TWI873435B - Substrate processing method, substrate processing device and processing liquid - Google Patents

Abstract

The present invention relates to a substrate processing method, a substrate processing device and a processing liquid. The substrate processing method includes a processing liquid supply process, a solidified film forming process and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The processing liquid contains a sublimable substance and a solvent. In the solidified film forming process, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming process, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. In the sublimation process, the solidified film sublimates. By the sublimation of the solidified film, the substrate is dried. Here, the sublimable substance is 4-nitrotoluene.

Description

Substrate processing method, substrate processing device and processing liquid

The present invention relates to a substrate processing method, a substrate processing device and a processing liquid. The substrate is, for example, a semiconductor wafer, a liquid crystal display substrate, an organic EL (Electroluminescence) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, and a solar cell substrate.

Patent document 1 discloses a substrate processing method for drying a substrate. Specifically, the substrate processing method of Patent document 1 includes a processing liquid supply process, a solidified film forming process and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The processing liquid contains a solvent and a sublimable substance. The sublimable substance is cyclohexanone oxime. In the solidified film forming process, the solvent evaporates to form a solidified film on the substrate. The solidified film contains cyclohexanone oxime. In the sublimation process, the solidified film sublimates. The solidified film changes into gas without passing through a liquid. According to the substrate processing method of Patent document 1, the substrate can be properly dried. [Prior art document] [Patent document]

[Patent document 1] Japanese Patent Publication No. 2021-9988

[The problem the invention is trying to solve]

Even with the conventional substrate processing methods, there are cases where the substrate cannot be dried properly. For example, even with the conventional substrate processing methods, there are cases where the pattern formed on the substrate collapses. For example, when the pattern is fine, there are cases where the conventional substrate processing methods cannot sufficiently suppress the collapse of the pattern.

The present invention is completed in view of this situation, and its purpose is to provide a substrate processing method, substrate processing device and processing liquid that can properly dry the substrate. [Technical means to solve the problem]

The present invention adopts the following structure to achieve such an object. That is, the present invention is a substrate processing method, which processes a substrate formed with a pattern, comprising: a processing liquid supplying step, which is to supply a processing liquid containing a sublimable substance and a solvent to the substrate; a solidified film forming step, which is to evaporate the solvent from the processing liquid on the substrate to form a solidified film containing the sublimable substance on the substrate; and a sublimation step, which is to sublime the solidified film; and the sublimable substance is 4-nitrotoluene.

The substrate processing method is used to process a substrate formed with a pattern. The substrate processing method includes a processing liquid supply process, a solidified film forming process and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The processing liquid contains a sublimable substance and a solvent. In the solidified film forming process, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming process, a solidified film is formed on the substrate. The solidified film contains a sublimable substance. In the sublimation process, the solidified film sublimates. By the sublimation of the solidified film, the substrate is dried. Here, the sublimable substance is 4-nitrotoluene. That is, the processing liquid contains 4-nitrotoluene and a solvent. Therefore, the solidified film contains 4-nitrotoluene. Therefore, the substrate is properly dried. Specifically, the pattern formed on the substrate is well protected to dry the substrate.

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

In the above substrate processing method, the above solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves 4-nitrotoluene well. Furthermore, isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the substrate is dried more appropriately.

The present invention is a substrate processing device, which comprises: a substrate holding part, which holds a substrate; and a processing liquid supply part, which supplies a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding part; and the sublimable substance is 4-nitrotoluene.

The substrate processing device includes a substrate holding portion and a processing liquid supply portion. The substrate holding portion holds the substrate. The processing liquid supply portion supplies the processing liquid to the substrate held by the substrate holding portion. The processing liquid contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, when the processing liquid is supplied to the substrate, the solvent evaporates well from the processing liquid on the substrate. Therefore, a cured film is formed well on the substrate. The cured film contains 4-nitrotoluene. Therefore, the cured film sublimates appropriately. By the sublimation of the cured film, the substrate is properly dried. As described above, according to the present substrate processing device, the substrate is properly dried.

In the substrate processing apparatus, the solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves 4-nitrotoluene well. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the substrate is dried more appropriately.

The present invention is a processing liquid used for drying a substrate with a pattern formed thereon. The processing liquid comprises a sublimable substance and a solvent, wherein the sublimable substance is 4-nitrotoluene.

The processing liquid is used to dry the substrate on which the pattern is formed. Specifically, the processing liquid is a drying auxiliary liquid. The processing liquid contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, the processing liquid is useful for drying the substrate. Specifically, by using the processing liquid, the pattern formed on the substrate is well protected and the substrate is dried. As described above, the substrate is properly dried using the processing liquid.

In the above-mentioned treatment liquid, the above-mentioned solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves 4-nitrotoluene well. Furthermore, isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the treatment liquid is more useful for drying the substrate. The substrate is dried more appropriately using the treatment liquid. [Effect of the invention]

According to the substrate processing method, substrate processing apparatus and processing liquid of the present invention, the substrate is properly dried.

Hereinafter, the substrate processing method, substrate processing apparatus and processing liquid of the present invention will be described with reference to the drawings.

<1. Substrate> The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL (Electroluminescence), a substrate for an FPD (Flat Panel Display), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a mask, or a substrate for a solar cell. The substrate W has a relatively thin flat plate shape. The substrate W has a generally circular shape when viewed from above.

1 schematically shows a portion of a substrate W. The substrate W has a pattern P. The pattern P is formed on the surface of the substrate W.

The pattern P, for example, has a concave-convex shape. The pattern P, for example, has a convex portion W1 and a concave portion A. The convex portion W1 is a part of the substrate W. The convex portion W1 is a structure. The convex portion W1, for example, includes at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN) and a polycrystalline silicon film. The convex portion W1, for example, bulges upward from the surface of the substrate W. The concave portion A is adjacent to the side of the convex portion W1. The concave portion A is a space. The concave portion A, for example, is open upward. The convex portion W1 is equivalent to a wall that divides the concave portion A.

<2. Processing liquid (drying auxiliary liquid)> In this manual, the processing liquid used for drying the substrate W is referred to as "processing liquid". The processing liquid has the function of assisting the drying of the substrate W. In other words, the processing liquid can be called a drying auxiliary liquid.

