JP2024120472A - Substrate processing method, substrate processing apparatus, and processing solution - Google Patents

Abstract

[Problem] To provide a substrate processing method, a substrate processing apparatus, and a processing liquid that can appropriately dry a substrate. [Solution] The present invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, the processing liquid is supplied to the substrate. The processing liquid includes a sublimable substance and a solvent. In the solidified film forming step, the solvent is evaporated from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film includes a sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by the sublimation of the solidified film. Here, the sublimable substance includes at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. [Selected Figure] FIG.

Description

The present invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid. The substrate is, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic electroluminescence (EL), a substrate for a flat panel display (FPD), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell.

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 supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to a substrate. The processing liquid includes a solvent and a sublimable substance. The sublimable substance is cyclohexanone oxime. In the solidified film forming step, the solvent is evaporated and a solidified film is formed on the substrate. The solidified film includes cyclohexanone oxime. In the sublimation step, the solidified film sublimes. The solidified film changes into a gas without passing through a liquid state. According to the substrate processing method of Patent Document 1, the substrate can be appropriately dried.

JP 2021-9988 A

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 the pattern formed on the substrate collapses. For example, when the pattern is fine, conventional substrate processing methods may not be able to sufficiently prevent the collapse of the pattern.

The present invention has been made in consideration of these circumstances, and aims to provide a substrate processing method, a substrate processing apparatus, and a processing liquid that can properly dry substrates.

In order to achieve this object, the present invention has the following configuration. That is, the present invention is a substrate processing method for processing a substrate on which a pattern is formed, comprising a processing liquid supplying step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate, a solidified film forming step of evaporating the solvent from the processing liquid on the substrate to form a solidified film containing the sublimable substance on the substrate, and a sublimation step of sublimating the solidified film, in which the sublimable substance contains at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate.

The substrate processing method is for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to the substrate. The processing liquid includes a sublimable substance and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film includes a sublimable substance. In the sublimation step, the solidified film sublimes. The substrate is dried by sublimation of the solidified film.

Here, the sublimable substance contains at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, in the solidified film formation process, the solidified film is suitably formed on the substrate.

The solidified film contains at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, in the sublimation process, the solidified film sublimes appropriately. That is, in the sublimation process, the substrate is dried appropriately. Specifically, in the sublimation process, the substrate is dried while the pattern formed on the substrate is suitably protected.

As described above, this substrate processing method allows the substrate to be properly dried.

In the above-mentioned substrate processing method, the solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves o-acetaniside, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate favorably. Therefore, the substrate is more appropriately dried.

The present invention is a substrate processing apparatus comprising a substrate holding unit for holding a substrate, and a processing liquid supply unit for supplying a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding unit, the sublimable substance containing at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate.

The substrate processing apparatus includes a substrate holding unit and a processing liquid supply unit. The substrate holding unit holds a substrate. The processing liquid supply unit supplies a processing liquid to the substrate held by the substrate holding unit. The processing liquid includes a sublimable substance and a solvent.

Here, the sublimable substance contains at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, when the treatment liquid is supplied to the substrate, a solidified film is suitably formed on the substrate.

The solidified film contains at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, the solidified film sublimes appropriately. In other words, the substrate is dried appropriately. Specifically, the substrate is dried while the pattern formed on the substrate is appropriately protected.

As described above, this substrate processing apparatus allows the substrate to be properly dried.

In the above-mentioned substrate processing apparatus, the solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves o-acetaniside, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate favorably. Therefore, the substrate is more appropriately dried.

The present invention relates to a treatment liquid used for drying a substrate on which a pattern is formed, the treatment liquid including a sublimable substance and a solvent, the sublimable substance including at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate.

The processing liquid is used to dry the substrate on which the pattern is formed. Specifically, the processing liquid is a drying assistant liquid. The processing liquid contains a sublimable substance and a solvent.

Here, the sublimable substance includes at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, by supplying the treatment liquid to the substrate, a solidified film is suitably formed on the substrate. Furthermore, the solidified film is suitably sublimated. That is, the substrate is suitably dried. Specifically, the substrate is dried while the pattern formed on the substrate is suitably protected.

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

In the above-mentioned treatment liquid, the solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves o-acetaniside, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate favorably. Therefore, the substrate is more appropriately dried using the treatment liquid. The treatment liquid is more useful for drying the substrate.

In the above-mentioned processing liquid, it is preferable that the processing liquid is supplied to the substrate, the solvent is evaporated from the processing liquid on the substrate, a solidified film containing the sublimable substance is formed on the substrate, and then the solidified film is sublimated. When the processing liquid is used in this manner, the substrate is more appropriately dried. When the processing liquid is used in this manner, the processing liquid is more useful for drying the substrate.

The substrate processing method, substrate processing apparatus, and processing solution of the present invention allow the substrate to be properly dried.

