid liquid g on the substrate W. The drying aid liquid g on the substrate W forms a liquid film G. The drying aid liquid g on the substrate W is appropriately referred to as the liquid film G. In the solidification film formation process, a solidified film K is formed on the substrate W. Furthermore, in the solidification film formation process, the substrate W is cooled.

[0369] In the solidification film formation process, the substrate W is cooled to, for example, a first cooling temperature.

[0370] In the solidification film formation process, the second surface WS2 is cooled directly. In the solidification film formation process, the substrate W is cooled by the cooling unit 51. Note that Figure 17 omits the illustration of the second surface WS2 and the cooling unit 51.

[0371] In the solidification film formation process, the substrate W is cooled by supplying a cooling liquid to it.

[0372] Specifically, the coolant supply unit 55 supplies coolant to the substrate W held by the substrate holding unit 13. More specifically, the valve 58 opens. The nozzle 56 discharges coolant. The coolant comes into contact with the second surface WS2. The coolant flows along the second surface WS2. For example, the coolant flows along the second surface WS2, from the center of the second surface WS2 to the periphery of the second surface WS2. The coolant removes heat from the second surface WS2. The second surface WS2 is cooled directly. The temperature of the second surface WS2 decreases. The temperature of the second surface WS2 decreases to, for example, a first cooling temperature.

[0373] Furthermore, the coolant is not supplied to the first surface WS1 of the substrate W. The coolant does not come into contact with the first surface WS1. The first surface WS1 is not directly cooled.

[0374] The first surface WS1 is cooled indirectly via the second surface WS2. The temperature of the first surface WS1 decreases. Specifically, the temperature of the pattern WP decreases. The temperature of the protrusion T decreases. The temperature of the first surface WS1 decreases, for example, to the first cooling temperature.

[0375] As a result, the temperature of the first surface WS1 is lower than the temperature of the ambient air surrounding the substrate W. The temperature of the first surface WS1 is lower than room temperature. Specifically, the temperature of the first surface WS1 is lower than the temperature of the gas J.

[0376] Furthermore, the coolant is not added to the liquid film G. The liquid film G is not directly cooled.

[0377] The liquid film G is in contact with the first surface WS1. The liquid film G is indirectly cooled through the first surface WS1.

[0378] The interface between the liquid film G and the first surface WS1 is called the "solid-liquid interface." The interface between the liquid film G and the gas J is called the "gas-liquid interface." The solid-liquid interface is located at the bottom of the liquid film G. The gas-liquid interface is located at the top of the liquid film G. The gas-liquid interface is located on the top surface G1 of the liquid film G. The portion of the liquid film G located near the solid-liquid interface cools faster than the portion of the liquid film G located near the gas-liquid interface. Therefore, the temperature of the portion of the liquid film G located near the solid-liquid interface is lower than the temperature of the portion of the liquid film G located near the gas-liquid interface.

[0379] The lower the temperature of the treatment solution g, the more easily the sublimable substance in the treatment solution g solidifies. The lower the temperature of the treatment solution g, the more easily the sublimable substance in the treatment solution g precipitates. Therefore, the lower the temperature of the treatment solution g, the more efficiently the solidified film K is formed. The lower the temperature of the treatment solution g, the more the formation of the solidified film K is promoted.

[0380] Therefore, the portion of the liquid film G located near the solid-liquid interface is the first to transform into the solidified film K. The bottom of the liquid film G is the first to transform into the solidified film K. In other words, the portion of the liquid film G located near the gas-liquid interface transforms into the solidified film K before the portion of the liquid film G located near the gas-liquid interface transforms into the solidified film K. The bottom of the liquid film G transforms into the solidified film K before the top of the liquid film G transforms into the solidified film K. The formation of the solidified film K near the solid-liquid interface occurs before the formation of the solidified film K near the gas-liquid interface. The location where the solidified film K first occurs in the solidified film formation process is, for example, the solid-liquid interface.

[0381] The solidified film K is formed uniformly over the entire first surface WS1, for example. The solidified film K is formed uniformly over the entire first surface WS1, for example. The solidified film K has a uniform thickness over the entire first surface WS1, for example. The solidified film K extends along the first surface WS1, for example. One solidified film K extends over the entire first surface WS1, for example. The solidified film K is not separated into multiple parts, for example. The solidified film K does not have holes that expose the first surface WS1 to the liquid film G or gas J. The solidified film K covers the entire first surface WS1, for example. The solidified film K is in contact with the entire first surface WS1, for example. The first surface WS1 has no portion in contact with the liquid film G, for example. The first surface WS1 has no portion in contact with the gas J.