The treatment liquid contains sublimable substances. Sublimable substances have sublimation properties. The so-called "sublimation property" refers to the property of a single substance, compound or mixture to transfer from a solid phase to a gas phase or from a gas phase to a solid phase without passing through a liquid.

The sublimable substance includes 4-nitrotoluene. The sublimable substance, for example, includes only 4-nitrotoluene. 4-Nitrotoluene is represented by the following chemical formula (1).

[Chemistry 1]

The treatment liquid contains a solvent. The solvent dissolves the sublimable substance. The sublimable substance in the treatment liquid dissolves in the solvent. That is, the treatment liquid contains the solvent and the sublimable substance dissolved in the solvent. The sublimable substance is equivalent to the solute of the treatment liquid.

The solvent has a relatively high vapor pressure at room temperature. For example, the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature.

Here, normal temperature includes room temperature. Normal temperature is, for example, a temperature in the range of 5°C to 35°C. Normal temperature is, for example, a temperature in the range of 10°C to 30°C. Normal temperature is, for example, a temperature in the range of 20°C to 25°C.

The volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid. For example, the volume ratio RV of the treatment liquid is preferably greater than 1 [Vol%] and less than 20 [Vol%]. Here, the volume ratio RV of the treatment liquid is the ratio of the volume of the sublimable substance contained in the treatment liquid to the volume of the solvent contained in the treatment liquid. In other words, the volume ratio RV of the treatment liquid is defined by the following formula. RV＝(Volume of sublimable substance contained in the treatment liquid)/(Volume of solvent contained in the treatment liquid)﹡100     [Vol%]

The solvent is, for example, an organic solvent. The solvent is, for example, alcohol.

The solvent includes, for example, isopropyl alcohol (IPA). The solvent includes, for example, only isopropyl alcohol (IPA). The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of 4-nitrotoluene at room temperature.

The processing liquid consists of, for example, only a sublimable substance and a solvent.

The treatment liquid consists of, for example, only 4-nitrotoluene and isopropyl alcohol.

<3. Overview of substrate processing apparatus> FIG. 2 is a top view showing the interior of a substrate processing apparatus 1 according to an embodiment. The substrate processing apparatus 1 processes a substrate W. The processing in the substrate processing apparatus 1 includes a drying process.

The substrate processing apparatus 1 includes a carrier 3 and a processing block 7. The processing block 7 is connected to the carrier 3. The carrier 3 supplies the substrate W to the processing block 7. The processing block 7 processes the substrate W. The carrier 3 collects the substrate W from the processing block 7.

In this specification, for convenience, the direction in which the carrier 3 and the processing block 7 are arranged is referred to as the "front-rear direction X". The front-rear direction X is horizontal. The direction from the processing block 7 toward the carrier 3 in the front-rear direction X is referred to as the "front". The direction opposite to the front is referred to as the "rear". The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y". One direction of the "width direction Y" is appropriately referred to as the "right". The direction opposite to the right is referred to as the "left". The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z". In each figure, for reference, front, back, right, left, top, and bottom are appropriately shown.

The carrier section 3 has a plurality of (for example, four) carrier mounting sections 4. Each carrier mounting section 4 mounts one carrier C. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, a FOUP (Front Opening Unified Pod), a SMIF (Standard Mechanical Interface), or an OC (Open Cassette).

The carrier portion 3 includes a transport mechanism 5. The transport mechanism 5 is disposed at the rear of the carrier mounting portion 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 can enter and exit the carrier C mounted on the carrier mounting portion 4. The transport mechanism 5 includes a robot 5a and a robot driving portion 5b. The robot 5a supports the substrate W. The robot driving portion 5b is connected to the robot 5a. The robot driving portion 5b moves the robot 5a. The robot driving portion 5b moves the robot 5a in, for example, the front-rear direction X, the width direction Y, and the vertical direction Z. The robot driving portion 5b rotates the robot 5a in, for example, a horizontal plane.

The processing block 7 is provided with 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 is provided with a robot 8a and a robot driving unit 8b. The robot 8a supports the substrate W. The robot driving unit 8b is connected to the robot 8a. The robot driving unit 8b moves the robot 8a. The robot driving unit 8b moves the robot 8a in the front-back direction X, the width direction Y, and the vertical direction Z, for example. The robot driving unit 8b rotates the robot 8a in a horizontal plane, for example.

The processing block 7 includes a plurality of processing units 11. The processing units 11 are disposed on the side of the transfer mechanism 8. Each processing unit 11 processes a substrate W.

The processing unit 11 includes a substrate holding portion 13. The substrate holding portion 13 holds a substrate W.

The transport mechanism 8 can enter and exit each processing unit 11. The transport mechanism 8 can deliver the substrate W to the substrate holding portion 13. The transport mechanism 8 can obtain the substrate W from the substrate holding portion 13.

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, 8 and the processing unit 11. The control unit 10 controls the transport mechanisms 5, 8 and the processing unit 11.

The control unit 10 is implemented by a central processing unit (CPU) that performs various processing, a RAM (Random-Access Memory) that serves as a work area for processing, a fixed disk or other storage medium, etc. The control unit 10 has various information pre-stored in the storage medium. The information possessed by the control unit 10 is, for example, the transport condition information for controlling the transport mechanism 5, 8. The information possessed by the control unit 10 is, for example, the processing condition information for controlling the processing unit 11. The processing condition information is also called a processing plan.

An operation example of the substrate processing apparatus 1 is briefly described.

The carrier 3 supplies the substrate W to the processing block 7 . Specifically, the transfer mechanism 5 delivers the substrate W from the carrier C to the transfer mechanism 8 in the processing block 7 .

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 portions 13 of the processing units 11 .

The processing unit 11 processes the substrate W held by the substrate holding portion 13. The processing unit 11 performs a drying process on the substrate W, for example.

After the processing unit 11 processes the substrate W, the transport mechanism 8 collects the substrate W from each processing unit 11. Specifically, the transport mechanism 8 receives the substrate W from each substrate holding portion 13. Then, the transport mechanism 8 delivers the substrate W to the transport mechanism 5.

The carrier 3 collects the substrate W from the processing block 7. Specifically, the transfer mechanism 5 transfers the substrate W from the transfer mechanism 8 to the carrier C.

<4. Structure of the processing unit 11> FIG. 4 is a diagram showing the structure of the processing unit 11. Each processing unit 11 has the same structure. The processing unit 11 is classified as a single-chip type. That is, each processing unit 11 processes only one substrate W at a time.

