TW202434711A - 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 comprises 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 comprises 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, the solidified film is formed on the substrate. The solidified film comprises a sublimable substance. In the sublimation process, the solidified film is sublimated. Due to the sublimation of the solidified film, the substrate is dried. Here, the sublimable substance comprises at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate.

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. For example, the substrate is 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 disc substrate, an optical disc substrate, a magneto-optical disk substrate, a photomask substrate or 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. If the substrate processing method of Patent document 1 is used, the substrate can be properly dried. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Application Publication No. 2021-9988.

[The problem that the invention wants to solve]

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

The present invention was developed in view of such a reason, and its purpose is to provide: a substrate processing method, a substrate processing device, and a processing liquid capable of properly drying a substrate. [Means for solving the problem]

The present invention is constructed as described below in order to achieve the above object. That is, the present invention is a substrate processing method for processing a substrate formed with a pattern, and comprises: a processing liquid supplying step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate; a solidified film forming step of evaporating the solvent from the processing liquid on the substrate, thereby forming a solidified film containing the sublimable substance on the substrate; and a sublimation step of sublimating the solidified film; the sublimable substance comprising at least one of the following substances: o-acetanisidide (also known as N-(2-methoxyphenyl)acetamide), N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid acid), 2-chlorophenylacetic acid, and dimethyl isophthalate.

The substrate processing method is a method for processing 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 includes 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 includes a sublimable substance. In the sublimation process, the solidified film is sublimated. Due to the sublimation of the solidified film, the substrate is dried.

Here, the sublimable substance includes at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, the cured film is well formed on the substrate in the cured film forming step.

The cured film includes at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, the cured film is appropriately sublimated in the sublimation process. That is, the substrate is appropriately dried in the sublimation process. Specifically, the pattern formed on the substrate is well protected and the substrate is dried in the sublimation process.

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

In the above substrate treatment method, the solvent is preferably isopropanol (IPA). IPA dissolves 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate well. Therefore, the substrate is dried more appropriately.

The present invention is a substrate processing device, which comprises: a substrate holding part, which is used to hold a substrate; and a processing liquid supply part, which is used to supply a processing liquid containing a sublimable substance and a solvent to the aforementioned substrate held by the aforementioned substrate holding part; the aforementioned sublimable substance contains at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate.

The substrate processing device includes a substrate holding part and a processing liquid supply part. The substrate holding part is used to hold the substrate. The processing liquid supply part is used to supply the processing liquid to the substrate held by the substrate holding part. The processing liquid contains a sublimable substance and a solvent.

Here, the sublimable substance includes at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, when the processing liquid is supplied to the substrate, a cured film is well formed on the substrate.

The cured film includes at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, the cured film is appropriately sublimated. That is, the substrate is appropriately dried. Specifically, the pattern formed on the substrate is well protected and the substrate is dried.

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

In the substrate processing apparatus described above, the solvent is preferably isopropyl alcohol. Isopropyl alcohol can dissolve 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate well. Therefore, the substrate is dried more appropriately.

The present invention is a processing liquid used for drying a substrate formed with a pattern; the processing liquid comprises: a sublimable substance; and a solvent; the sublimable substance comprises at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate.

The processing liquid is used for drying the substrate with the pattern formed thereon. Specifically, the processing liquid is a drying auxiliary liquid. The processing liquid contains a sublimable substance and a solvent.

Here, the sublimable substance includes at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, by supplying the processing liquid to the substrate, a cured film is well formed on the substrate. Further, the cured film is appropriately sublimated. That is, the substrate is appropriately dried. Specifically, the pattern formed on the substrate is well protected and the substrate is dried.

As described above, the substrate is properly dried using the treatment liquid. The treatment liquid is useful for the purpose of drying the substrate.

In the above-mentioned treatment liquid, the aforementioned solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate well. Therefore, the substrate is more properly dried using the treatment liquid. The treatment liquid is more useful for the purpose of drying the substrate.

In the above-mentioned treatment liquid, it is preferred that: the treatment liquid is supplied to the substrate, and after the solvent evaporates from the treatment liquid on the substrate to form a cured film containing the sublimable substance on the substrate, the cured film is sublimated. When the treatment liquid is used in this way, the substrate is more appropriately dried. When the treatment liquid is used in this way, the treatment liquid is more useful for the purpose of drying the substrate. [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.

The following is a description of the substrate processing method, substrate processing device, and processing liquid of the present invention with reference to the drawings. [1. Substrate W]

For example, the substrate W is a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL, a substrate for an FPD, a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a mask, or a substrate for a solar cell. The substrate W has a thin flat plate shape. The substrate W has a slightly 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.

For example, the pattern P has a concave-convex shape. For example, the pattern P 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. For example, the convex portion W1 is composed of at least any one of the following substances: a silicon oxide film ( _SiO2 film), a silicon nitride film (SiN film), and a polycrystalline silicon film (poly-silicon film). For example, the convex portion W1 is raised 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. For example, the concave portion A 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 specification, the processing liquid used for drying the substrate W is simply referred to as "processing liquid". The processing liquid has the function of assisting the drying of the substrate W. The processing liquid can be alternatively referred to as "drying assisting liquid".

