TWI829236B - Substrate processing method, substrate processing device and processing liquid - Google Patents

Abstract

The invention relates to a substrate processing method, a substrate processing device and a processing liquid. The substrate processing method includes a processing liquid supply process, a cured film forming process, and a sublimation process. In the processing liquid supply step, the processing liquid g is supplied to the substrate W. The treatment liquid g contains a main sublimable substance, a sub-sublimable substance and a solvent. In the cured film forming process, the solvent evaporates from the treatment 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 main sublimable substance and a sub-sublimable substance. In the sublimation process, the cured film is sublimated. By sublimation of the cured film, the substrate W is dried. Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime.

Description

Substrate processing method, substrate processing device and processing liquid

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

Patent Document 1 discloses a substrate processing method for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supply process, a cured film forming process, and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The treatment liquid contains a first sublimable substance, a second sublimable substance, and a solvent. In the cured film forming process, the solvent evaporates from the treatment liquid on the substrate to form a cured film on the substrate. The cured film contains a first sublimable substance and a second sublimable substance. In the sublimation process, the cured film is sublimated. In the sublimation process, the cured film changes into a gas without passing through liquid. The cured film is removed from the substrate by sublimation of the cured film. By sublimation of the cured film, the substrate is dried. [Prior technical literature] [Patent Document]

[Patent document 1] Japanese Patent Application Publication No. 2020-10015

[Problem to be solved by the invention]

Even with previous substrate processing methods, there are cases where the substrate cannot be properly dried. For example, even with previous substrate processing methods, there are cases where patterns formed on the substrate collapse. For example, when the pattern is fine, previous substrate processing methods may not be able to sufficiently suppress the collapse of the pattern.

The present invention was made in view of such circumstances, and an object thereof is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid that can appropriately dry a substrate. [Technical means to solve problems]

In order to achieve this object, the present invention adopts the following configuration. That is, the present invention is a substrate processing method that processes a substrate on which a pattern is formed, including a processing liquid supply step of supplying a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate. ; A cured film forming step, which is to evaporate the above-mentioned solvent from the above-mentioned treatment liquid on the substrate to form a cured film containing the above-mentioned main sublimable substance and the above-mentioned secondary sublimable substance on the substrate; and a sublimation step, which is to solidify the above-mentioned Film sublimation; the main sublimable substance is cyclohexanone oxime, and the secondary sublimable substance is at least one of camphor and acetone oxime.

The substrate processing method is used to process a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supply process, a cured film forming process, and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The treatment liquid contains a main sublimable substance, a sub-sublimable substance and a solvent. In the cured film forming process, the solvent evaporates from the treatment liquid on the substrate. In the cured film forming process, a cured film is formed on the substrate. The cured film contains a main sublimable substance and a sub-sublimable substance. In the sublimation process, the cured film is sublimated. By sublimation of the cured film, the substrate is dried. Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime. Therefore, the substrate is properly dried. Specifically, the substrate is dried in a state where the pattern formed on the substrate is well protected.

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

In the substrate processing method, the volume of the secondary sublimable substance contained in the processing liquid is 0.5% or more and 20% or less of the volume of the main sublimable substance contained in the processing liquid. The treatment liquid contains relatively few sublimable substances. Therefore, the sub-sublimable substance has less influence on the thickness of the treatment liquid on the substrate. Therefore, it is easy to control the thickness of the processing liquid on the substrate in the processing liquid supply process. Therefore, it is easy to control the thickness of the cured film. As a result, the substrate is further appropriately dried.

Furthermore, the present invention is a substrate processing method that processes a substrate on which a pattern is formed, including a processing liquid supply step of supplying a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate. ; A cured film forming step, which is to evaporate the above-mentioned solvent from the above-mentioned treatment liquid on the substrate to form a cured film containing the above-mentioned main sublimable substance and the above-mentioned secondary sublimable substance on the substrate; and a sublimation step, which is to solidify the above-mentioned Film sublimation; in the above-mentioned cured film forming process, the above-mentioned treatment liquid on the substrate generates a plurality of main crystal nuclei of the above-mentioned main sublimable substance and a plurality of subsidiary crystal nuclei of the above-mentioned sub-sublimable substance, and the above-mentioned main crystal nuclei grow on the substrate The main crystal of the above-mentioned main sublimable substance is formed, and the above-mentioned auxiliary crystal nucleus grows on the substrate to become the auxiliary crystal of the above-mentioned sub-sublimable substance.

The substrate processing method is used to process a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supply process, a cured film forming process, and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The treatment liquid contains a main sublimable substance, a sub-sublimable substance and a solvent. In the cured film forming process, the solvent evaporates from the treatment liquid on the substrate. In the cured film forming process, a cured film is formed on the substrate. The cured film contains a main sublimable substance and a sub-sublimable substance. In the sublimation process, the cured film is sublimated. By sublimation of the cured film, the substrate is dried.