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

The interior of the housing 12 is maintained at room temperature. The temperature of the gas inside the housing 12 is maintained at room temperature. Therefore, the substrate W is processed in a room temperature environment.

The interior of the housing 12 is maintained at normal pressure. The pressure of the gas inside the housing 12 is maintained at normal pressure. Therefore, the substrate W is processed in a normal pressure environment.

Here, normal pressure includes standard atmospheric pressure (1 atmosphere, 101325 Pa). Normal pressure is, for example, pressure in the range of 0.7 atmospheres to 1.3 atmospheres. In this specification, pressure values are expressed as absolute pressures based on absolute vacuum.

The substrate holding portion 13 is provided inside the housing 12. The substrate holding portion 13 holds one substrate W. The substrate holding portion 13 holds the substrate W in a substantially horizontal position.

The substrate holding portion 13 is located below the substrate W held by the substrate holding portion 13 . The substrate holding portion 13 contacts at least one of the lower surface of the substrate W and the peripheral portion of the substrate W. The lower surface of the substrate W is also referred to as the back surface of the substrate W. The substrate holding portion 13 does not contact the upper surface of the substrate W.

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

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.

The supply unit 15 includes a first supply unit 15a, a second supply unit 15b, a third supply unit 15c, a fourth supply unit 15d, and a fifth supply unit 15e. The first supply unit 15a supplies a treatment solution. The second supply unit 15b supplies a chemical solution. The third supply unit 15c supplies a rinse solution. The fourth supply unit 15d supplies a replacement solution. The fifth supply unit 15e supplies a dry gas.

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

As mentioned above, the interior of the housing 12 is at normal temperature and pressure. Therefore, the processing liquid is used in a normal temperature environment. The processing liquid is used in a normal pressure environment.

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

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

The replacement liquid supplied by the fourth supply unit 15d is, for example, an organic solvent. The replacement liquid is, for example, isopropyl alcohol (IPA).

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

The first supply unit 15a has a nozzle 16a. Similarly, the second to fifth supply units 15b-15e have nozzles 16b-16e, respectively. The nozzles 16a-16e are respectively disposed inside the housing 12. The nozzle 16a sprays a treatment liquid. The nozzle 16b sprays a chemical solution. The nozzle 16c sprays a rinse liquid. The nozzle 16d sprays a replacement liquid. The nozzle 16e sprays a dry gas.

The first supply section 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is opened, the nozzle 16a sprays the treatment liquid. When the valve 18a is closed, the nozzle 16a does not spray the treatment liquid. Similarly, the second to fifth supply sections 15b-15e include pipes 17b-17e and valves 18b-18e, respectively. The pipes 17b-17e are connected to the nozzles 16b-16e, respectively. The valves 18b-18e are provided on the pipes 17b-17e, respectively. Valves 18b-18e control the spraying of chemical solution, flushing liquid, replacement liquid and drying gas respectively.

At least a portion of the pipe 17a may be disposed outside the housing 12. The pipes 17b to 17e may be arranged in the same manner as the pipe 17a. The valve 18a may be disposed outside the housing 12. The valves 18b to 18e may be arranged in the same manner as the valve 18a.

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

The second supply section 15b is connected to the second supply source 19b. The second supply section 15b is connected to the second supply source 19b. The second supply source 19b is connected to, for example, the pipe 17b. The second supply source 19b delivers a medicine solution to the second supply section 15b. Similarly, the third to fifth supply sections 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. The third to fifth supply sections 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. The third to fifth supply sources 19c-19e are connected to, for example, the pipes 17c-17e, respectively. The third supply source 19c delivers a flushing solution to the third supply section 15c. The fourth supply source 19d delivers a replacement solution to the fourth supply section 15d. The fifth supply source 19e supplies dry gas to the fifth supply portion 15e.

The first supply source 19a is disposed outside the housing 12. Similarly, the second to fifth supply sources 19b to 19e are disposed outside the housing 12, respectively.

The first supply source 19a may supply the processing liquid to a plurality of processing units 11. Alternatively, the first supply source 19a may supply the processing liquid to only one processing unit 11. The same is true for the second to fifth supply sources 19b to 19e.

The second supply source 19b may be an element of the substrate processing device 1. For example, the second supply source 19b may be a chemical solution tank provided in the substrate processing device 1. Alternatively, the second supply source 19b may not be an element of the substrate processing device 1. For example, the second supply source 19b may be a physical device provided outside the substrate processing device 1. Similarly, the third to fifth supply sources 19c-19e may be elements of the substrate processing device 1, respectively. Alternatively, the third to fifth supply sources 19c-19e may not be elements of the substrate processing device 1, respectively.

The processing unit 11 may further include a cup (not shown). The cup is disposed inside the housing 12. The cup is disposed around the substrate holding portion 13. The cup receives liquid scattered from the substrate W held on the substrate holding portion 13.

Refer to Fig. 3. The control unit 10 controls the rotary drive unit 14. The control unit 10 controls the supply unit 15. The control unit 10 controls the valves 18a-18e.

<5. Configuration of the first supply source 19a> Refer to Figure 4. The first supply source 19a further generates a processing liquid.

The configuration example of the first supply source 19a is shown below. The first supply source 19a is divided into a generation unit 21 and a pressure-feeding unit 31. The generation unit 21 generates the processing liquid. The pressure-feeding unit 31 delivers the processing liquid to the first supply portion 15a.

The generating unit 21 includes a tank 22 and supply parts 23a and 23b. The supply part 23a supplies the sublimable substance to the tank 22. The supply part 23b supplies the solvent to the tank 22. The sublimable substance and the solvent are mixed in the tank 22. The sublimable substance and the solvent become the processing liquid g in the tank 22.

The tank 22 is set in a normal temperature environment. The tank 22 is set in a normal pressure environment. Therefore, the processing liquid g is generated in a normal temperature environment. The processing liquid g is generated in a normal pressure environment.

Furthermore, the generation unit 21 stores the processing liquid g. Specifically, the processing liquid g is stored in the tank 22. The processing liquid g is stored in a normal temperature environment. The processing liquid g is stored in a normal pressure environment.