The processing liquid contains a sublimable substance. A sublimable substance has the property of sublimation. "Sublimation" refers to the property of an element, compound or mixture to change from a solid to a gas without passing through a liquid, or from a gas to a solid without passing through a liquid.

Sublimable substances are, for example, compounds a, b, c, d, e, and f. Compound a: o-acetamidoanisole. Compound b: N-ethyl-p-toluenesulfonamide. Compound c: 4-chlorophenylacetic acid. Compound d: 4-methoxyphenylacetic acid. Compound e: 2-chlorophenylacetic acid. Compound f: dimethyl isophthalate.

N-ethyl-4-methylbenzenesulfonamide is also known as "N-ethyl-4-methylbenzenesulfonamide". 4-Chlorophenylacetic acid is also known as "2-(4-chlorophenyl)acetic acid". 4-Methoxyphenylacetic acid is also known as "2-(4-methoxyphenyl)acetic acid". 2-Chlorophenylacetic acid is also known as "2-(2-chlorophenyl)acetic acid". Dimethyl isophthalate is also known as "dimethyl benzene-1,3-dicarboxylate".

The sublimable substance includes at least one of compounds a, b, c, d, e, and f. For example, the sublimable substance includes compound a. For example, the sublimable substance includes compound a and compound b. For example, the sublimable substance includes compounds a to f.

For example, the sublimable substance is composed of at least one of compounds a to f. For example, the sublimable substance is composed of compound a. For example, the sublimable substance is composed of compound a and compound b. For example, the sublimable substance is composed of compounds a to f.

For example, the sublimable substance is at least any one of compounds a to f. For example, the sublimable substance is compound a. For example, the sublimable substance is compound a and compound b. For example, the sublimable substance is compounds a to f.

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

The solvent has a relatively high vapor pressure. 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. For example, normal temperature is a temperature in the range of 5°C to 35°C. For example, normal temperature is a temperature in the range of 10°C to 30°C. For example, normal temperature is a temperature in the range of 20°C to 25°C.

For example, the solvent is an organic solvent. For example, the solvent is alcohol.

For example, the solvent comprises isopropyl alcohol. For example, the solvent consists only of isopropyl alcohol. For example, the solvent is isopropyl alcohol.

For example, the treatment solution consists only of the sublimable substance and the solvent.

For example, the treatment liquid consists of only compound a and isopropyl alcohol. For example, the treatment liquid consists of only compounds a to f and isopropyl alcohol.

The volume of the sublimable substance contained in the processing liquid is smaller than the volume of the solvent contained in the processing liquid. For example, the volume ratio RV of the processing liquid is preferably 1 Vol% (volume percentage concentration) or more and 20 Vol% or less. Here, the volume ratio RV of the processing liquid is the ratio of the volume of the sublimable substance contained in the processing liquid to the volume of the solvent contained in the processing liquid. In other words, the volume ratio RV of the processing liquid is defined by the following formula. RV = (volume of sublimable substance contained in the processing liquid) / (volume of solvent contained in the processing liquid) × 100 (unit: Vol%) [3. Overview of substrate processing device 1]

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 an indexer unit 3 and a processing block 7. The processing block 7 is connected to the indexer unit 3. The indexer unit 3 supplies a substrate W to the processing block 7. The processing block 7 processes the substrate W. The indexer unit 3 collects the substrate W from the processing block 7.

For the sake of simplicity, in this manual, the direction in which the index section 3 and the processing block 7 are arranged is referred to as the "front-rear direction X". The front-rear direction X is horizontal. In the front-rear direction X, the direction from the processing block 7 toward the index section 3 is referred to as the "front". The direction opposite to the front is referred to as the "rear". The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y". One of the directions 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". Front, back, left, right, top, and bottom are appropriately marked in each figure for reference.

The indexing unit 3 has a plurality of (e.g., four) carrier loading units 4. Each carrier loading unit 4 is loaded with a carrier C. The carrier C accommodates a plurality of substrates W. For example, the carrier C is a front opening unified pod (FOUP), a standard mechanical interface (SMIF), or an open cassette (OC).

The indexing portion 3 is provided with a transport mechanism 5. The transport mechanism 5 is arranged at the rear of the carrier loading portion 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 can access the carrier C loaded on the carrier loading portion 4. The transport mechanism 5 is provided with a hand 5a and a hand driving portion 5b. The hand 5a supports the substrate W. The hand driving portion 5b is connected to the hand 5a. The hand driving portion 5b moves the hand 5a. For example, the hand driving portion 5b moves the hand 5a in the front-rear direction X, the width direction Y, and the vertical direction Z. For example, the hand driving portion 5b rotates the hand 5a in a horizontal plane.