[0382] The pattern WP is formed on the first surface WS1. Therefore, the solidified film K is formed uniformly, for example, over the entire pattern WP. The solidified film K is formed uniformly over the entire pattern WP. The solidified film K has a uniform thickness over the entire pattern WP. For example, the solidified film K extends along the pattern WP. For example, one solidified film K extends over the entire pattern WP. For example, the solidified film K is not separated into multiple parts. For example, the solidified film K does not have holes that expose the pattern WP to the liquid film G or gas J. The solidified film K covers the entire pattern WP, for example. The solidified film K is in contact with the entire pattern WP, for example. The pattern WP does not have any parts that come into contact with the liquid film G. The pattern WP does not have any parts that come into contact with the gas J.

[0383] Figure 18 schematically shows the substrate W in the solidification film formation process of a modified embodiment. The solidification film K further increases. For example, the solidification film K increases from the bottom of the liquid film G toward the top of the liquid film G. For example, the solidification film K increases toward the upper surface G1 of the liquid film G.

[0384] The solidified film K increases uniformly, for example, across the entire first surface WS1. The thickness of the solidified film K does not vary excessively, for example, across the entire first surface WS1.

[0385] Therefore, the solidified film K increases uniformly, for example, across the entire pattern WP. The thickness of the solidified film K does not vary excessively, for example, across the entire pattern WP.

[0386] For convenience, refer to Figure 8. Eventually, the entire liquid film G disappears from the substrate W. The liquid film G does not remain in the recess A. The entire first solvent disappears from the substrate W. The first solvent also does not remain in the recess A. Only the solidified film K remains on the substrate W. Only the solidified film K remains on the first surface WS1.

[0387] Step S18: Sublimation process In the sublimation process, the solidified film K sublimes.

[0388] In the sublimation process, a drying gas is supplied to the substrate W. Specifically, the sixth supply unit 15f supplies the drying gas to the substrate W held by the substrate holding unit 13. The drying gas is supplied to the first surface WS1. The drying gas is supplied to the solidified film K. The solidified film K is exposed to the drying gas. The solidified film K sublimes suitably. The solidified film K changes suitably into a gas without passing through a liquid state.

[0389] The sixth supply unit 15f is an example of a drying gas supply unit in the present invention.

[0390] Furthermore, the substrate W is cooled during the sublimation process. The process of cooling the substrate W during the sublimation process is substantially the same as the process of cooling the substrate W during the solidification film formation process.

[0391] In the sublimation process, the substrate W is cooled to, for example, a first cooling temperature. In the sublimation process, the second surface WS2 is cooled directly. In the sublimation process, the substrate W is cooled by the cooling unit 51. In the sublimation process, the substrate W is cooled by supplying a cooling liquid to the substrate W.

[0392] For example, the cooling unit 51 continues to cool the substrate W from the solidification film formation process to the sublimation process. For example, the cooling unit 51 does not interrupt the cooling of the substrate W between the solidification film formation process and the sublimation process.

[0393] Specifically, the coolant supply unit 55 supplies coolant to the substrate W held by the substrate holding unit 13. The coolant is supplied to the second surface WS2. The coolant is not supplied to the first surface WS1. The coolant is not supplied to the solidification film K. The second surface WS2 is cooled directly. The first surface WS1 is not cooled directly. The first surface WS1 is cooled indirectly via the second surface WS2. The solidification film K is not cooled directly. The solidification film K is cooled indirectly via the first surface WS1.

[0394] The solidified film K is cooled. Therefore, the solidified film K is difficult to melt. That is, the solidified film K is difficult to change into a liquid. Consequently, the solidified film K sublimes more favorably. The solidified film K changes into a gas more favorably, without passing through a liquid state.

[0395] For convenience, refer to Figures 9 and 10. The solidified film K sublimes. By sublimation, the solidified film K is removed from the substrate W. The substrate W is dried.

[0396] Subsequently, the sixth supply unit 15f stops supplying the drying gas. Specifically, valve 18f closes. Nozzle 16f stops blowing out the drying gas. Furthermore, the cooling unit 51 stops cooling the substrate W. Specifically, the coolant supply unit 55 stops supplying the coolant. More specifically, valve 58 closes. Nozzle 56 stops discharging the coolant.

[0397] (8-3) Technical significance of cooling substrate W Examples 1 and 3 illustrate the technical significance of cooling the substrate W. Example 1 was described in "1-6. Technical Significance of the Hydrophilization Process" of the First Embodiment.