The supply section 23a includes, for example, a pipe 24a and a valve 25a. The pipe 24a is connected to the tank 22. The pipe 24a communicates with the tank 22. The valve 25a is provided on the pipe 24a. When the valve 25a is opened, the supply section 23a supplies the sublimation substance to the tank 22. When the valve 25a is closed, the supply section 23a does not supply the sublimation substance to the tank 22. Similarly, the supply section 23b includes a pipe 24b and a valve 25b. The pipe 24b is connected to the tank 22. The pipe 24b communicates with the tank 22. The valve 25b is provided on the pipe 24b. The valve 25b controls the supply of the solvent to the tank 22.

Furthermore, the amount of the sublimable substance in the tank 22 is controlled by the valve 25a. The amount of the solvent in the tank 22 is controlled by the valve 25b. Therefore, the volume ratio RV of the treatment liquid g in the tank 22 is controlled by the valves 25a and 25b.

The valves 25a and 25b may include flow regulating valves, for example. The valves 25a and 25b may include flow regulating valves and on-off valves, for example.

The supply section 23a is connected to the supply source 26a. The supply section 23a is connected to the supply source 26a. For example, the supply source 26a is connected to the pipe 24a. The supply source 26a transports the sublimable substance to the supply section 23a. Similarly, the supply section 23b is connected to the supply source 26b. The supply section 23b is connected to the supply source 26b. For example, the supply source 26b is connected to the pipe 24b. The supply source 26b transports the solvent to the supply section 23b.

The pressure-feeding unit 31 includes a pipe 32 and a joint 33. The pipe 32 is connected to the tank 22. The pipe 32 is connected to the tank 22. The joint 33 is connected to the pipe 32. The joint 33 is further connected to the pipe 17a. The pipe 32 is connected to the pipe 17a via the joint 33. The pipe 32 is connected to the pipe 17a via the joint 33. Therefore, the tank 22 is connected to the first supply unit 15a via the pipe 32 and the joint 33. The tank 22 is connected to the first supply unit 15a via the pipe 32 and the joint 33. The tank 22 is connected to the nozzle 16a. The tank 22 is connected to the nozzle 16a.

The pressure-feeding unit 31 further includes a pump 34 and a filter 35. The pump 34 is disposed in the piping 32. When the pump 34 is operated, the pump 34 delivers the treatment liquid g from the tank 22 to the first supply portion 15a. When the pump 34 is operated, the pump 34 pressure-feeds the treatment liquid g from the tank 22 to the first supply portion 15a. When the pump 34 stops operating, the pump 34 does not deliver the treatment liquid g from the tank 22 to the first supply portion 15a. When the pump 34 stops operating, the pump 34 does not pressure-feed the treatment liquid g from the tank 22 to the first supply portion 15a. The filter 35 is disposed in the piping 32. The treatment liquid g passes through the filter 35. The filter 35 filters the treatment liquid g. The filter 35 removes foreign matter from the treatment liquid g.

Refer to Fig. 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-feeding unit 31. The control unit 10 controls the pump 34.

The control unit 10 has the processing liquid condition information for controlling the first supply source 19a. The processing liquid condition information includes, for example, a target value related to the volume ratio RV of the processing liquid g. The processing liquid condition information is pre-stored in the storage medium of the control unit 10.

<6. Example of the operation of the first supply source 19a and the processing unit 11> FIG. 5 is a flowchart showing the procedure of the substrate processing method of the implementation method. The substrate processing method includes step S1 and steps S11-S18. Step S1 is performed by the first supply source 19a. Steps S11-S18 are actually performed by the processing unit 11. Step S1 and steps S11-S18 are performed synchronously. The first supply source 19a and the processing unit 11 operate according to the control of the control unit 10.

Each step S1, S11-S18 is described with appropriate reference to FIG. 4.

Step S1: Processing liquid generation process In the processing liquid generation process, a processing liquid g is generated.

The generation unit 21 generates the processing liquid g. Specifically, the supply unit 23a supplies the sublimable substance to the tank 22. The supply unit 23b supplies the solvent to the tank 22. The processing liquid g is generated in the tank 22. The processing liquid g is stored in the tank 22.

The control unit 10 controls the valves 25a and 25b. Thus, the control unit 10 adjusts the volume ratio RV of the processing liquid g in the tank 22 to the target value specified by the processing liquid condition information.

Step S11: Rotation start process The substrate holding part 13 holds the substrate W. The substrate W is held in a substantially horizontal position. The rotation drive part 14 rotates the substrate holding part 13. Thereby, the substrate W held in the substrate holding part 13 starts to rotate.

In the following steps S12-S17, the substrate W, for example, continues to rotate.

Step S12: Chemical solution supply process In the chemical solution supply process, the chemical solution is supplied to the substrate W.

The second supply unit 15b supplies the chemical solution to the substrate W held by the substrate holding unit 13. Specifically, the valve 18b is opened. The nozzle 16b sprays the chemical solution. The chemical solution is supplied to the upper surface of the substrate W. For example, the chemical solution etches the substrate W. For example, the chemical solution removes the natural oxide film from the substrate W.

Thereafter, the second supply unit 15b stops supplying the chemical solution to the substrate W. Specifically, the valve 18b is closed and the nozzle 16b stops ejecting the chemical solution.

Step S13: Rinse liquid supply process In the rinse liquid supply process, the rinse liquid is supplied to the substrate W.

The third supply unit 15c supplies the rinse liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18c is opened. The nozzle 16c sprays the rinse liquid. The rinse liquid is supplied to the upper surface of the substrate W. For example, the rinse liquid cleans the substrate W. For example, the rinse liquid removes the chemical solution from the substrate W.

Thereafter, the third supply unit 15c stops supplying the rinse liquid to the substrate W. Specifically, the valve 18c is closed. The nozzle 16c stops ejecting the rinse liquid.

Step S14: Replacement liquid supply process In the replacement liquid supply process, the replacement liquid is supplied to the substrate W.

The fourth supply unit 15d supplies the replacement liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18d is opened. The nozzle 16d sprays the replacement liquid. The replacement liquid is supplied to the upper surface of the substrate W. The replacement liquid removes the rinse liquid from the substrate W. The rinse liquid on the substrate W is replaced by the replacement liquid.

Thereafter, the fourth supply unit 15d stops supplying the replacement liquid to the substrate W. Specifically, the valve 18d is closed. The nozzle 16d stops ejecting the replacement liquid.