The processing block 7 is equipped with a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 and the transport mechanism 5 can receive and transfer the substrate W to each other. The transport mechanism 8 is equipped with a hand 8a and a hand driving part 8b. The hand 8a supports the substrate W. The hand driving part 8b is connected to the hand 8a. The hand driving part 8b moves the hand 8a. For example, the hand driving part 8b moves the hand 8a in the front-back direction X, the width direction Y, and the vertical direction Z. For example, the hand driving part 8b rotates the hand 8a in a horizontal plane.

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

The processing unit 11 is provided with a substrate holding portion 13. The substrate holding portion 13 is configured to hold a substrate W. The substrate holding portion 13 is provided with at least one of a vacuum chuck, a Bernoulli chuck, and a chuck pin. The vacuum chuck and the Bernoulli chuck respectively hold the substrate W by suction. For example, the vacuum chuck holds the center of the substrate W by suction. For example, the Bernoulli chuck also holds the center of the substrate W by suction. The chuck pin holds the substrate W. For example, the chuck pin holds the end surface of the substrate W.

The transport mechanism 8 can access each processing unit 11 . The transport mechanism 8 can transfer the substrate W to the substrate holding portion 13 . The transport mechanism 8 can take 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 realized by the following components and the like: a central processing unit (CPU) for executing various processing; a random access memory (RAM) as a working area for calculation processing; and a storage medium such as a hard disk drive (HDD). The control unit 10 has various information pre-stored in a storage medium. For example, the information possessed by the control unit 10 is the transport condition information for controlling the transport mechanisms 5 and 8. For example, the information possessed by the control unit 10 is the processing condition information for controlling the processing unit 11. The processing condition information is also called a processing recipe.

Referring to Fig. 2, an operation example of the substrate processing apparatus 1 will be briefly described.

The transport mechanisms 5 and 8 transport the substrate W from the carrier C to the processing unit 11. Specifically, the transport mechanism 5 transports the substrate W from the carrier C. Then, the transport mechanism 5 transports the substrate W from the carrier C to the transport mechanism 8. The transport mechanism 8 transports the substrate W from the transport mechanism 5 to the processing unit 11. The transport mechanism 8 transfers the substrate W to the substrate holding portion 13 of the processing unit 11.

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

After the processing unit 11 processes the substrate W, the transport mechanisms 5 and 8 transport the substrate W from each processing unit 11 to the carrier C. Specifically, the transport mechanism 8 obtains the substrate W from the substrate holding portion 13 of the processing unit 11. The transport mechanism 8 transports the substrate W from the processing unit 11 to the transport mechanism 5. The transport mechanism 8 transports the substrate W from the transport mechanism 5 to the carrier C. The transport mechanism 8 transports the substrate W into the carrier C. [4. Structure of the processing unit 11]

FIG4 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 blade 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 is substantially box-shaped. The substrate W is processed inside the housing 12.

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

The interior of the frame 12 is maintained at normal pressure. The pressure of the gas inside the frame 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; 101325Pa). For example, normal pressure is the pressure in the range of 0.7 atmospheres to 1.3 atmospheres. In this specification, the pressure value is expressed as an absolute pressure based on an absolute vacuum.

The substrate holding portion 13 is disposed inside the frame 12. The substrate holding portion 13 holds a 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 is provided with a rotation drive unit 14. At least a portion of the rotation drive unit 14 is disposed inside the frame 12. The rotation drive unit 14 is connected to the substrate holding unit 13. The rotation drive unit 14 rotates the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates integrally with the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates around a rotation axis B. For example, the rotation axis B extends in the vertical direction Z through the center of the substrate W.

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 the above-mentioned treatment liquid. The second supply unit 15b supplies the chemical solution. The third supply unit 15c supplies the rinse liquid. The fourth supply unit 15d supplies the replacement liquid. The fifth supply unit 15e supplies the dry gas.

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

As described above, the interior of the frame 12 is at room temperature and pressure. Therefore, the processing liquid is used in an environment of room temperature and pressure.

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

For example, the cleaning liquid supplied by the third supply unit 15c is deionized water (DIW).

For example, the replacement liquid supplied by the fourth supply unit 15d is an organic solvent. For example, the replacement liquid is isopropyl alcohol.

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

The first supply unit 15a has a nozzle 16a. Similarly, the second supply unit 15b to the fifth supply unit 15e have nozzles 16b to 16e, respectively. The nozzles 16a to 16e are respectively disposed inside the frame 12. The nozzle 16a sprays a treatment liquid. The nozzle 16b sprays a chemical solution. The nozzle 16c sprays a cleaning 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 supply section 15b to the fifth supply section 15e include pipes 17b to 17e and valves 18b to 18e, respectively. The pipes 17b to 17e are connected to the nozzles 16b to 16e, respectively. The valves 18b to 18e are provided on the pipes 17b to 17e, respectively. Valves 18b to 18e control the spraying of chemical solution, cleaning fluid, replacement fluid and drying gas respectively.

At least a part of the pipe 17a may be disposed outside the housing 12. The same applies to the pipes 17b to 17e, and they 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 portion 15a. For example, the first supply source 19a is connected to the pipe 17a. The first supply source 19a is connected to the first supply portion 15a. The first supply source 19a delivers the processing liquid to the first supply portion 15a.