FIG. 2 is a diagram illustrating a schematic view of a portion of a substrate. 1 is a plan view showing an inside of a substrate processing apparatus according to an embodiment; FIG. 2 is a control block diagram of the substrate processing apparatus. FIG. 2 is a diagram showing a configuration of a processing unit and a first supply source. 3 is a flowchart showing a procedure of a substrate processing method according to an embodiment. 4A to 4C are diagrams illustrating a substrate in a treatment liquid supplying step. 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. FIG. 2 is a diagram illustrating a substrate during a sublimation process. FIG. 2 is a diagram illustrating a substrate during a sublimation process. FIG. 13 is a diagram showing a configuration of a processing unit and a first supply source according to a modified embodiment.

The substrate processing method, substrate processing apparatus, and processing liquid of the present invention will be described below 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 electroluminescence (EL), a substrate for a flat panel display (FPD), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell. The substrate W has a thin, flat plate shape. The substrate W has a substantially circular shape in a plan view.

Figure 1 is a schematic diagram of 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 has, for example, an uneven shape. The pattern P has, for example, 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 is composed of, for example, at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN), and a polysilicon film. The convex portion W1 protrudes upward from the surface of the substrate W, for example. 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 is, for example, open upward. The convex portion W1 corresponds to a wall that defines 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 a "processing liquid." The processing liquid has a function of assisting in drying the substrate W. The processing liquid can be referred to as a drying assistant liquid.

The treatment liquid contains a sublimable substance. A sublimable substance has sublimation properties. "Sublimation" refers to the property of a single substance, compound, or mixture undergoing a phase transition from solid to gas, or from gas to solid, without passing through a liquid state.

The sublimable substance is, for example, compound a, b, c, d, e, or f.
Compound a: o-acetanisidide (N-(2-Methoxyphenyl)acetamide)
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-p-toluenesulfonamide is also called N-ethyl-4-methylbenzenesulfonamide. 4-Chlorophenylacetic acid is also called 2-(4-chlorophenyl)acetic acid. 4-Methoxyphenylacetic acid is also called 2-(4-methoxyphenyl)acetic acid. 2-Chlorophenylacetic acid is also called 2-(2-chlorophenyl)acetic acid. Dimethyl isophthalate is also called dimethyl benzene-1,3-dicarboxylate.

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

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

For example, the sublimable substance is at least one of compounds a-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 compound a-f.

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

The solvent has a relatively high vapor pressure at room temperature. For example, it is preferable that the vapor pressure of the solvent at room temperature is 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 or higher and 35°C or lower. Normal temperature is, for example, a temperature in the range of 10°C or higher and 30°C or lower. Normal temperature is, for example, a temperature in the range of 20°C or higher and 25°C or lower.

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

The solvent includes, for example, isopropyl alcohol (IPA). The solvent consists, for example, of only isopropyl alcohol. The solvent is, for example, isopropyl alcohol.

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

The treatment liquid consists, for example, of only compound a and isopropyl alcohol. The treatment liquid consists, for example, of only compounds a-f and isopropyl alcohol.

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 1 [Vol %] or more and 20 [Vol %] or less. 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 treatment liquid)/(volume of solvent contained in treatment liquid)*100 [Vol %]

3. Overview of the Substrate Processing Apparatus
2 is a plan view showing the inside of the substrate processing apparatus 1 according to the embodiment. The substrate processing apparatus 1 processes substrates W. The processes in the substrate processing apparatus 1 include 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 substrates W to the processing block 7. The processing block 7 processes the substrates W. The indexer unit 3 retrieves the substrates W from the processing block 7.

For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is referred to as the "front-rear direction X." The front-rear direction X is horizontal. Within the front-rear direction X, the direction from the processing block 7 toward the indexer unit 3 is referred to as the "front." The direction opposite to the front is referred to as the "rear." The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y." One direction in the "width direction Y" is referred to as the "right" as appropriate. The direction opposite to the right is referred to as the "left." The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z." In each figure, for reference, front, back, right, left, top, and bottom are indicated as appropriate.

The indexer unit 3 has multiple (e.g., four) carrier placement units 4. Each carrier placement unit 4 places one carrier C. The carrier C stores multiple 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 indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is disposed behind the carrier placement unit 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 is accessible to the carrier C placed on the carrier placement unit 4. The transport mechanism 5 includes a hand 5a and a hand drive unit 5b. The hand 5a supports the substrate W. The hand drive unit 5b is connected to the hand 5a. The hand drive unit 5b moves the hand 5a. The hand drive unit 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand drive unit 5b rotates the hand 5a, for example, in a horizontal plane.

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

The processing block 7 includes multiple processing units (chambers) 11. The processing units 11 are disposed to the side of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

The processing unit 11 includes a substrate holder 13. The substrate holder 13 is configured to hold a substrate W. The substrate holder 13 includes at least one of a vacuum chuck, a Bernoulli chuck, and a chuck pin. The vacuum chuck and the Bernoulli chuck each suction-hold the substrate W. The vacuum chuck suction-holds, for example, the center of the substrate W. The Bernoulli chuck also suction-holds, for example, the center of the substrate W. The chuck pin grips the substrate W. The chuck pin grips, for example, the edge surface of the substrate W.