[0398] The conditions for Example 3 are described below. The process for processing the substrate W is the same between Example 1 and Example 3. That is, in Example 3 as well, the substrate W is processed in the etching step, the first rinsing step, the hydrophilization step, the second rinsing step, the first substitution step, the first supply step, the solidification film formation step, and the sublimation step. In the solidification film formation step and the sublimation step of Example 3, the substrate W is cooled. Except for the fact that the substrate W is cooled in the solidification film formation step and the sublimation step, the conditions for Example 3 are the same as those for Example 1. Note that in the solidification film formation step and the sublimation step of Example 1, the substrate W is not cooled.

[0399] Each substrate W processed in Example 1 and Example 3 was evaluated by its collapse rate.

[0400] The collapse rate of the substrate W processed in Example 3 was lower than that of the substrate W processed in Example 1.

[0401] Therefore, in Example 3, the substrate W was dried more effectively. In Example 3, the pattern WP was protected more effectively. In Example 3, the collapse of the pattern WP was prevented more effectively. In Example 3, the substrate W was dried with the pattern WP more effectively protected. The quality of the process in Example 3 was further improved from the quality of the process in Example 1.

[0402] (8-4) Effects of the modified embodiment This modified embodiment also produces the same effects as the first embodiment. For example, the substrate processing method of this modified embodiment comprises a hydrophilization step, a first supply step, a solidification film formation step, and a sublimation step. The sublimable substance includes an organic compound containing an oxime group. Therefore, in the solidification film formation step, the solidification film K is appropriately formed along the pattern WP. Thus, the substrate W is appropriately dried.

[0403] Furthermore, this modified embodiment provides the following effects.

[0404] During the solidification film formation process, the substrate W is cooled. Therefore, the formation of the solidification film K is further promoted during this process. As a result, the solidification film K is formed more favorably along the pattern WP. Consequently, the substrate W is dried more effectively.

[0405] In the solidification film formation process, the substrate W is cooled to a first cooling temperature. This further promotes the formation of the solidified film K.

[0406] The first cooling temperature is, for example, lower than the temperature of the ambient air surrounding the substrate W. Specifically, in the solidification film formation process, the substrate W is cooled to a temperature lower than the ambient air surrounding it. This further promotes the formation of the solidification film K.

[0407] The first cooling temperature is, for example, lower than room temperature. Specifically, in the solidification film formation process, the substrate W is cooled to a temperature lower than room temperature. This further promotes the formation of the solidification film K.

[0408] The first cooling temperature is, for example, lower than the temperature of the gas J. Specifically, in the solidification film formation process, the substrate W is cooled to a temperature lower than the temperature of the gas J inside the housing 12 that contains the substrate W. Therefore, the formation of the solidification film K is further promoted.

[0409] The first cooling temperature is, for example, 10 degrees Celsius or lower. Specifically, in the solidification film formation process, the substrate W is cooled to a temperature of 10 degrees Celsius or lower. This further promotes the formation of the solidification film K.

[0410] The first cooling temperature is, for example, higher than 0 degrees. Specifically, in the solidification film formation process, the substrate W is cooled to a temperature higher than 0 degrees. Therefore, the temperature of the substrate W is not excessively low. Thus, in the solidification film formation process, the atmosphere surrounding the substrate W is less likely to condense on the substrate W. In the solidification film formation process, the gas J is less likely to condense on the substrate W. Therefore, the substrate W is dried more effectively.

[0411] The first cooling temperature is, for example, higher than 0 degrees and 10 degrees or lower. Specifically, in the solidification film formation process, the substrate W is cooled to a temperature higher than 0 degrees and 10 degrees or lower. As a result, the formation of the solidification film K is further promoted. Furthermore, in the solidification film formation process, the atmosphere surrounding the substrate W is less likely to condense on the substrate W. In the solidification film formation process, the gas J is less likely to condense on the substrate W. Therefore, the substrate W is dried more effectively.

[0412] In the solidification film formation process, the second surface WS2 is directly cooled. The second surface WS2 is located on the opposite side of the first surface WS1 where the pattern WP is formed. Therefore, the formation of the solidification film K near the solid-liquid interface is favorably promoted. Specifically, the solidification film K is efficiently formed at the interface between the first surface WS1 and the drying aid liquid g. Thus, the solidification film K is formed even more favorably along the pattern WP. Consequently, the substrate W is dried even more appropriately.

[0413] In the solidification film formation process, the substrate W is cooled by supplying a cooling liquid to it. Therefore, the substrate W is suitably cooled during the solidification film formation process.

[0414] During the sublimation process, the substrate W is cooled. As a result, the solidified film K sublimes nicely during the sublimation process. Therefore, the substrate W is dried more effectively.