The second supply part 15b is connected to the second supply source 19b. For example, the piping 17b is connected to the second supply source 19b. The second supply part 15b is connected to the second supply source 19b. The second supply source 19b delivers the liquid medicine to the second supply part 15b. Similarly, the third supply part 15c to the fifth supply part 15e are respectively connected to the third supply source 19c to the fifth supply source 19e. For example, the piping 17c to the piping 17e are respectively connected to the third supply source 19c to the fifth supply source 19e. The third supply part 15c to the fifth supply part 15e are respectively connected to the third supply source 19c to the fifth supply source 19e. The third supply source 19c delivers the cleaning liquid to the third supply part 15c. The fourth supply source 19d delivers the replacement liquid to the fourth supply portion 15d. The fifth supply source 19e delivers the dry gas to the fifth supply portion 15e.

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

The second supply source 19b may also be one of the elements of the substrate processing apparatus 1. For example, the second supply source 19b may also be a chemical solution tank provided in the substrate processing apparatus 1. Alternatively, the second supply source 19b may not be one of the elements of the substrate processing apparatus 1. For example, the second supply source 19b may also be a utility equipment disposed outside the substrate processing apparatus 1. Similarly, the third supply source 19c to the fifth supply source 19e may also be one of the elements of the substrate processing apparatus 1. Alternatively, the third supply source 19c to the fifth supply source 19e may also not be one of the elements of the substrate processing apparatus 1.

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

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 valves 18a to 18e. [5. Configuration of the first supply source 19a]

Refer to Fig. 4. The first supply source 19a further generates a processing liquid g.

The configuration example of the first supply source 19a is described 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 g. The pressure-feeding unit 31 delivers the processing liquid g 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 an environment of normal temperature. The tank 22 is set in an environment of normal pressure. Therefore, the processing liquid g is generated in an environment of normal temperature. The processing liquid g is generated in an environment of normal pressure.

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

For example, the supply unit 23a includes a pipe 24a and a valve 25a. The pipe 24a is connected to the tank 22. The pipe 24a is connected to the tank 22. The valve 25a is provided on the pipe 24a. When the valve 25a is opened, the supply unit 23a supplies the sublimation substance to the tank 22. When the valve 25a is closed, the supply unit 23a does not supply the sublimation substance to the tank 22. Similarly, the supply unit 23b includes a pipe 24b and a valve 25b. The pipe 24b is connected to the tank 22. The pipe 24b is connected to 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.

For example, valves 25a and 25b may include flow regulating valves, respectively. For example, valves 25a and 25b may include flow regulating valves and on-off valves.

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

The pressure-feeding unit 31 includes a pipe 32 and a connector 33. The pipe 32 is connected to the tank 22. The pipe 32 is connected to the tank 22. The connector 33 is connected to the pipe 32. The connector 33 is further connected to the pipe 17a. The pipe 32 is connected to the pipe 17a through the connector 33. The pipe 32 is connected to the pipe 17a through the connector 33. Therefore, the tank 22 is connected to the first supply part 15a through the pipe 32 and the connector 33. The tank 22 is connected to the first supply part 15a through the pipe 32 and the connector 33. Therefore, 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 transports the processing liquid g from the tank 22 to the first supply portion 15a. When the pump 34 stops operating, the pump 34 does not transport the processing liquid g from the tank 22 to the first supply portion 15a. The filter 35 is disposed in the piping 32. The processing liquid g passes through the filter 35. The filter 35 filters the processing liquid g. The filter 35 removes foreign matter from the processing liquid g.

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 processing liquid condition information for controlling the first supply source 19a. For example, the processing liquid condition information includes a target value of 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. Operation example of the first supply source 19a and the processing unit 11]

FIG5 is a flow chart showing the sequence of the substrate processing method of the embodiment. The substrate processing method includes step S1 and steps S11 to S18. Step S1 is performed by the first supply source 19a. Steps S11 to S18 are substantially performed by the processing unit 11. Step S1 is performed in parallel with steps S11 to S18. The first supply source 19a and the processing unit 11 operate in accordance with the control of the control unit 10.

Referring to FIG. 4 , each step of steps S1 and S11 to S18 will be described.

Step S1: Processing liquid generating step In the processing liquid generating step, processing liquid g is generated.

The generation unit 21 generates the treatment liquid g. Specifically, the supply unit 23a supplies the sublimation substance to the tank 22. The supply unit 23b supplies the solvent to the tank 22. The sublimation substance and the solvent are mixed in the tank 22. That is, the treatment liquid g is generated in the tank 22. The treatment 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 defined 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. Thus, the substrate W held by the substrate holding part 13 starts to rotate.

In steps S12 to S17 described below, for example, the substrate W is continuously rotated.

Step S12: Chemical solution supplying process. In the chemical solution supplying 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 to the substrate W. Specifically, the valve 18b is closed, and the nozzle 16b stops ejecting the chemical solution.