The transport mechanism 8 can access each processing unit 11. The transport mechanism 8 can deliver a substrate W to the substrate holder 13. The transport mechanism 8 can take a substrate W from the substrate holder 13.

Figure 3 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 is capable of communicating with the transport mechanisms 5 and 8 and the processing unit 11. The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11.

The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a random-access memory (RAM) that serves as a working area for the processes, and a storage medium such as a fixed disk. The control unit 10 has various information that is pre-stored in the storage medium. The information held by the control unit 10 is, for example, transport condition information for controlling the transport mechanisms 5 and 8. The information held by the control unit 10 is, for example, processing condition information for controlling the processing unit 11. The processing condition information is also called a processing recipe.

Refer to Figure 2. An example of the operation 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 unloads the substrate W from the carrier C. The transport mechanism 5 then 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 passes the substrate W to the substrate holder 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 holder 13. The processing unit 11 performs, for example, a drying process on the substrate W.

After the processing units 11 process 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 takes the substrate W from the substrate holder 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 loads the substrate W into the carrier C.

4. Configuration of Processing Unit 11
4 is a diagram showing the configuration of the processing units 11. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer processing units, that is, each processing unit 11 processes only one substrate W at a time.

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

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

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

Here, normal pressure includes standard atmospheric pressure (1 atmosphere, 101,325 Pa). Normal pressure is, for example, a pressure in the range of 0.7 atmospheres or more and 1.3 atmospheres or less. In this specification, pressure values are indicated as absolute pressures based on an absolute vacuum.

The above-mentioned substrate holding unit 13 is installed inside the housing 12. The substrate holding unit 13 holds one substrate W. The substrate holding unit 13 holds the substrate W in a substantially horizontal position.

The substrate holding part 13 is positioned below the substrate W that it holds. The substrate holding part 13 contacts at least one of the lower surface of the substrate W and the peripheral edge of the substrate W. The lower surface of the substrate W is also called the backside of the substrate W. The substrate holding part 13 does not contact the upper surface of the substrate W.

The processing unit 11 includes a rotation drive unit 14. At least a portion of the rotation drive unit 14 is installed inside the housing 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. The rotation axis B passes through the center of the substrate W, for example, and extends in the vertical direction Z.

The processing unit 11 includes a supply section 15. The supply section 15 supplies a liquid or gas to the substrate W held by the substrate holding section 13. Specifically, the supply section 15 supplies a liquid or gas to the upper surface of the substrate W held by the substrate holding section 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 processing liquid. The second supply unit 15b supplies a chemical liquid. The third supply unit 15c supplies a rinsing liquid. The fourth supply unit 15d supplies a replacement liquid. The fifth supply unit 15e supplies a drying gas.

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

As described above, the inside of the housing 12 is at room temperature and pressure. Therefore, the processing liquid is used in a room 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 contains, 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.

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

The first supply unit 15a includes a nozzle 16a. Similarly, the second to fifth supply units 15b-15e include nozzles 16b-16e, respectively. The nozzles 16a-16e are each installed inside the housing 12. The nozzle 16a ejects a processing liquid. The nozzle 16b ejects a chemical liquid. The nozzle 16c ejects a rinsing liquid. The nozzle 16d ejects a replacement liquid. The nozzle 16e ejects a drying gas.

The first supply unit 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is open, the nozzle 16a ejects the processing liquid. When the valve 18a is closed, the nozzle 16a does not eject the processing liquid. Similarly, the second to fifth supply units 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. The valves 18b-18e control the ejection of the chemical liquid, the rinse liquid, the replacement liquid, and the drying gas, respectively.

At least a portion of pipe 17a may be provided outside the housing 12. Pipes 17b-17e may be arranged in the same manner as pipe 17a. Valve 18a may be provided outside the housing 12. Valves 18b-18e may be arranged in the same manner as 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, for example, a pipe 17a. The first supply source 19a is in communication with the first supply unit 15a. The first supply source 19a sends the processing liquid to the first supply unit 15a.

The second supply unit 15b is connected to the second supply source 19b. For example, the pipe 17b is connected to the second supply source 19b. The second supply unit 15b is connected to the second supply source 19b. The second supply source 19b sends a chemical solution to the second supply unit 15b. Similarly, the third to fifth supply units 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. For example, the pipes 17c-17e are connected to the third to fifth supply sources 19c-19e, respectively. The third to fifth supply units 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. The third supply source 19c sends a rinse liquid to the third supply unit 15c. The fourth supply source 19d sends a replacement liquid to the fourth supply unit 15d. The fifth supply source 19e sends a dry gas to the fifth supply unit 15e.

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

The first supply source 19a may supply processing liquid to multiple processing units 11. Alternatively, the first supply source 19a may supply processing liquid to only one processing unit 11. The same applies to the second to fifth supply sources 19b to 19e.