[0415] In the sublimation process, the substrate W is cooled to a first cooling temperature. As a result, the solidified film K sublimes appropriately.

[0416] The first cooling temperature is, for example, lower than the ambient temperature surrounding the substrate W. Specifically, in the sublimation process, the substrate W is cooled to a temperature lower than the ambient temperature surrounding the substrate W. As a result, the solidified film K sublimes favorably.

[0417] The first cooling temperature is, for example, lower than room temperature. Specifically, in the sublimation process, the substrate W is cooled to a temperature lower than room temperature. As a result, the solidified film K sublimes favorably.

[0418] The first cooling temperature is, for example, lower than the temperature of the gas J. Specifically, in the sublimation process, the substrate W is cooled to a temperature lower than the temperature of the gas J inside the housing 12 that contains the substrate W. As a result, the solidified film K sublimes favorably.

[0419] The first cooling temperature is, for example, 10 degrees Celsius or lower. Specifically, in the sublimation process, the substrate W is cooled to a temperature of 10 degrees Celsius or lower. As a result, the solidified film K sublimes favorably.

[0420] The first cooling temperature is, for example, higher than 0 degrees. Specifically, in the sublimation process, the substrate W is cooled to a temperature higher than 0 degrees. Therefore, the temperature of the substrate W is not excessively low. Thus, in the sublimation process, the atmosphere surrounding the substrate W is less likely to condense on the substrate W. In the sublimation process, the gas J is less likely to condense on the substrate W. Therefore, the substrate W is dried more effectively.

[0421] The first cooling temperature is, for example, higher than 0 degrees and 10 degrees or lower. Specifically, in the sublimation process, the substrate W is cooled to a temperature higher than 0 degrees and 10 degrees or lower. As a result, the solidified film K sublimes suitably. Furthermore, in the sublimation process, the atmosphere surrounding the substrate W is less likely to condense on the substrate W. In the sublimation process, the gas J is less likely to condense on the substrate W. Therefore, the substrate W is dried more appropriately.

[0422] During the sublimation process, the second surface WS2 is directly cooled. The second surface WS2 is located on the opposite side of the first surface WS1 where the pattern WP is formed. Therefore, the substrate W is dried while the pattern WP is suitably protected. Consequently, the substrate W is dried more effectively.

[0423] In the sublimation process, the substrate W is cooled by supplying a cooling liquid to it. Therefore, the substrate W is suitably cooled during the sublimation process.

[0424] In the sublimation process, a drying gas is supplied to the substrate W. As a result, the solidified film K sublimes appropriately.

[0425] The drying gas has a dew point lower than, for example, the first cooling temperature. Therefore, the drying gas is less likely to condense on the substrate W. Consequently, the substrate W is dried more effectively.

[0426] The dry gas has a dew point lower than, for example, the second cooling temperature. Therefore, the dry gas is less likely to condense on the substrate W.

[0427] The drying gas is, for example, an inert gas. Therefore, the drying gas does not condense on the substrate W.

[0428] In the sublimation process, drying gas is supplied to the first surface WS1. Therefore, condensation on the first surface WS1 is effectively prevented. Consequently, condensation on the pattern WP is effectively prevented. Therefore, the substrate W is dried more effectively.

[0429] The substrate processing apparatus 1 includes a cooling unit 51. The cooling unit 51 cools the substrate W. Therefore, the substrate W is suitably cooled. Consequently, the substrate W is processed more appropriately.

[0430] The cooling unit 51 directly cools the second surface WS2. Therefore, the substrate W is cooled more effectively. Consequently, the substrate W is processed more appropriately.

[0431] The cooling unit 51 includes a coolant supply unit 55. The coolant supply unit 55 supplies coolant to the substrate W. Therefore, the cooling unit 51 effectively cools the substrate W.

[0432] The coolant supply unit 55 supplies coolant to the second surface WS2. As a result, the cooling unit 51 effectively cools the second surface WS2.

[0433] The coolant supply unit 55 is equipped with a nozzle 56. The nozzle 56 discharges coolant. Therefore, the coolant supply unit 55 optimally supplies coolant to the substrate W.

[0434] When the substrate W is held by the substrate holding section 13, the second surface WS2 faces downward. The nozzle 56 is positioned below the substrate W held by the substrate holding section 13. Therefore, the coolant supply section 55 supplies coolant to the second surface WS2 effectively.

[0435] In the solidification film formation process, the cooling unit 51 cools the substrate W. This further promotes the formation of the solidification film K. As a result, the solidification film K is formed more favorably along the pattern WP. Consequently, the substrate W is dried more appropriately.