Step S13: Cleaning liquid supplying process. In the cleaning liquid supplying process, the cleaning liquid is supplied to the substrate W.

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

Thereafter, the third supply unit 15c stops supplying the cleaning liquid to the substrate W. Specifically, the valve 18c is closed, and the nozzle 16c stops ejecting the cleaning 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 ejects the replacement liquid. The replacement liquid is supplied to the upper surface of the substrate W. The replacement liquid removes the cleaning liquid from the substrate W. The cleaning 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, and the nozzle 16d stops ejecting the replacement liquid.

Step S15: Processing liquid supplying process. The processing liquid g is supplied to the substrate W in the processing liquid supplying process.

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 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 supplying portion 15a. The first supplying portion 15a stops supplying the processing liquid g to the substrate W. Specifically, the pump 34 stops. The valve 18a is closed. The nozzle 16a stops ejecting the processing liquid g.

Fig. 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. When the substrate W is held by the substrate holding portion 13, the protrusion W1 extends 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.

All patterns P are immersed in the liquid film G. All convex portions W1 are immersed in the liquid film G. The concave portions A are filled with the liquid film G. All concave portions A are filled only with the liquid film G.

The liquid film G has an upper surface G1. The upper surface G1 is located at a position higher than the pattern P. The entire 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. Specifically, the upper surface G1 is located at a position higher than the convex portion W1. The entire 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.

In addition, the replacement liquid has been removed from the substrate W by the processing liquid g. Therefore, the replacement liquid does not exist on the substrate W. The replacement liquid does not remain in the concave 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 to the gas J. The convex portion W1 is not in contact with the gas J. The convex portion W1 is not exposed to 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 upper surface G1 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. Therefore, the pattern P does not bear the surface tension of the processing liquid g. The convex portion W1 does not bear the surface tension of the processing liquid g.

The height position of the upper surface G1 may be further adjusted in the process of supplying the processing liquid. For example, the nozzle 16a may adjust the height position of the upper surface G1 while supplying the processing liquid g to the substrate W. For example, the height position of the upper surface G1 may be adjusted after the nozzle 16a stops supplying the processing liquid g. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation time of the substrate W.

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

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

FIG. 7 schematically shows a substrate W in the cured film forming process. As described above, the solvent has a relatively high vapor pressure. At room temperature, the vapor pressure of the solvent is higher than the vapor pressure of 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. 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.

Finally, the sublimation substance in the liquid film G begins to precipitate on the substrate W. That is, the sublimation substance is transformed from the solute of the processing liquid g into a solid-phase sublimation substance. The solid-phase sublimation substance 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.

Due to the precipitation of sublimation substances, the liquid film G gradually changes into a solidified film K. Due to the evaporation of the solvent and the precipitation of sublimation substances, the liquid film G gradually decreases. Due to the precipitation of sublimation substances, the solidified film K gradually increases.

First, the upper portion of the liquid film G is transformed 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 isolates 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 convex portion W1 does not intersect with the air-liquid interface. Therefore, the pattern P does not bear the surface tension of the processing liquid g. The convex portion W1 does not bear the surface tension of the processing liquid g.

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. The liquid film G does not exert an influential force on the protrusion W1, and the liquid film G decreases. The solvent does not exert an influential force on the protrusion W1, and the solvent is removed from the substrate W.

FIG8 schematically shows a substrate W in the cured film forming step. For example, FIG8 schematically shows the substrate W at the end of the cured film forming step. At the end of the cured film forming step, all the liquid film G disappears from the substrate W. The liquid film G does not remain in the concave portion A. All the solvent disappears from the substrate W. The solvent also does not remain in the concave portion A.

At the end of the solidified film forming step, only the solidified film K exists on the substrate W. The concave portion A is filled with the solidified film K. All the concave portions A are filled only with the solidified film K. The pattern P is in contact with the solidified film K. The solidified film K supports the pattern P. The solidified film K protects the pattern P. For example, the solidified film K prevents the pattern P from collapsing. The protrusion W1 is in contact with the solidified film K. The solidified film K supports the protrusion W1. The solidified film K protects the protrusion W1. For example, the solidified film K prevents the protrusion W1 from collapsing.

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

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. As the cured film K sublimates, 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, and the nozzle 16e stops spraying the dry gas.

FIG9 schematically shows the substrate W in the sublimation process. As the solidified film K sublimates, the solidified film K gradually decreases. As the solidified film K sublimates, the solidified film K gradually becomes thinner. The pattern P begins to be exposed to the gas J. The protrusion W1 begins to be exposed to the gas J.

When the cured film K sublimates, the cured film K does not exert a force that affects the pattern P. The cured film K does not exert a force that affects the pattern P, and the cured film K is removed from the substrate W. When the cured film K sublimates, the cured film K does not exert a force that affects the convex portion W1. The cured film K does not exert a force that affects the convex portion W1, and the cured film K is removed from the substrate W.