Step S15: Processing liquid supply process In the processing liquid supply process, the processing liquid g is supplied to the substrate W.

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

Thereafter, the pressure feeding unit 31 stops supplying the processing liquid g to the first supply unit 15a. The first supply unit 15a stops supplying the processing liquid g to the substrate W. Specifically, the pump 34 is stopped. The valve 18a is closed. The nozzle 16a stops ejecting the processing liquid g.

6 schematically shows the substrate W in the process of supplying the processing liquid. When the substrate W is held by the substrate holding portion 13, the pattern P is located on the upper surface of the substrate W. When the substrate W is held by the substrate holding portion 13, the pattern P faces upward.

The processing liquid g on the substrate W forms a liquid film G. The liquid film G is located on the substrate W. The liquid film G is in contact with the substrate W. The liquid film G covers the substrate W. The liquid film G covers the upper surface of the substrate W.

The pattern P is completely immersed in the liquid film G. The convex portion W1 is completely immersed in the liquid film G. The concave portion A is filled with the liquid film G. The concave portion A is completely filled with the liquid film G only.

The liquid film G has an upper surface G1. The upper surface G1 is located at a position higher than the entire pattern P. The upper surface G1 does not intersect with the pattern P. The upper surface G1 is located at a position higher than the entire convex portion W1. The upper surface G1 does not intersect with the convex portion W1.

Furthermore, the replacement liquid has been removed from the substrate W by the processing liquid g. Therefore, no replacement liquid exists on the substrate W. No replacement liquid remains in the recessed portion A.

The gas J exists above the liquid film G. The pattern P is not in contact with the gas J. The pattern P is not exposed in the gas J. The convex portion W1 is not in contact with the gas J. The convex portion W1 is not exposed in the gas J.

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 is equivalent to the gas-liquid interface between the liquid film G and the gas J. Therefore, the pattern P does not intersect with the gas-liquid interface between the liquid film G and the gas J. The convex portion W1 does not intersect with the gas-liquid interface between the liquid film G and the gas J.

In the process of supplying the treatment liquid, the height position of the upper surface G1 can be further adjusted. For example, the height position of the upper surface G1 can be adjusted while the treatment liquid g is supplied to the substrate W by the nozzle 16a. For example, the height position of the upper surface G1 can be adjusted after the nozzle 16a stops supplying the treatment liquid g. For example, the height position of the upper surface G1 can be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface G1 can be adjusted by adjusting the rotation time of the substrate W.

Here, adjusting the height position of the upper surface G1 is equivalent to adjusting the thickness H of the liquid film G. The thickness H of the liquid film G is, for example, the distance in the vertical direction Z between the lower end W1a of the protrusion W1 and the upper surface G1.

Step S16: Cured film forming process In the cured film forming process, the solvent evaporates from the processing liquid g on the substrate W. In the cured film forming process, a cured film is formed on the substrate W. The cured film contains a sublimable substance.

FIG7 schematically shows a substrate W in the process of forming a cured film. As described above, the solvent has a relatively high vapor pressure. At room temperature, the solvent has a higher vapor pressure than the sublimable substance. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W. The solvent changes smoothly from liquid to gas.

When the solvent evaporates from the processing liquid g on the substrate W, the solvent is removed from the processing liquid g on the substrate W. As the solvent evaporates from the processing liquid g on the substrate W, the amount of solvent contained in the liquid film G decreases. As the amount of solvent contained in the liquid film G decreases, the volume ratio RV of the liquid film G increases.

Soon, the sublimation substance in the liquid film G begins to precipitate on the substrate W. That is, the sublimation substance changes from the solute of the processing liquid g to the sublimation substance in the solid phase. The sublimation substance in the solid phase forms a solid film K. The solid film K does not contain a solvent. The solid film K is solid. The solid film K is formed on the substrate W.

The liquid film G gradually decreases due to the evaporation of the solvent and the precipitation of the sublimation substance. The liquid film G gradually changes into a solidified film K due to the precipitation of the sublimation substance. The solidified film K gradually increases due to the precipitation of the sublimation substance.

First, the upper portion of the liquid film G changes into a solidified film K. The solidified film K is located above the liquid film G. The solidified film K covers the upper surface G1 of the liquid film G.

When the solidified film K covers the entire upper surface G1, the solidified film K separates the liquid film G from the gas J. The liquid film G is in contact with the solidified film K. The gas J 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.

Therefore, the pattern P does not intersect with the air-liquid interface. The liquid film G does not exert a significant force on the pattern P. The convex portion W1 does not intersect with the air-liquid interface. The liquid film G does not exert a significant force on the convex portion W1.

As the solidified film K increases, the height position of the upper surface G1 gradually decreases. As the solidified film K increases, the thickness H of the liquid film G gradually decreases. When the liquid film G does not exert a significant force on the protrusion W1, the liquid film G decreases. When the solvent does not exert a significant force on the protrusion W1, the solvent is removed from the substrate W.

FIG8 schematically shows the substrate W in the cured film forming step. FIG8 schematically shows the substrate W at the end of the cured film forming step, for example. Only the cured film K exists on the substrate W. At the end of the cured film forming step, the liquid film G completely disappears from the substrate W. The liquid film G does not remain in the concave portion A. The solvent completely disappears from the substrate W. The solvent also does not remain in the concave portion A.

The concave portion A is filled with the cured film K. The concave portion A is filled entirely with the cured film K. The pattern P is in contact with the cured film K. The cured film K supports the pattern P. The cured film K protects the pattern P. For example, the cured film K prevents the pattern P from collapsing. The convex portion W1 is in contact with the cured film K. The cured film K supports the convex portion W1. The cured film K protects the convex portion W1. For example, the cured film K prevents the convex portion W1 from collapsing.

Step S17: Sublimation process In the sublimation process, the cured film K sublimates.

The fifth supply unit 15e supplies dry gas to the substrate W held by the substrate holding unit 13. Specifically, the valve 18e is opened. The nozzle 16e sprays dry gas. The nozzle 16e sprays dry gas to the substrate W. The dry gas is supplied to the upper surface of the substrate W. The dry gas is supplied to the cured film K. The cured film K is exposed to the dry gas. Thereby, the cured film K sublimates. The cured film K changes into gas without passing through a liquid. By the sublimation of the cured film K, the cured film K is removed from the substrate W.