[0436] During the sublimation process, the cooling unit 51 cools the substrate W. As a result, the solidified film K sublimes appropriately. Therefore, the substrate W is dried more effectively.

[0437] The substrate processing apparatus 1 includes a sixth supply unit 15f. The sixth supply unit 15f supplies drying gas to the substrate W. The drying gas is less likely to condense on the substrate W. Therefore, the substrate W is dried more effectively.

[0438] The sixth supply unit 15f supplies drying gas to the first surface WS1. Therefore, condensation on the first surface WS1 is effectively prevented. Consequently, condensation on the pattern WP is effectively prevented. Thus, the substrate W is treated more appropriately.

[0439] In the sublimation process, the sixth supply unit 15f supplies drying gas to the substrate W. As a result, the solidified film K sublimes appropriately. Therefore, the substrate W is properly dried. Furthermore, the drying gas is less likely to condense on the substrate W. Therefore, the substrate W is dried even more appropriately.

[0440] (8-5) Further modifications of the modified embodiment The cooling unit 51 in the modified embodiment described above includes a coolant supply unit 55. However, it is not limited to this. The cooling unit 51 may include at least one of the coolant supply unit 55, a cooling gas supply unit, and a cooling plate.

[0441] The cooling gas supply unit will now be described. The cooling gas supply unit supplies cooling gas to the substrate W. The substrate W is cooled by the cooling gas. The cooling gas supply unit cools the substrate W to, for example, a first cooling temperature. The cooling gas has, for example, a first cooling temperature. The cooling gas has, for example, a second cooling temperature. The cooling gas is, for example, at least one of air and an inert gas. It is preferable that the cooling gas has a dew point lower than the first cooling temperature. It is preferable that the cooling gas has a dew point lower than the second cooling temperature.

[0442] The cooling gas supply unit supplies cooling gas to the second surface WS2, for example. The cooling gas comes into contact with the second surface WS2, for example. The cooling gas flows along the second surface WS2, for example. The cooling gas removes heat from the second surface WS2, for example.

[0443] The cooling gas supply unit does not supply cooling gas to the first surface WS1, for example.

[0444] The cooling gas supply unit includes, for example, a nozzle. The nozzle of the cooling gas supply unit blows out cooling gas. The nozzle of the cooling gas supply unit is positioned below the substrate W held by the substrate holding unit 13. For example, the nozzle of the cooling gas supply unit may be a nozzle 56. That is, the cooling gas supply unit and the coolant supply unit 55 may share a nozzle 56. The nozzle 56 may discharge coolant and also discharge cooling gas. Alternatively, the nozzle of the cooling gas supply unit may be a different component from the nozzle 56.

[0445] The cooling gas supply unit may further include piping and a valve. The piping is connected to a nozzle. The piping delivers cooling gas to the nozzle. A valve is provided in the piping. The valve controls the discharge of the cooling gas.

[0446] The cooling plate is described below. The cooling plate is in contact with the substrate W. The substrate W is cooled by the cooling plate. The cooling plate cools the substrate W to, for example, a first cooling temperature. The cooling plate has, for example, a first cooling temperature. The cooling plate has, for example, a second cooling temperature.

[0447] The substrate W is placed on a cooling plate. The cooling plate contacts, for example, the second surface WS2. The cooling plate makes surface contact with, for example, the second surface WS2. The cooling plate makes contact with, for example, the entire second surface WS2. For example, the cooling plate removes heat from the second surface WS2.

[0448] The cooling plate does not come into contact with, for example, the first surface WS1.

[0449] The cooling unit 51 may further include a configuration for adjusting the temperature of the cooling plate. For example, the cooling unit 51 may include a flow path. The flow path is formed, for example, inside the cooling plate. A heat transfer fluid flows through the flow path. The heat transfer fluid adjusts the temperature of the cooling plate. For example, the cooling unit 51 may include a heat exchanger. The heat exchanger adjusts the temperature of the cooling plate. The heat exchanger is, for example, attached to the cooling plate. For example, the cooling unit 51 may include a Peltier element. The Peltier element adjusts the temperature of the cooling plate. For example, the Peltier element is, for example, attached to the cooling plate.

[0450] The cooling plate is positioned below the substrate W held by the substrate holder 13. The cooling plate may be rotatably mounted. For example, the cooling plate may rotate about axis B. Alternatively, the cooling plate may be non-rotatably mounted. For example, the cooling plate may be fixed to the housing 12. The cooling plate may be movable in the vertical direction Z relative to the substrate W held by the substrate holder 13. Alternatively, the cooling plate may be non-movable in the vertical direction Z relative to the substrate W held by the substrate holder 13. The cooling plate may be, for example, at least a part of the substrate holder 13. The cooling plate may be, for example, at least a part of the support member 13a. Alternatively, the cooling plate may be a separate member from the substrate holder 13.