When the solidified film K sublimates, the solidified film K does not change into liquid. Therefore, liquid is not generated on the substrate W in the sublimation process. Liquid does not exist on the substrate W in the sublimation process. Liquid does not exist in the concave portion A in the sublimation process. The gas-liquid interface is not generated near the pattern P in the sublimation process. Therefore, the pattern P does not intersect with the gas-liquid interface in the sublimation process. The gas-liquid interface is not generated near the convex portion W1 in the sublimation process. Therefore, the convex portion W1 does not intersect with the gas-liquid interface in the sublimation process.

FIG. 10 schematically shows a substrate W in a sublimation process. For example, FIG. 10 schematically shows a substrate W at the end of the sublimation process. At the end of the sublimation process, all the solidified film K disappears from the substrate W. The solidified film K does not exist on the substrate W. The liquid does not exist on the substrate W. All the patterns P are exposed to the gas J. All the protrusions W1 are exposed to the gas J. All the concave portions A are filled only with the gas J. The substrate W is dried.

The processing in the above-mentioned processing liquid supply process, solidified film forming process and sublimation process is an example of dry processing. The processing in the above-mentioned processing liquid supply process, solidified film forming process and sublimation process is equivalent to the use example of processing liquid g. The use example of processing liquid g is summarized as follows. Processing liquid g is supplied to substrate W, and the solvent is evaporated from processing liquid g on substrate W, and after solidified film K containing sublimable substance is formed on substrate W, solidified film K is sublimated. Processing liquid g is used under normal temperature environment. Processing liquid g is used under 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 ends the processing of the substrate W. [7. Technical significance of the processing liquid g]

The technical significance of processing liquid g is explained according to Examples 1 to 6.

The conditions of Example 1 are described below. In Example 1, the substrate W is subjected to a series of processes including a chemical solution supplying step, a cleaning solution supplying step, a replacement solution supplying step, a processing solution supplying step, a cured film forming step, and a sublimation step.

The chemical liquid used in the chemical 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 cleaning liquid used in the cleaning liquid supply process is deionized water.

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

The treatment liquid g used in the treatment liquid supply step is composed of a sublimable substance and a solvent. The sublimable substance is compound a. Specifically, the sublimable substance is o-acetamidoanisole. The solvent is isopropyl alcohol. 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, dry gas is supplied to the substrate W while the substrate W is rotated at a rotation speed of 1500 rpm.

The conditions of Example 2 are described below. In Example 2, the sublimable substance is compound b. Specifically, in Example 2, the sublimable substance is N-ethyl-p-toluenesulfonamide. Regarding other conditions, Example 2 is the same as Example 1.

The conditions of Example 3 are described. In Example 3, the sublimable substance is compound c. Specifically, in Example 3, the sublimable substance is 4-chlorophenylacetic acid. Regarding other conditions, Example 3 is the same as Example 1.

The conditions of Example 4 are described. In Example 4, the sublimable substance is compound d. Specifically, in Example 4, the sublimable substance is 4-methoxyphenylacetic acid. Regarding other conditions, Example 4 is the same as Example 1.

The conditions of Example 5 are described. In Example 5, the sublimable substance is compound e. Specifically, in Example 5, the sublimable substance is 2-chlorophenylacetic acid. Regarding other conditions, Example 5 is the same as Example 1.

The conditions of Example 6 are described. In Example 6, the sublimable substance is compound f. Specifically, in Example 6, the sublimable substance is dimethyl isophthalate. Regarding other conditions, Example 6 is the same as Example 1.

Each substrate W processed in Examples 1 to 6 was evaluated based on the average collapse rate Ea.

The average collapse rate Ea is obtained as follows. The average collapse rate Ea is the average value of a plurality of local collapse rates Ei. The local collapse rate Ei is the collapse rate in the local band Fi. i is an arbitrary natural number between 1 and NF. The number NF is the number of local bands Fi. The number NF is a natural number greater than 2. Each local band Fi is a tiny area of the substrate W. For example, each local band Fi is magnified 50,000 times using a scanning electron microscope. The observer observes the pattern P in each local band Fi. The observer observes the convex portions W1 in each local band Fi one by one. The observer evaluates the convex portions W1 in each local band Fi one by one. The observer judges the convex portions W1 in each local band Fi one by one. Specifically, the observer determines whether the convex portion W1 has collapsed for each convex portion W1. The observer classifies each convex portion W1 into either a collapsed convex portion W1 or an uncollapsed convex portion W1. Here, the number of convex portions W1 observed in the local band Fi is NAi. The number of collapsed convex portions W1 in the local band Fi is NBi. The number NBi is less than the number NAi. The local collapse rate Ei is the ratio of the number NBi to the number NAi. For example, the local collapse rate Ei is defined by the following formula. Ei=NBi/NAi×100 (%) The average collapse rate Ea is the value obtained by dividing the sum of the local collapse rates Ei by the number NF.

In Example 1, the average collapse rate Ea is 1.35%. In Example 2, the average collapse rate Ea is 1.95%. In Example 3, the average collapse rate Ea is 3.14%. In Example 4, the average collapse rate Ea is 2.12%. In Example 5, the average collapse rate Ea is 1.93%. In Example 6, the average collapse rate Ea is 4.70%.