Thereafter, the fifth supply unit 15e stops supplying the dry gas to the cured film K. Specifically, the valve 18e is closed. The nozzle 16e stops ejecting the dry gas.

Fig. 9 schematically shows the substrate W in the sublimation process. As the cured film K sublimates, the cured film K gradually decreases. As the cured film K sublimates, the cured film K gradually becomes thinner.

The pattern P begins to be exposed in the gas J. The convex portion W1 begins to be exposed in the gas J.

When the cured film K sublimates, the cured film K does not become liquid. Therefore, in the sublimation process, no liquid exists on the substrate W. In the sublimation process, no liquid exists in the concave portion A. In the sublimation process, no air-liquid interface is generated near the pattern P.

Therefore, the pattern P does not intersect with the air-liquid interface. The cured film K does not exert a significant force on the pattern P. When the cured film K does not exert a significant force on the pattern P, the cured film K is removed from the substrate W. The convex portion W1 does not intersect with the air-liquid interface. The cured film K does not exert a significant force on the convex portion W1. When the cured film K does not exert a significant force on the convex portion W1, the cured film K is removed from the substrate W.

FIG. 10 schematically shows the substrate W in the sublimation process. FIG. 10 schematically shows the substrate W at the end of the sublimation process, for example. At the end of the sublimation process, the solidified film K disappears completely from the substrate W. No liquid exists on the substrate W. The pattern P is completely exposed to the gas J. The convex portion W1 is completely exposed to the gas J. The concave portion A is completely filled with only the gas J. The substrate W is dried.

The processes in the above-mentioned treatment liquid supply process, solidified film forming process and sublimation process are examples of drying processes. The processes in the above-mentioned treatment liquid supply process, solidified film forming process and sublimation process are equivalent to examples of using treatment liquid g. Treatment liquid g is used in a normal temperature environment. Treatment liquid g is used in a normal pressure environment.

Step S18: Rotation stop process The rotation drive unit 14 stops the rotation of the substrate holding unit 13. The substrate W held by the substrate holding unit 13 stops rotating. The substrate W is stationary. The processing unit 11 completes the processing of the substrate W.

<7. Technical significance of treatment liquid g> The technical significance of treatment liquid g is explained through experimental examples and comparative examples.

In the experimental example, the substrate W is subjected to a series of processes including a chemical solution supply process, a rinse solution supply process, a replacement solution supply process, a treatment solution supply process, a cured film formation process, and a sublimation process.

The liquid used in the liquid supply process is hydrofluoric acid. Hydrofluoric acid is a mixture of hydrogen fluoride and water. The volume ratio of hydrogen fluoride to water is as follows. Hydrogen fluoride: water = 1:10 (volume ratio)

The rinse liquid used in the rinse liquid supply process is deionized water (DIW).

The replacement fluid used in the replacement fluid supply process is isopropyl alcohol.

The treatment liquid g used in the treatment liquid supply process contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. The solvent is isopropyl alcohol (IPA). The volume ratio RV of the treatment liquid g is 2.5 [Vol%].

In the cured film forming step, the substrate W was rotated at a rotation speed of 1500 rpm.

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

The conditions of the comparative example are explained. The only difference between the comparative example and the experimental example is the sublimable substance. In the comparative example, the sublimable substance is cyclohexanone oxime. Regarding other conditions, the comparative example is the same as the experimental example.

Each substrate W processed in the experimental example and the comparative example is evaluated by the average collapse rate Fa. The average collapse rate Fa is the average value of a plurality of local collapse rates Fi.

Each local collapse rate Fi is the collapse rate of the local area Pi. Here, i is any natural number from 1 to N. N is the number of local areas Pi. Each local area Pi is a tiny area of the substrate W. Each local area Pi is magnified to 50,000 times, for example, by a scanning electron microscope. The observer observes the pattern P (convexity W1) in each local area Pi. The observer evaluates the convexity W1 in each local area Pi one by one. The observer determines the convexity W1 in each local area Pi one by one. Specifically, the observer determines whether the convexity W1 has collapsed for each convexity W1. The observer counts the number Ei of the evaluated convexities W1 in each local area Pi. The observer counts the number Ei of the determined convexities W1 in each local area Pi. The observer counts the number ei of convex parts W1 that collapsed in each local area Pi. The number ei is less than the number Ei. The local collapse rate Fi is the ratio of the coefficient ei to the number Ei. The local collapse rate Fi is defined by the following formula, for example. Fi＝ei/Ei﹡100       (%)

The average collapse rate Fa is the value obtained by dividing the sum of the local collapse rates Fi of each local area Pi by the number N of local areas Pi.

In the experimental example, the average collapse rate Fa is 2.70%. In the comparative example, the average collapse rate Fa is 4.45%. The average collapse rate Fa in the experimental example is lower than the average collapse rate Fa in the comparative example. In the experimental example, the pattern P of the substrate W is less likely to collapse than that in the comparative example.

Therefore, in the experimental example, the pattern P formed on the substrate W is more appropriately protected than in the comparative example. That is, in the experimental example, the substrate W is more appropriately dried than in the comparative example.

<8. Effect of the Implementation Method> The substrate processing method of the implementation method is used to process a substrate W formed with a pattern P. The substrate processing method includes a processing liquid supply process, a solidified film forming process, and a sublimation process. In the processing liquid supply process, the processing liquid g is supplied to the substrate W. The processing liquid g contains a sublimable substance and a solvent. In the solidified film forming process, the solvent evaporates from the processing liquid g on the substrate W. In the solidified film forming process, a solidified film K is formed on the substrate W. The solidified film K contains a sublimable substance. In the sublimation process, the solidified film K sublimates. By the sublimation of the solidified film, the substrate W is dried. Here, the sublimable substance is 4-nitrotoluene. That is, the processing liquid g contains 4-nitrotoluene and a solvent. Therefore, the solidified film K contains 4-nitrotoluene. Therefore, the substrate W is properly dried. Specifically, the pattern P formed on the substrate W is well protected and the substrate W is dried.

The solvent is isopropyl alcohol. Isopropyl alcohol dissolves 4-nitrotoluene well. Therefore, it is easy to use the processing liquid g containing 4-nitrotoluene as a sublimable substance. For example, in the processing liquid supply process, the processing liquid g containing 4-nitrotoluene is appropriately supplied to the substrate W.

Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, in the cured film forming step, isopropyl alcohol evaporates well from the processing liquid g on the substrate W. Therefore, in the cured film forming step, the cured film K is well formed on the substrate W. Therefore, the substrate W is dried more appropriately.

The substrate processing method includes a processing liquid generating step. In the processing liquid generating step, the processing liquid g is generated. Therefore, the processing liquid g is well prepared.

As described above, isopropyl alcohol dissolves 4-nitrotoluene well. Therefore, in the process of generating the processing liquid, the processing liquid g containing 4-nitrotoluene is generated well.

As described above, isopropyl alcohol dissolves 4-nitrotoluene well. Therefore, the treated liquid g containing 4-nitrotoluene can be well stored.

The substrate processing apparatus 1 includes a substrate holding portion 13 and a first supply portion 15a. The substrate holding portion 13 holds a substrate W. The processing liquid supply portion 15a supplies a processing liquid g to the substrate W held by the substrate holding portion 13. The processing liquid g contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, when the processing liquid g is supplied to the substrate W, the solvent evaporates well from the processing liquid g on the substrate W. Therefore, a cured film K is formed well on the substrate W. The cured film K contains 4-nitrotoluene. Therefore, the cured film K sublimates appropriately. By the sublimation of the cured film K, the substrate W is dried appropriately. As described above, according to the substrate processing apparatus 1, the substrate W is dried appropriately.

The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves 4-nitrotoluene well. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the substrate W is dried more appropriately.

The processing liquid g is used to dry the substrate W on which the pattern P is formed. Specifically, the processing liquid g is a drying auxiliary liquid. The processing liquid g contains a sublimable substance and a solvent. The sublimable substance is 4-nitrotoluene. Therefore, the processing liquid g is useful for drying the substrate W. Specifically, by using the processing liquid g, the pattern P formed on the substrate W is well protected and the substrate W is dried. As described above, the substrate W is properly dried using the processing liquid g.

The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves 4-nitrotoluene well. Isopropyl alcohol evaporates more easily than 4-nitrotoluene. Therefore, the processing liquid g is more useful for making the substrate W more dry. The substrate W is dried more appropriately using the processing liquid g.

As described above, isopropyl alcohol dissolves 4-nitrotoluene well. Therefore, the handling of the treatment solution g containing 4-nitrotoluene is relatively easy. For example, it is relatively easy to prepare the treatment solution g containing 4-nitrotoluene. For example, it is relatively easy to generate the treatment solution g containing 4-nitrotoluene. For example, it is relatively easy to store the treatment solution g containing 4-nitrotoluene. For example, it is relatively easy to use the treatment solution g containing 4-nitrotoluene.

<9. Variations of implementation> The present invention is not limited to the implementation method and can be varied and implemented as described below.

(1) In the embodiment, the processing liquid g is generated before the processing liquid g is supplied to the first supply part 15a. In the embodiment, the first supply source 19a generates the processing liquid in the tank 22. However, this is not limited to this. For example, the processing liquid g may be generated when the processing liquid g is supplied to the first supply part 15a. For example, the first supply source 19a may also generate the processing liquid g in the flow path of supplying the processing liquid g to the first supply part 15a.

Fig. 11 is a diagram showing the configuration of the processing unit 11 and the first supply source 19a of a modified embodiment. The same reference numerals are given to the same configurations as those of the embodiment, and detailed descriptions thereof are omitted.

The first supply source 19a includes a first tank 41 and a second tank 42. The first tank 41 stores the sublimable substance. For example, the first tank 41 may store the sublimable substance and the solvent. The second tank 42 stores the solvent. For example, the second tank 42 stores only the solvent.

The first supply source 19a includes a mixing section 44. The mixing section 44 is connected to the first tank 41 and the second tank 42. The mixing section 44 is connected to the first tank 41 and the second tank 42. The mixing section 44 generates the processing liquid g.

The mixing section 44 is connected to the first supply section 15a. The mixing section 44 is connected to the first supply section 15a. The mixing section 44 supplies the processing liquid g to the first supply section 15a.

Specifically, the mixing section 44 includes pipes 45a, 45b and a joint 46. The pipe 45a is connected to the first tank 41. The pipe 45a is connected to the first tank 41. The pipe 45b is connected to the second tank 42. The pipe 45b is connected to the second tank 42. The joint 46 is connected to the pipes 45a and 45b. The joint 46 is connected to the pipes 45a and 45b. The joint 46 is further connected to the pipe 17a. The joint 46 is further connected to the pipe 17a. The pipes 45a and 45b are connected to the pipe 17a via the joint 46. The pipes 45a and 45b are connected to the pipe 17a via the joint 46.

The mixing unit 44 includes pumps 47a and 47b. The pumps 47a and 47b are provided in the pipes 45a and 45b, respectively. The pump 47a delivers the sublimable substance from the first tank 41 to the joint 46 via the pipe 45a. The pump 47b delivers the solvent from the second tank 42 to the joint 46 via the pipe 45b.

The mixing unit 44 includes filters 48a and 48b. The filters 48a and 48b are provided in the pipes 45a and 45b, respectively. The sublimable substance passes through the filter 48a. The filter 48a filters the sublimable substance. The solvent passes through the filter 48b. The filter 48b filters the solvent.

The mixing section 44 includes valves 49a and 49b. The valves 49a and 49b are provided in the pipes 45a and 45b, respectively. The valve 49a adjusts the flow rate of the sublimable substance flowing through the pipe 45a. The valve 49b adjusts the flow rate of the solvent flowing through the pipe 45b. The valves 49a and 49b may include flow regulating valves, for example. The valves 49a and 49b may also include flow regulating valves and on-off valves, for example.

The operation example of the first supply source 19a in the modified embodiment is explained. In the treatment liquid supply process, the first supply source 19a generates the treatment liquid g and transports the treatment liquid g to the first supply part 15a. Specifically, valves 49a and 49b are opened. Pump 47a transports the sublimation substance from the first tank 41 to the joint 46. Pump 47a presses the sublimation substance from the first tank 41 to the joint 46. Pump 47b transports the solvent from the second tank 42 to the joint 46. Pump 47b presses the solvent from the second tank 42 to the joint 46. The sublimation substance and the solvent are mixed in the joint 46. The sublimation substance and the solvent become the treatment liquid g in the joint 46. Furthermore, the processing liquid g flows to the first supply portion 15a from the joint 46. The nozzle 16a ejects the processing liquid g.