The second supply source 19b may be an element of the substrate processing apparatus 1. For example, the second supply source 19b may be a chemical tank provided in the substrate processing apparatus 1. Alternatively, the second supply source 19b may not be an element of the substrate processing apparatus 1. For example, the second supply source 19b may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the third to fifth supply sources 19c-19e may each be an element of the substrate processing apparatus 1. Alternatively, the third to fifth supply sources 19c-19e may each not be an element of the substrate processing apparatus 1.

The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12. The cup is disposed around the substrate holder 13. The cup catches liquid splashed from the substrate W held by the substrate holder 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 the valves 18a-18e.

5. Configuration of first supply source 19a
See Figure 4. The first source 19a also produces a processing liquid.

An example of the configuration of the first supply source 19a is shown. The first supply source 19a is divided into a generation unit 21 and a pressure-feeding unit 31. The generation unit 21 generates the treatment liquid. The pressure-feeding unit 31 sends the treatment liquid to the first supply section 15a.

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

The tank 22 is placed in an environment of normal temperature. The tank 22 is placed in an environment of normal pressure. Therefore, the treatment liquid g is produced in an environment of normal temperature. The treatment liquid g is produced 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 at room temperature. The processing liquid g is stored in an environment at normal pressure.

The supply unit 23a includes, for example, 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 open, the supply unit 23a supplies the sublimable substance to the tank 22. When the valve 25a is closed, the supply unit 23a does not supply the sublimable 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 sublimable material in tank 22 is controlled by valve 25a. The amount of solvent in tank 22 is controlled by valve 25b. Thus, the volume ratio RV of the treatment liquid g in tank 22 is controlled by valves 25a and 25b.

Valves 25a and 25b may each include, for example, a flow control valve. Valves 25a and 25b may each include, for example, a flow control valve and an on-off valve.

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

The pumping 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. Therefore, the tank 22 is connected to the nozzle 16a. The tank 22 is connected to the nozzle 16a.

The pumping unit 31 further includes a pump 34 and a filter 35. The pump 34 is provided in the piping 32. When the pump 34 is operating, the pump 34 sends the processing liquid g from the tank 22 to the first supply section 15a. When the pump 34 stops operating, the pump 34 does not send the processing liquid g from the tank 22 to the first supply section 15a. The filter 35 is provided 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 is capable of communicating 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 pumping 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. The processing liquid condition information includes, for example, a target value for the volume ratio RV of the processing liquid g. The processing liquid condition information is pre-stored in a storage medium of the control unit 10.

6. Operational Example of First Supply Source 19a and Processing Unit 11
5 is a flow chart showing the procedure of the substrate processing method of the embodiment. 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 substantially performed by the processing unit 11. Step S1 is performed in parallel with steps S11-S18. The first supply source 19a and the processing unit 11 operate according to the control of the controller 10.

Each step S1, S11-S18 will be explained with reference to FIG. 4 as appropriate.

Step S1: Treatment Liquid Producing Step In the treatment liquid producing step, the treatment liquid g is produced.

The generation unit 21 generates the processing liquid g. Specifically, the supply unit 23a supplies a sublimable substance to the tank 22. The supply unit 23b supplies a solvent to the tank 22. The sublimable substance and the solvent are mixed in the tank 22. That is, 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. As a result, the control unit 10 adjusts the volume ratio RV of the treatment liquid g in the tank 22 to the target value specified in the treatment liquid condition information.

Step S11: Rotation Start Step 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. As a result, the substrate W held by the substrate holding part 13 starts to rotate.

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

Step S12: Chemical Liquid Supplying Step In the chemical liquid supplying step, a chemical liquid is supplied to the substrate W.

The second supply unit 15b supplies the chemical liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18b opens. The nozzle 16b ejects the chemical liquid. The chemical liquid is supplied to the upper surface of the substrate W. For example, the chemical liquid etches the substrate W. For example, the chemical liquid removes a native oxide film from the substrate W.

Then, the second supply unit 15b stops supplying the chemical liquid to the substrate W. Specifically, the valve 18b closes. The nozzle 16b stops ejecting the chemical liquid.

Step S13: Rinsing Liquid Supplying Step In the rinsing liquid supplying step, a rinsing liquid is supplied to the substrate W.

The third supply unit 15c supplies the rinsing liquid to the substrate W held by the substrate holder 13. Specifically, the valve 18c opens. The nozzle 16c ejects the rinsing liquid. The rinsing liquid is supplied to the upper surface of the substrate W. For example, the rinsing liquid cleans the substrate W. For example, the rinsing liquid removes chemicals from the substrate W.

Then, the third supply unit 15c stops supplying the rinsing liquid to the substrate W. Specifically, the valve 18c closes. The nozzle 16c stops ejecting the rinsing liquid.

Step S14: Substitute Liquid Supplying Step In the substitute liquid supplying step, a substitute liquid is supplied to the substrate W.