[0451] In the sublimation process of the modified embodiment described above, the substrate W was cooled. However, this is not limited to this. For example, the substrate W does not need to be cooled for at least a portion of the sublimation process. For example, the cooling of the substrate W may be terminated before the sublimation process is completed.

[0452] In the first supply step of the modified embodiment described above, the substrate W was not cooled. However, this is not limited to this. For example, the substrate W may be cooled for at least a portion of the first supply step. For example, cooling of the substrate W may be started before the first supply step is completed. For example, cooling of the substrate W may be started before the solidification film formation step is started.

[0453] In the modified embodiment described above, the substrate W was processed inside the housing 12 during the solidification film formation process. The processing unit 11 performing the solidification film formation process was the same as the processing unit 11 performing the first supply process. However, it is not limited to this. In the solidification film formation process, the substrate W may be processed outside the housing 12. The processing unit performing the solidification film formation process may be different from the processing unit 11 performing the first supply process. The configuration of the processing unit performing the solidification film formation process may be different from the configuration of the processing unit 11 performing the first supply process. The processing unit 11 performing the first supply process does not have, for example, a cooling unit 51. The processing unit performing the solidification film formation process may have, for example, a cooling unit. In this case, the cooling unit provided in the processing unit performing the solidification film formation process cools the substrate W inside the processing unit performing the solidification film formation process. The cooling unit provided in the processing unit performing the solidification film formation process does not cool the substrate W held by the substrate holding unit 13.

[0454] In the modified embodiment described above, the substrate W was processed inside the housing 12 during the sublimation process. The processing unit 11 performing the sublimation process was the same as the processing unit 11 performing the first supply process. However, it is not limited to this. In the sublimation process, the substrate W may be processed outside the housing 12. The processing unit performing the sublimation process may be different from the processing unit 11 performing the first supply process. The configuration of the processing unit performing the sublimation process may be different from the configuration of the processing unit 11 performing the first supply process. The processing unit 11 performing the first supply process does not have, for example, a cooling unit 51. The processing unit performing the sublimation process may have, for example, a cooling unit. In this case, the cooling unit provided in the processing unit performing the sublimation process cools the substrate W inside the processing unit performing the sublimation process. The cooling unit provided in the processing unit performing the sublimation process does not cool the substrate W held by the substrate holding unit 13.

[0455] In the solidification film formation process of the modified embodiment described above, the substrate W may be treated in an atmosphere consisting of a dry gas. In the solidification film formation process, the substrate W may be treated in an atmosphere consisting only of a dry gas. In the solidification film formation process, the gas J inside the housing 12 may consist only of a dry gas. In the solidification film formation process, the housing 12 may be sealed. In the solidification film formation process, the inside of the housing 12 may be isolated from the outside of the housing 12. This further effectively prevents condensation on the substrate W during the solidification film formation process.

[0456] In the sublimation process of the modified embodiment described above, the substrate W may be processed in an atmosphere consisting of a dry gas. In the sublimation process, the substrate W may be processed in an atmosphere consisting only of a dry gas. In the sublimation process, the gas J inside the housing 12 may consist only of a dry gas. In the sublimation process, the housing 12 may be sealed. In the sublimation process, the inside of the housing 12 may be isolated from the outside of the housing 12. This further effectively prevents condensation on the substrate W during the sublimation process.

[0457] (9) The substrate processing method of the first embodiment comprises an etching step, a first rinsing step, a second rinsing step, and a first replacement step. However, it is not limited to this. For example, at least one of the etching step, the first rinsing step, the second rinsing step, and the first replacement step may be omitted. For example, the etching step, the first rinsing step, the second rinsing step, and the first replacement step may all be omitted.

[0458] (10) The substrate processing method of the second embodiment comprises an etching step, a first rinsing step, a hydrophilization step, a second rinsing step, a second substitution step, and a third substitution step. However, it is not limited to these steps. For example, at least one of the etching step, the first rinsing step, the hydrophilization step, the second rinsing step, the second substitution step, and the third substitution step may be omitted. For example, all of the etching step, the first rinsing step, the hydrophilization step, the second rinsing step, the second substitution step, and the third substitution step may be omitted.