The average collapse rate Ea of Examples 1 to 6 is sufficiently low. Therefore, the collapse of the pattern P in Examples 1 to 6 has been well suppressed. In other words, the pattern P in Examples 1 to 6 has been well protected. Therefore, the substrate W in Examples 1 to 6 has been properly dried. Specifically, the pattern P formed on the substrate W has been well protected and the substrate W has been dried. [8. Effect of the embodiment]

The substrate processing method of the embodiment is a method for processing 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 is sublimated. Due to the sublimation of the solidified film, the substrate W is dried.

Here, the sublimable substance includes at least one of compounds a to f. Specifically, the sublimable substance includes at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, the cured film K is well formed on the substrate W in the cured film forming step.

The cured film K includes at least one of the compounds a to f. Therefore, the cured film K is appropriately sublimated in the sublimation process. That is, the substrate W is appropriately dried in the sublimation process. Specifically, the pattern P formed on the substrate W is well protected and the substrate W is dried in the sublimation process.

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

The solvent is isopropyl alcohol. Isopropyl alcohol dissolves compound a well. Similarly, isopropyl alcohol dissolves compounds b to f well. Therefore, it is easy to use the processing liquid g. Specifically, it is easy to supply the processing liquid g to the substrate W in the processing liquid supply process. Therefore, the processing liquid g is properly supplied to the substrate W. Therefore, the substrate W is more properly dried.

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. Therefore, it is easier to use the processing liquid g.

In the process of generating the treatment liquid, the treatment liquid g is generated by mixing the sublimable substance and the solvent. Therefore, it is easy to generate the treatment liquid g.

In the process liquid generation step, the process liquid g is stored in the tank 22. Therefore, it is easy to store the process liquid g. Therefore, it is easier to use the process liquid g.

As described above, the solvent is isopropyl alcohol. Therefore, the treatment liquid g can be easily disposed. The disposal of the treatment liquid g includes at least one of the preparation of the treatment liquid g, the generation of the treatment liquid g, the storage of the treatment liquid g, and the use of the treatment liquid g.

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 first 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.

Here, the sublimable substance includes at least one of the compounds a to f. Therefore, the cured film K is well formed on the substrate W.

The cured film K includes at least one of the compounds a to f. Therefore, the cured film K is appropriately sublimated. That is, the substrate W is appropriately dried. Specifically, the pattern P formed on the substrate W is well protected and the substrate W is dried.

As described above, according to the substrate processing apparatus 1, the substrate W is properly dried.

The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves compounds a to f well. Therefore, it is easy to use the processing liquid g. Specifically, it is easy for the first supply unit 15a to supply the processing liquid g to the substrate W held by the substrate holding unit 13. Therefore, the processing liquid g is properly supplied to the substrate W. Therefore, the substrate W is dried more well.

The processing liquid g is used for drying 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.

Here, the sublimable substance includes at least one of the compounds a to f. Therefore, by supplying the processing liquid g to the substrate W, the cured film K is well formed on the substrate W. Furthermore, the cured film K is appropriately sublimated. That is, the substrate W is appropriately dried. Specifically, 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 treatment liquid g. The treatment liquid g is useful for the purpose of drying the substrate W.

The solvent is isopropyl alcohol. As mentioned above, isopropyl alcohol dissolves compounds a to f well. Therefore, it is easy to use the treatment liquid g. Therefore, the substrate W is more properly dried by using the treatment liquid g. The treatment liquid g is more useful for drying the substrate W.

Furthermore, the treatment liquid g can be easily disposed of. For example, it is easy to prepare the treatment liquid g. For example, it is easy to generate the treatment liquid g. For example, it is easy to store the treatment liquid g. For example, it is easy to use the treatment liquid g.

The processing liquid g is supplied to the substrate W. The solvent evaporates from the processing liquid g on the substrate W. A solidified film K containing a sublimable substance is formed on the substrate W. Thereafter, the solidified film K sublimates. When the processing liquid g is used in this way, the substrate W is more appropriately dried. When the processing liquid g is used in this way, the processing liquid g is more useful for the purpose of drying the substrate W. [9. Modified Implementation Form]

The present invention is not limited to the implementation form and can be implemented in the following modified forms.

(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 g in the tank 22. However, the present invention 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 generate the processing liquid g in the flow path for 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 the modified embodiment. In addition, since the same symbols are attached to the same configuration as the embodiment, the detailed description will be 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 stores the solvent together with the sublimable substance. 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 further 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 connector 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 connector 46 is connected to the pipes 45a and 45b. The connector 46 is connected to the pipes 45a and 45b. The connector 46 is further connected to the pipe 17a. The connector 46 is further connected to the pipe 17a. The pipes 45a and 45b are connected to the pipe 17a through the connector 46. The pipes 45a and 45b are connected to the pipe 17a through the connector 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 connector 46 via the pipe 45a. The pump 47b delivers the solvent from the second tank 42 to the connector 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. For example, the valves 49a and 49b may each include a flow regulating valve. For example, the valves 49a and 49b may each include a flow regulating valve and an on-off valve.