The fourth supply unit 15d supplies the replacement liquid to the substrate W held by the substrate holder 13. Specifically, the valve 18d opens. The nozzle 16d ejects the replacement liquid. The replacement liquid is supplied to the top surface of the substrate W. The replacement liquid removes the rinsing liquid from the substrate W. The rinsing liquid on the substrate W is replaced with the replacement liquid.

After that, the fourth supply unit 15d stops supplying the replacement liquid to the substrate W. Specifically, the valve 18d closes. The nozzle 16d stops ejecting the replacement liquid.

Step S15: Processing Liquid Supplying Step In the processing liquid supplying step, the processing liquid g is supplied to the substrate W.

The pressure-feeding unit 31 supplies the processing liquid g to the first supply section 15a. The first supply section 15a supplies the processing liquid g to the substrate W held by the substrate holder 13. Specifically, the pump 34 sends the processing liquid g from the tank 22 to the first supply section 15a. The valve 18a opens. 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.

Then, the pressure-feeding unit 31 stops supplying the processing liquid g to the first supply section 15a. The first supply section 15a stops supplying the processing liquid g to the substrate W. Specifically, the pump 34 stops. The valve 18a closes. The nozzle 16a stops ejecting the processing liquid g.

Figure 6 is a schematic diagram of a substrate W in a processing liquid supplying process. When the substrate W is held by the substrate holding part 13, the pattern P is located on the upper surface of the substrate W. When the substrate W is held by the substrate holding part 13, the pattern P faces upward. When the substrate W is held by the substrate holding part 13, the convex part 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.

The entire pattern P is immersed in the liquid film G. The entire protrusion W1 is immersed in the liquid film G. The recess A is filled with the liquid film G. The entire recess A is filled only with the liquid film G.

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

The substitute liquid has already been removed from the substrate W by the processing liquid g. Therefore, the substitute liquid is not present on the substrate W. The substitute liquid does not remain in the recess A.

Gas J exists above liquid film G. Pattern P does not come into contact with gas J. Pattern P is not exposed to gas J. Convex portion W1 does not come into contact with gas J. Convex portion W1 is not exposed to gas J.

Gas J contacts liquid film G. Gas J contacts upper surface G1. Upper surface G1 corresponds to the gas-liquid interface between liquid film G and gas J. Therefore, pattern P does not intersect with the gas-liquid interface between liquid film G and gas J. Convex portion W1 does not intersect with the gas-liquid interface between liquid film G and gas J. Therefore, pattern P is not subjected to the surface tension of treatment liquid g. Convex portion W1 is not subjected to the surface tension of treatment liquid g.

In the processing liquid supplying process, the height position of the upper surface G1 may further be adjusted. For example, the height position of the upper surface G1 may be adjusted while the nozzle 16a is 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 corresponds 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 convex portion W1 and the upper surface G1.

Step S16: Solidified Film Forming Step In the solidified film forming step, the solvent evaporates from the processing liquid g on the substrate W. In the solidified film forming step, a solidified film is formed on the substrate W. The solidified film includes a sublimable substance.

Figure 7 is a diagram showing a substrate W in the solidified film formation 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 a liquid to a gas.

As the solvent evaporates from the processing liquid g on the substrate W, the solvent leaves 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.

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

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

First, the upper part of the liquid film G turns 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 gas-liquid interface. The protruding portion W1 does not intersect with the gas-liquid interface. Therefore, the pattern P is not subjected to the surface tension of the treatment liquid g. The protruding portion W1 is not subjected to the surface tension of the treatment 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 decreases without exerting a significant force on the protruding portion W1. The solvent leaves the substrate W without exerting a significant force on the protruding portion W1.

Figure 8 is a diagram showing a substrate W during the solidified film formation process. Figure 8 shows a schematic diagram of the substrate W, for example, at the end of the solidified film formation process. At the end of the solidified film formation process, all of the liquid film G has disappeared from the substrate W. No liquid film G remains in the recess A. All of the solvent has disappeared from the substrate W. No solvent remains in the recess A.

At the end of the solidified film formation process, only the solidified film K is present on the substrate W. The recess A is filled with the solidified film K. The entire recess A is filled with only 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 Step In the sublimation step, the solidified 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 opens. The nozzle 16e ejects dry gas. The nozzle 16e blows the dry gas onto the substrate W. The dry gas is supplied to the upper surface of the substrate W. The dry gas is supplied to the solidified film K. The solidified film K is exposed to the dry gas. This causes the solidified film K to sublime. The solidified film K changes into gas without passing through a liquid state. The solidified film K is removed from the substrate W by sublimation of the solidified film K.

Then, the fifth supply unit 15e stops supplying the dry gas to the solidified film K. Specifically, the valve 18e closes. The nozzle 16e stops blowing the dry gas.

Figure 9 is a diagram showing a substrate W in the sublimation process. As the solidified film K sublimes, the solidified film K gradually decreases. As the solidified film K sublimes, the solidified film K gradually becomes thinner. The pattern P begins to be exposed to the gas J. The protruding portion W1 begins to be exposed to the gas J.