[0459] (11) In the first embodiment, when the first supply step is started, a liquid (e.g., the first replacement liquid) is present on the substrate W. That is, in the first supply step, the drying aid liquid g is supplied to the substrate W, which is not yet dry. However, this is not limited to this. For example, when the first supply step is started, the liquid (e.g., the first replacement liquid) does not have to be present on the substrate W. For example, in the first supply step, the drying aid liquid g may be supplied to the substrate W, which is already dry.

[0460] Similarly, in the second embodiment, when the second supply step was started, a liquid (e.g., the third replacement liquid) was present on the substrate W. That is, in the second supply step, the drying aid liquid g was supplied to the substrate W, which was not yet dry. However, this is not limited to this. For example, when the second supply step was started, the liquid (e.g., the third replacement liquid) did not have to be present on the substrate W. For example, in the second supply step, the drying aid liquid g may be supplied to the substrate W, which was already dry.

[0461] (12) In the first supply step of the first embodiment, the drying auxiliary liquid g removed the first replacement liquid from the substrate W. In the second supply step of the second embodiment, the drying auxiliary liquid g removed the third replacement liquid from the substrate W. However, it is not limited to these. For example, in at least one of the first supply step and the second supply step, the drying auxiliary liquid g may wash the substrate W. For example, in at least one of the first supply step and the second supply step, the drying auxiliary liquid g may remove foreign matter adhering to the substrate W. For example, in at least one of the first supply step and the second supply step, the drying auxiliary liquid g may dissolve foreign matter adhering to the substrate W. Foreign matter is, for example, resist residue.

[0462] (13) In the solidification film formation process of the first and second embodiments, the drying gas was not supplied to the substrate W. However, this is not limited to the first and second embodiments. In the solidification film formation process, the drying gas may be supplied to the substrate W. In the solidification film formation process, the drying gas may be supplied to the drying auxiliary liquid g on the substrate W. According to this modified embodiment, in the solidification film formation process, the drying auxiliary liquid g on the substrate W is exposed to the drying gas. Therefore, in the solidification film formation process, the solvent evaporates efficiently from the drying auxiliary liquid g on the substrate W. In the solidification film formation process, the solidified film K is efficiently formed on the substrate W.

[0463] (14) In the first and second embodiments, the pattern WP on the substrate W may be formed on the substrate W before the processing unit 11 processes the substrate W. Alternatively, the pattern WP may be formed on the substrate W in an etching step (step S11), for example.

[0464] (15) The first and second embodiments and the modified embodiments described in (1) to (14) above may be further modified as appropriate by substituting or combining each component with the components of other modified embodiments. [Explanation of Symbols]

[0465] 1 ... Substrate processing equipment 10 ... Control Unit 11… Processing Unit 13... Board holding part 15 … Supply section 15a... 1st supply section 15c... Third supply section (hydrophilization section) 15f… Supply Unit No. 6 (Dry Gas Supply Unit) 15g… 7th supply section (hydrophobic section) 51 … Cooling section g … Drying auxiliary liquid G... Liquid film of drying aid G1 ... Top surface of the liquid film J... gas K... Solidified film K1 ... Top surface of the solidified film L... Interface between the side of the protrusion and the drying aid. L1 … 1st area L2…Second area M…sublimable substance N ... First solvent W… Circuit board WS… Surface of the substrate WS1 ... The first surface of the substrate WP… Pattern T... protruding part T1… Side of the convex part A... recessed

Claims

1. A substrate processing method for processing a substrate having a pattern formed on its surface, A hydrophilization process to form hydroxyl groups on the surface of the substrate, A first supply step involves supplying a substrate having hydroxyl groups with a drying aid containing a sublimable substance containing an organic compound containing oxime groups and a first solvent, thereby bonding the hydroxyl groups and the oxime groups and attracting the sublimable substance to the surface of the substrate. A solidification film formation step involves evaporating the first solvent from the drying aid liquid on the substrate to form a solidified film containing the sublimable substance on the substrate, A sublimation step for sublimating the solidified film, Equipped with, The sublimable substance comprises at least one of cyclohexanone oxime and pinacolin oxime. Substrate processing method.

2. In the substrate processing method described in claim 1, In the hydrophilization step, an ammonia-hydrogen peroxide aqueous solution is supplied to the substrate. Substrate processing method.

3. In the substrate processing method described in claim 1, Prior to the hydrophilization step, an etching step is performed in which an etching solution is supplied to the substrate to remove the oxide film on the substrate, Furthermore, Substrate processing method.

4. In the substrate processing method described in claim 3, A first rinsing step is performed after the etching step and before the hydrophilization step, in which a first rinsing solution is supplied to the substrate. Furthermore, Substrate processing method.