According to this modified embodiment, it is not necessary to store the processing liquid g before supplying the processing liquid g to the first supply unit 15a. Therefore, the volume ratio RV of the processing liquid is accurately managed. Therefore, the substrate W is dried more appropriately.

Furthermore, the first supply source 19a does not include the groove 22. Therefore, the structure of the first supply source 19a is simplified. The first supply source 19a is miniaturized.

(2) The substrate processing method of the embodiment includes a chemical solution supply process, a rinse liquid supply process, and a replacement liquid supply process. However, it is not limited to this. For example, at least one of the chemical solution supply process, the rinse liquid supply process, and the replacement liquid supply process may be omitted. For example, all of the chemical solution supply process, the rinse liquid supply process, and the replacement liquid supply process may be omitted.

(3) In the embodiment, when the processing liquid supply process is performed, liquid (e.g., replacement liquid) exists on the substrate W. That is, in the processing liquid supply process, the processing liquid g is supplied to the substrate W in a non-dry state. However, the present invention is not limited thereto. For example, when the processing liquid supply process is performed, liquid (e.g., replacement liquid) may not exist on the substrate W. For example, in the processing liquid supply process, the processing liquid g may be supplied to the substrate W in a dry state.

(4) In the process of supplying the processing liquid of the embodiment, the processing liquid g removes the replacement liquid from the substrate W. However, the present invention is not limited thereto. For example, in the process of supplying the processing liquid, the processing liquid g can also clean the substrate W. For example, in the process of supplying the processing liquid, the processing liquid g can also remove foreign matter attached to the substrate W. For example, in the process of supplying the processing liquid, the processing liquid g can also dissolve foreign matter attached to the substrate W. The foreign matter is, for example, anti-etching agent residue.

(5) In the cured film forming step of the embodiment, dry gas is not supplied to the substrate W. However, the present invention is not limited thereto. In the cured film forming step, dry gas may be supplied to the substrate W. In the cured film forming step, dry gas may be supplied to the processing liquid g on the substrate W. According to this variation of the embodiment, in the cured film forming step, the processing liquid g on the substrate W is exposed to the dry gas. Therefore, in the cured film forming step, the solvent evaporates efficiently from the processing liquid g on the substrate W. In the cured film forming step, the cured film K is efficiently formed on the substrate W.

(6) In the embodiment, for example, the pattern P on the substrate W may be formed on the substrate W before the processing unit 11 processes the substrate W. Alternatively, the pattern P may be formed on the substrate W while the processing unit 11 processes the substrate W. The pattern P may also be formed on the substrate W during the chemical solution supply process (step S12).

(7) With regard to the implementation methods and the various variations of the implementation methods described in (1) to (6) above, appropriate changes may be made by replacing each component with a component of another variation of the implementation method or combining them with the components.

1: substrate processing device 3: carrier 4: carrier loading section 5: transport mechanism 5a: robot 5b: robot drive section 7: processing block 8: transport mechanism 8a: robot 8b: robot drive section 10: control section 11: processing unit 14: rotation drive section 13: substrate holding section 15: supply section 15a: first supply section (processing liquid supply section) 19a: first supply source 11: processing unit 12: housing 13: substrate holding section 14: rotation drive section 15: supply section 15a: first supply section 15b: second supply section 15c: third supply section 15d: 4th supply section 15e: 5th supply section 16a: Nozzle 16b: Nozzle 16c: Nozzle 16d: Nozzle 16e: Nozzle 17a: Piping 17b: Piping 17c: Piping 17d: Piping 17e: Piping 18a: Valve 18b: Valve 18c: Valve 18d: Valve 18e: Valve 19a: 1st supply source 19b: 2nd supply source 19c: 3rd supply source 19d: 4th supply source 19e: 5th supply source 21: Generating unit 22: Tank 23a: Supply section 23b: Supply section 24a: piping 24b: piping 25a: valve 25b: valve 26a: supply source 26b: supply source 31: pressure unit 32: piping 33: connector 34: pump 35: filter 41: first tank 42: second tank 44: mixing section 45a: piping 45b: piping 46: connector 47a: pump 47b: pump 48a: filter 48b: filter 49a: valve 49b: valve A: concave part B: rotation axis C: carrier g: treatment liquid G: liquid film of treatment liquid G1: upper surface of liquid film H: thickness of liquid film J: gas K: cured film P: pattern S1, S11-S18: steps W: substrate W1: convex part W1a: lower end of convex part

FIG. 1 is a diagram schematically showing a portion of a substrate. FIG. 2 is a top view showing the interior of a substrate processing apparatus according to an embodiment. FIG. 3 is a control block diagram of the substrate processing apparatus. FIG. 4 is a diagram showing the configuration of a processing unit and a first supply source. FIG. 5 is a flow chart showing the procedure of a substrate processing method according to an embodiment. FIG. 6 is a diagram schematically showing a substrate in a processing liquid supply process. FIG. 7 is a diagram schematically showing a substrate in a cured film forming process. FIG. 8 is a diagram schematically showing a substrate in a cured film forming process. FIG. 9 is a diagram schematically showing a substrate in a sublimation process. FIG. 10 is a diagram schematically showing a substrate in a sublimation process. FIG. 11 is a diagram showing the configuration of a processing unit and a first supply source according to a modified embodiment.

S1, S11-S18: Steps

Claims (5)

A substrate processing method is used to process a substrate formed with a pattern, comprising: a processing liquid supplying step, in which a processing liquid containing a sublimable substance and a solvent is supplied to the substrate; a solidified film forming step, in which the solvent is evaporated from the processing liquid on the substrate to form a solidified film containing the sublimable substance on the substrate; and a sublimation step, in which the solidified film is sublimated; and the sublimable substance is 4-nitrotoluene. The substrate processing method of claim 1, wherein the solvent is isopropyl alcohol. A substrate processing device comprises: a substrate holding part that holds a substrate; and a processing liquid supply part that supplies a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding part; and the sublimable substance is 4-nitrotoluene. As in claim 3, the substrate processing device, wherein the solvent is isopropyl alcohol. A treatment liquid is used to dry a substrate with a pattern formed thereon, and the treatment liquid contains a sublimable substance and a solvent, the sublimable substance is 4-nitrotoluene, and the solvent is isopropyl alcohol.