When the solidified film sublimes, the solidified film K does not exert a significant force on the pattern P. The solidified film K leaves the substrate W without exerting a significant force on the pattern P. When the solidified film sublimes, the solidified film K does not exert a significant force on the protrusion W1. The solidified film K leaves the substrate W without exerting a significant force on the protrusion W1.

When the solidified film K sublimes, the solidified film K does not change into a liquid. Therefore, in the sublimation process, no liquid is generated on the substrate W. In the sublimation process, no liquid is present on the substrate W. In the sublimation process, no liquid is present in the recess A. In the sublimation process, no gas-liquid interface is generated near the pattern P. Therefore, in the sublimation process, the pattern P does not intersect with the gas-liquid interface. In the sublimation process, the protrusion W1 does not intersect with the gas-liquid interface.

Figure 10 is a diagram showing a substrate W during the sublimation process. Figure 10 shows a schematic diagram of the substrate W, for example, at the end of the sublimation process. At the end of the sublimation process, the entire solidified film K has disappeared from the substrate W. The solidified film K is not present on the substrate W. No liquid is present on the substrate W. The entire pattern P is exposed to the gas J. The entire protrusion W1 is exposed to the gas J. The entire recess A is filled only with the gas J. The substrate W is dried.

The above-mentioned processes in the processing liquid supply process, solidified film formation process, and sublimation process are examples of drying processes. The above-mentioned processes in the processing liquid supply process, solidified film formation process, and sublimation process correspond to examples of using processing liquid g. Examples of using processing liquid g are summarized below. Processing liquid g is supplied to substrate W, the solvent evaporates from processing liquid g on substrate W, a solidified film K containing a sublimable substance is formed on substrate W, and then solidified film K sublimes. Processing liquid g is used in an environment at room temperature. Processing liquid g is used in an environment at normal pressure.

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

7. Technical significance of processing solution g
The technical significance of processing solution g will be explained with reference to Examples 1-6.

The conditions of Example 1 will be described. In Example 1, the substrate W undergoes a series of processes including a chemical liquid supply process, a rinse liquid supply process, a replacement liquid supply process, a processing liquid supply process, a solidified film formation process, and a sublimation process.

The chemical used in the chemical supplying step 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.

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

The processing solution g used in the processing solution supplying process is composed of a sublimable substance and a solvent. The sublimable substance is compound a. Specifically, the sublimable substance is o-acetaniside. The solvent is isopropyl alcohol. The volume ratio RV of the processing solution g is 2.5 [Vol%].

In the solidified film formation process, the substrate W is rotated at a rotational speed of 1500 rpm.

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

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

The conditions of Example 3 are explained below. In Example 3, the sublimable substance is compound c. Specifically, in Example 3, the sublimable substance is 4-chlorophenylacetic acid. Other than this, the conditions of Example 3 are the same as those of Example 1.

The conditions of Example 4 are explained below. In Example 4, the sublimable substance is compound d. Specifically, in Example 4, the sublimable substance is 4-methoxyphenylacetic acid. Other than this, the conditions of Example 4 are the same as those of Example 1.

The conditions of Example 5 are explained below. In Example 5, the sublimable substance is compound e. Specifically, in Example 5, the sublimable substance is 2-chlorophenylacetic acid. Other than this, the conditions of Example 5 are the same as those of Example 1.

The conditions of Example 6 are explained below. In Example 6, the sublimable substance is compound f. Specifically, in Example 6, the sublimable substance is dimethyl isophthalate. Other conditions in Example 6 are the same as those in Example 1.

Each substrate W processed in Examples 1-6 was evaluated by 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 area Fi. i is any natural number from 1 to NF. The number NF is the number of local areas Fi. The number NF is a natural number of 2 or more. Each local area Fi is a microscopic region of the substrate W. Each local area Fi is magnified 50,000 times by a scanning electron microscope, for example. An observer observes the pattern P in each local area Fi. The observer observes the convex portions W1 in each local area Fi one by one. The observer evaluates the convex portions W1 in each local area Fi one by one. The observer judges the convex portions W1 in each local area Fi one by one. Specifically, the observer judges whether or not each 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 a non-collapsed convex portion W1. Here, the number of convex portions W1 observed in a local area Fi is defined as NAi. The number of collapsed convex portions W1 in a local area Fi is defined as NBi. The number NBi is equal to or less than the number NAi. The local collapse rate Ei is the ratio of the number NBi to the number NAi. The local collapse rate Ei is defined, for example, by the following formula.
Ei=NBi/NAi*100 (%)
The average collapse rate Ea is the sum of the local collapse rates Ei divided by the number NF.

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

The average collapse rate Ea of Example 1-6 was sufficiently low. Therefore, in Example 1-6, the collapse of the pattern P was suitably suppressed. In other words, in Example 1-6, the pattern P was suitably protected. Therefore, in Example 1-6, the substrate W was appropriately dried. Specifically, the substrate W was dried while the pattern P formed on the substrate W was suitably protected.