5. In the substrate processing method described in claim 1, A second rinsing step is performed after the hydrophilization step and before the first supply step, in which a second rinsing solution is supplied to the substrate. Furthermore, Substrate processing method.

6. In the substrate processing method described in claim 5, A first replacement step is performed after the second rinsing step and before the first supply step, in which the first replacement liquid is supplied to the substrate. Furthermore, Substrate processing method.

7. In the substrate processing method described in claim 1, In the aforementioned solidification film formation step, the substrate is cooled. Substrate processing method.

8. A substrate processing method for processing a substrate having a pattern formed on its surface, A hydrophobicization process in which a water-repellent agent is applied to the surface of the substrate, A second supply step involves supplying a drying aid liquid containing a sublimable substance and a first solvent to a substrate to which the water-repellent agent is attached. A solidification film formation step involves evaporating the first solvent from the drying aid liquid on the substrate to form a solidified film containing the sublimable substance on the substrate, A sublimation step for sublimating the solidified film, Equipped with, The sublimable substance includes an organic compound containing an oxime group, The substrate processing method is A third replacement step is performed after the hydrophobicization step and before the second supply step, in which a third replacement liquid is supplied to the substrate. Furthermore, Substrate processing method.

9. In the substrate processing method described in claim 8, In the hydrophobicization step, a mixture containing the water-repellent agent and the second solvent is supplied to the substrate. Substrate processing method.

10. In the substrate processing method described in claim 8, Prior to the hydrophobicization step, a hydrophilization step is performed to form hydroxyl groups on the surface of the substrate, Furthermore, Substrate processing method.

11. In the substrate processing method described in claim 10, Prior to the hydrophilization step, an etching step is performed in which an etching solution is supplied to the substrate to remove the oxide film on the substrate, Furthermore, Substrate processing method.

12. In the substrate processing method according to claim 11, A first rinsing step is performed after the etching step and before the hydrophilization step, in which a first rinsing solution is supplied to the substrate. Furthermore, Substrate processing method.

13. In the substrate processing method described in claim 10, A second rinsing step is performed after the hydrophilization step and before the hydrophobicization step, in which a second rinsing solution is supplied to the substrate. Furthermore, Substrate processing method.

14. In the substrate processing method described in claim 13, A second replacement step is performed after the second rinsing step and before the hydrophobicization step, in which a second replacement liquid is supplied to the substrate. Furthermore, Substrate processing method.

15. In the substrate processing method described in claim 14, The composition of the third replacement solution is the same as the composition of the second replacement solution. Substrate processing method.

16. In the substrate processing method described in claim 14, The composition of the third replacement solution is different from the composition of the second replacement solution. Substrate processing method.

17. In the substrate processing method described in claim 8, In the third substitution step, the water repellent adhering to the surface of the substrate is not removed, and the unreacted portion of the water repellent is removed from the substrate. Substrate processing method.

18. In the substrate processing method according to any one of claims 1 to 17, The sublimable substance does not contain fluorocarbon compounds. Substrate processing method.

19. A substrate processing method for processing a substrate having a pattern formed on its surface, A hydrophilization process to form hydroxyl groups on the surface of the substrate, A first supply step involves supplying a substrate having a hydroxyl group with a drying aid containing a sublimable substance containing an organic compound containing an oxime group and a first solvent, thereby bonding the hydroxyl group and the oxime group. A solidification film formation step in which, while cooling the substrate, the first solvent is evaporated from the drying aid liquid on the substrate to form a solidified film containing the sublimable substance on the substrate, A sublimation step in which the substrate is cooled while a drying gas is supplied to the substrate to sublimate the solidified film, Equipped with, From the solidification film formation step to the sublimation step, the substrate is continuously cooled. Substrate processing method.

20. A substrate processing method for processing a substrate having a pattern formed on its surface, A hydrophobicization process in which a water-repellent agent is applied to the surface of the substrate, A second supply step involves supplying a drying aid liquid containing a sublimable substance and a first solvent to a substrate to which the water-repellent agent is attached. A solidification film formation step in which, while cooling the substrate, the first solvent is evaporated from the drying aid liquid on the substrate to form a solidified film containing the sublimable substance on the substrate, A sublimation step in which the substrate is cooled while a drying gas is supplied to the substrate to sublimate the solidified film, Equipped with, The sublimable substance includes an organic compound containing an oxime group, From the solidification film formation step to the sublimation step, the substrate is continuously cooled. The substrate processing method is A third replacement step is performed after the hydrophobicization step and before the second supply step, in which a third replacement liquid is supplied to the substrate. Furthermore, Substrate processing method.

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