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 sublimable substance from the first tank 41 to the connector 46. Pump 47b transports the solvent from the second tank 42 to the connector 46. The sublimable substance and the solvent are mixed in the connector 46. The sublimable substance and the solvent become the treatment liquid g in the connector 46. Furthermore, the treatment liquid g flows from the connector 46 to the first supply part 15a. The nozzle 16a sprays the treatment liquid g.

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

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

(2) The substrate processing method of the embodiment includes a chemical solution supply process, a cleaning solution supply process, and a replacement solution supply process. However, the present invention is not limited thereto. For example, at least one of the chemical solution supply process, the cleaning solution supply process, and the replacement solution supply process may be omitted. For example, all of the chemical solution supply process, the cleaning solution supply process, and the replacement solution supply process may be omitted.

(3) In the embodiment, the liquid (e.g., replacement liquid) is present on the substrate W when the processing liquid supply process is performed. That is, the processing liquid g is supplied to the substrate W in an undried state in the processing liquid supply process. However, the present invention is not limited thereto. For example, the liquid (e.g., replacement liquid) may not be present on the substrate W when the processing liquid supply process is performed. For example, the processing liquid g may be supplied to the substrate W in an already dried state in the processing liquid supply process.

(4) In the processing liquid supply process of the embodiment, the processing liquid G has removed the replacement liquid from the substrate W. However, the present invention is not limited to this. For example, in the processing liquid supply process, the processing liquid G can also clean the substrate W. For example, in the processing liquid supply process, the processing liquid G can also remove foreign matter attached to the substrate W. For example, in the processing liquid supply process, the processing liquid G can also dissolve foreign matter attached to the substrate W. For example, the foreign matter is resist 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. 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 in the cured film forming step. According to this modified embodiment, the processing liquid g on the substrate W is exposed to dry gas in the cured film forming step. Therefore, 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 in the cured film forming step.

(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 when the processing unit 11 processes the substrate W. For example, the pattern P may be formed on the substrate W during the chemical solution supply process (step S12).

(7) For the various modified implementation forms described in the implementation form and in (1) to (6) above, each structure can be further replaced or combined, so as to appropriately change it into the structure of other modified implementation forms.

1: substrate processing device 3: indexing unit 4: carrier loading unit 5,8: transport mechanism 5a,8a: hand 5b,8b: hand drive unit 7: processing block 10: control unit 11: processing unit 12: frame 13: substrate holding unit 14: rotation drive unit 15: supply unit 15a: first supply unit (processing liquid supply unit) 15b: second supply unit 15c: third supply unit 15d: fourth supply unit 15e: fifth supply unit 16a,16b,16c,16d,16e: nozzle 17a, 17b, 17c, 17d, 17e, 24a, 24b, 32, 45a, 45b: Piping 18a, 18b, 18c, 18d, 18e, 25a, 25b, 49a, 49b: Valve 19a: First supply source 19b: Second supply source 19c: Third supply source 19d: Fourth supply source 19e: Fifth supply source 21: Generating unit 22: Tank 23a, 23b: Supply unit 26a, 26b: Supply source 31: Pressure unit 33, 46: Connector 34, 47a, 47b: Pump 35, 48a, 48b: Filter 41: First tank 42: Second tank 44: Mixing part A: Concave part B: Rotation axis C: Carrier g: Processing liquid G: Liquid film G1: Upper surface H: Thickness J: Gas K: Cured film P: Pattern S1, S11 to S18: Steps W: Substrate W1: Convex part W1a: Bottom end X: Front and back direction Y: Width direction Z: Vertical direction

[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 of 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 sequence of a substrate processing method of 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. [Figure 11] is a diagram showing the structure of the processing unit and the first supply source of the modified implementation form.

S1, S11 to S18: Steps

Claims (7)

A substrate processing method is used to process a substrate formed with a pattern, and comprises: 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, thereby forming a solidified film containing the sublimable substance on the substrate; and a sublimation step, in which the solidified film is sublimated; the sublimable substance comprises at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. The substrate processing method as recited in claim 1, wherein the solvent is isopropyl alcohol. A substrate processing device comprises: a substrate holding portion for holding a substrate; and a processing liquid supply portion for supplying a processing liquid containing a sublimable substance and a solvent to the aforementioned substrate held by the aforementioned substrate holding portion; the aforementioned sublimable substance comprises at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. A substrate processing apparatus as recited in claim 3, wherein the solvent is isopropyl alcohol. A treatment liquid is used for drying a substrate having a pattern formed thereon; the treatment liquid comprises: a sublimable substance; and a solvent; the sublimable substance comprises at least one of the following substances: 2-acetamidoanisole, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. The treatment solution as recited in claim 5, wherein the solvent is isopropyl alcohol. The processing liquid as recited in claim 5, wherein the processing liquid is supplied to the substrate, and after the solvent evaporates from the processing liquid on the substrate to form a cured film containing the sublimable substance on the substrate, the cured film sublimates.