8. Effects of the embodiment
The substrate processing method of the embodiment is for processing a substrate W on which a pattern P is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid g is supplied to the substrate W. The processing liquid g contains a sublimable substance and a solvent. In the solidified film forming step, the solvent is evaporated from the processing liquid g on the substrate W. In the solidified film forming step, a solidified film K is formed on the substrate W. The solidified film K contains a sublimable substance. In the sublimation step, the solidified film K is sublimated. The substrate W is dried by the sublimation of the solidified film K.

Here, the sublimable substance contains at least one of compounds a-f. Specifically, the sublimable substance contains at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. Therefore, in the solidified film formation process, the solidified film K is suitably formed on the substrate W.

The solidified film K contains at least one of the compounds a-f. Therefore, in the sublimation process, the solidified film K sublimes appropriately. That is, in the sublimation process, the substrate W is dried appropriately. Specifically, in the sublimation process, the substrate W is dried while the pattern P formed on the substrate W is suitably protected.

As described above, this substrate processing method allows the substrate W to be properly dried.

The solvent is isopropyl alcohol. Compound a dissolves well in isopropyl alcohol. Similarly, compounds b-f dissolve well in isopropyl alcohol. This makes it easy to use the treatment liquid g. Specifically, it is easy to supply the treatment liquid g to the substrate W in the treatment liquid supplying step. Thus, the treatment 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, processing liquid g is generated. Therefore, processing liquid g is preferably prepared. Therefore, it is easier to use processing liquid g.

In the treatment liquid generation process, the treatment liquid g is generated by mixing a sublimable substance with a solvent. Therefore, it is easy to generate the treatment liquid g.

In the treatment liquid production process, the treatment liquid g is stored in the tank 22. This makes it easy to store the treatment liquid g. This makes it even easier to use the treatment liquid g.

As mentioned above, the solvent is isopropyl alcohol. This makes the treatment liquid easy to handle. Handling the treatment liquid includes at least one of preparing the treatment liquid, producing the treatment liquid, storing the treatment liquid, and using the treatment liquid.

The substrate processing apparatus 1 includes a substrate holding unit 13 and a first supply unit 15a. The substrate holding unit 13 holds a substrate W. The first supply unit 15a supplies a processing liquid g to the substrate W held by the substrate holding unit 13. The processing liquid g contains a sublimable substance and a solvent.

Here, the sublimable substance contains at least one of compounds a-f. Therefore, the solidified film K is suitably formed on the substrate W.

The solidified film K contains at least one of the compounds a-f. Therefore, the solidified film K sublimes appropriately. In other words, the substrate W is dried appropriately. Specifically, the substrate W is dried while the pattern P formed on the substrate W is suitably protected.

As described above, the substrate processing apparatus 1 allows the substrate W to be properly dried.

The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves the compounds a-f favorably. For this reason, 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. Thus, the processing liquid g is appropriately supplied to the substrate W. 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.

Here, the sublimable substance contains at least one of the compounds a-f. Therefore, by supplying the processing liquid g to the substrate W, the solidified film K is suitably formed on the substrate W. Furthermore, the solidified film K is suitably sublimated. In other words, the substrate W is suitably dried. Specifically, the substrate W is dried while the pattern P formed on the substrate W is suitably protected.

As described above, the substrate W is properly dried using the processing liquid g. The processing liquid g is useful for drying the substrate W.

The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves the compounds a-f favorably. Therefore, it is easy to use the treatment liquid g. Therefore, the substrate W is more appropriately dried using the treatment liquid g. The treatment liquid g is more useful for drying the substrate W.

Furthermore, the treatment liquid g is easy to handle. 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. The solidified film K is then sublimated. When the processing liquid g is used in this manner, the substrate W is dried more appropriately. When the processing liquid g is used in this manner, the processing liquid g is more useful for drying the substrate W.

9. Modified embodiment
The present invention is not limited to the embodiments, and can be modified as follows.

(1) In the embodiment, the processing liquid g is generated before the processing liquid g is supplied to the first supply unit 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 unit 15a. For example, the first supply source 19a may generate the processing liquid g in a flow path that supplies the processing liquid g to the first supply unit 15a.

Figure 11 is a diagram showing the configuration of the processing unit 11 and the first supply source 19a in the modified embodiment. Note that the same components as in the embodiment are given the same reference numerals and detailed descriptions are omitted.

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

The 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 in communication with the first tank 41 and the second tank 42. The mixing section 44 produces a treatment liquid g. The mixing section 44 is further connected to the first supply section 15a. The mixing section 44 is in communication with the first supply section 15a. The mixing section 44 supplies the treatment liquid g to the first supply section 15a.

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

The mixing section 44 includes pumps 47a and 47b. The pumps 47a and 47b are provided on the pipes 45a and 45b, respectively. The pump 47a sends the sublimable substance from the first tank 41 to the joint 46 through the pipe 45a. The pump 47b sends the solvent from the second tank 42 to the joint 46 through the pipe 45b.

The mixing section 44 includes filters 48a and 48b. Filters 48a and 48b are provided on pipes 45a and 45b, respectively. The sublimable substance passes through filter 48a. Filter 48a filters the sublimable substance. The solvent passes through filter 48b. 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. Each of the valves 49a and 49b may include, for example, a flow rate control valve. Each of the valves 49a and 49b may include, for example, a flow rate control valve and an on-off valve.

An example of the operation of the first supply source 19a in the modified embodiment will be described. In the treatment liquid supply process, the first supply source 19a generates treatment liquid g and sends the treatment liquid g to the first supply unit 15a. Specifically, the valves 49a and 49b are opened. The pump 47a sends the sublimable substance from the first tank 41 to the joint 46. The pump 47b sends the solvent from the second tank 42 to the joint 46. The sublimable substance and the solvent are mixed in the joint 46. The sublimable substance and the solvent become the treatment liquid g in the joint 46. Furthermore, the treatment liquid g flows from the joint 46 to the first supply unit 15a. The nozzle 16a ejects the treatment liquid g.

According to this modified embodiment, there is no need to store the processing liquid g before it is supplied to the first supply unit 15a. Therefore, the volume ratio RV of the processing liquid is precisely controlled. As a result, the substrate W is dried more appropriately.

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

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

(3) In the embodiment, when the processing liquid supplying process was performed, a liquid (e.g., a replacement liquid) was present on the substrate W. That is, in the processing liquid supplying process, the processing liquid g was supplied to the substrate W in a non-dried state. However, this is not limited to this. For example, when the processing liquid supplying process was performed, a liquid (e.g., a replacement liquid) may not be present on the substrate W. For example, in the processing liquid supplying process, the processing liquid g may be supplied to the substrate W in a dried state.

(4) In the processing liquid supplying process of the embodiment, the processing liquid g removes the replacement liquid from the substrate W. However, this is not limited to this. For example, in the processing liquid supplying process, the processing liquid g may clean the substrate W. For example, in the processing liquid supplying process, the processing liquid g may remove foreign matter adhering to the substrate W. For example, in the processing liquid supplying process, the processing liquid g may dissolve foreign matter adhering to the substrate W. The foreign matter is, for example, resist residue.

(5) In the solidified film formation process of the embodiment, a dry gas was not supplied to the substrate W. However, this is not limited to this. In the solidified film formation process, a dry gas may be supplied to the substrate W. In the solidified film formation process, a dry gas may be supplied to the processing liquid g on the substrate W. According to this modified embodiment, in the solidified film formation process, the processing liquid g on the substrate W is exposed to the dry gas. Therefore, in the solidified film formation process, the solvent evaporates efficiently from the processing liquid g on the substrate W. In the solidified film formation process, the solidified film K is efficiently formed on the substrate W.

(6) In an 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. The pattern P may be formed on the substrate W, for example, in the chemical liquid supplying process (step S12).

(7) The embodiment and each of the modified embodiments described above in (1) to (6) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment.

REFERENCE SIGNS LIST 1 ... substrate processing apparatus 10 ... control section 11 ... processing unit 13 ... substrate holder 15 ... supply section 15a ... first supply section (processing liquid supply section)
19a: First supply source A: Concave portion g: Processing liquid G: Liquid film of processing liquid K: Solidified film P: Pattern W: Substrate W1: Convex portion

Claims (7)

A substrate processing method for processing a substrate having a pattern formed thereon, comprising the steps of:
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 treatment liquid on the substrate to form a solidified film containing the sublimable substance on the substrate;
a sublimation step of sublimating the solidified film;
Equipped with
The method for processing a substrate, wherein the sublimable substance includes at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. 2. The substrate processing method according to claim 1,
The method for processing a substrate, wherein the solvent is isopropyl alcohol. A substrate processing apparatus, comprising:
A substrate holder for holding a substrate;
a processing liquid supply unit that supplies a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding unit;
Equipped with
The substrate processing apparatus, wherein the sublimable substance includes at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. 4. The substrate processing apparatus according to claim 3,
The substrate processing apparatus, wherein the solvent is isopropyl alcohol. A processing liquid used for drying a substrate on which a pattern is formed, comprising:
The treatment liquid is
A sublimable material;
A solvent;
Including,
The sublimable substance comprises at least one of o-acetanisidide, N-ethyl-p-toluenesulfonamide, 4-chlorophenylacetic acid, 4-methoxyphenylacetic acid, 2-chlorophenylacetic acid, and dimethyl isophthalate. The treatment liquid according to claim 5 ,
The solvent is isopropyl alcohol. The treatment liquid according to claim 5 ,
The processing liquid is supplied to the substrate, the solvent is evaporated from the processing liquid on the substrate, a solidified film containing the sublimable substance is formed on the substrate, and then the solidified film is sublimated.

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