In the cured film forming process, the processing liquid on the substrate generates a plurality of main crystal nuclei of the main sublimable material and a plurality of secondary crystal nuclei of the sub-sublimable material. In the cured film forming process, main crystal nuclei grow into main crystals of the main sublimable substance on the substrate. In the cured film forming process, secondary crystal nuclei grow into secondary crystals of the secondary sublimable substance on the substrate. At least one of the main crystal and the subsidiary crystal is relatively small. In other words, at least one of the main crystal and the subsidiary crystal is not too large. Therefore, even if a microspace is formed between the main crystal and the sub-crystal, the microspace is relatively small. In other words, a tiny space is not too big. Therefore, the cured film can well support the pattern formed on the substrate. Therefore, the substrate is dried in a state where the pattern formed on the substrate is well protected.

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

In the substrate processing method, in the cured film forming step, it is preferable that the secondary crystal grows at a position between the plurality of main crystals. Vice crystals effectively make tiny spaces smaller. Therefore, the pattern formed on the substrate is better protected.

In the substrate processing method, in the cured film forming step, it is preferable that the secondary crystal nuclei are generated at positions between the plurality of main crystal nuclei. The secondary crystals grow well between the plurality of main crystals.

In the substrate processing method, in the cured film forming step, it is preferable that the main crystal grows before the secondary crystal. The secondary crystal is smaller than the main crystal. Therefore, the secondary crystal makes the tiny space smaller more effectively.

In the above substrate processing method, in the cured film forming step, it is preferable that the main crystal nuclei are formed earlier than the secondary crystal nuclei. It is easier for the main crystal to grow than the secondary crystal.

In the above substrate processing method, in the cured film forming step, it is preferable that the secondary crystal grows before the main crystal. The main crystal is smaller than the accessory crystal. Therefore, the main crystal makes the tiny space smaller more effectively.

In the substrate processing method, in the cured film forming step, it is preferable that the secondary crystal nuclei are formed earlier than the main crystal nuclei. It is easier for secondary crystals to grow than primary crystals.

Furthermore, the present invention is a substrate processing method that processes a substrate on which a pattern is formed, including a processing liquid supply step of supplying a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate. ; A cured film forming step, which is to evaporate the above-mentioned solvent from the above-mentioned treatment liquid on the substrate, and form a cured film containing the above-mentioned main sublimable substance and the above-mentioned secondary sublimable substance on the substrate; and a sublimation step, which is to make the above-mentioned sublimable substance The cured film sublimates; from the process of supplying the process liquid to the process of forming the cured film, the process liquid on the substrate is maintained at the first temperature.

The substrate processing method is used to process a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supply process, a cured film forming process, and a sublimation process. In the processing liquid supply process, the processing liquid is supplied to the substrate. The treatment liquid contains a main sublimable substance, a sub-sublimable substance and a solvent. In the cured film forming process, the solvent evaporates from the treatment liquid on the substrate. In the cured film forming step, a cured film is formed on the substrate. The cured film contains a main sublimable substance and a sub-sublimable substance. In the sublimation process, the cured film is sublimated. By sublimation of the cured film, the substrate is dried.

From the processing liquid supply process to the cured film formation process, the processing liquid on the substrate is maintained at the first temperature. Therefore, in the cured film forming process, the solvent evaporates smoothly from the treatment liquid on the substrate. Therefore, in the cured film forming process, an appropriate cured film is formed on the substrate. Therefore, the cured film well protects the pattern formed on the substrate from the influence of the processing liquid. The substrate is dried in a state where the pattern formed on the substrate is well protected.

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

In the above substrate processing method, the first temperature is preferably lower than both the melting point of the main sublimable material and the melting point of the secondary sublimable material. The sublimable substances contained in the cured film tend to remain in a solid state. The sub-sublimable substances contained in the cured film also tend to remain in a solid state. Therefore, in the cured film forming process, the cured film is formed more appropriately.

In the above substrate processing method, the first temperature is preferably a temperature close to the lowest melting point of the melting point of the main sublimable material and the melting point of the secondary sublimable material. The solvent evaporates rapidly from the treatment solution on the substrate. In other words, the evaporation rate of the solvent is greatly improved. Therefore, in the cured film forming process, a more appropriate cured film is formed on the substrate. Therefore, the cured film better protects the pattern formed on the substrate from the influence of the processing liquid.

Furthermore, the present invention is a substrate processing apparatus including: a substrate holding unit that holds a substrate; and a processing liquid supply unit that supplies a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate held by the substrate. The above-mentioned main sublimable substance is cyclohexanone oxime, and the above-mentioned secondary sublimable substance is at least one of camphor and acetone oxime.

The substrate processing apparatus includes a substrate holding unit and a processing liquid supply unit. The substrate holding portion holds the substrate. The processing liquid supply unit supplies the processing liquid to the substrate held by the substrate holding unit. The treatment liquid contains a main sublimable substance, a sub-sublimable substance and a solvent. Therefore, when the processing liquid is supplied to the substrate, the solvent evaporates from the processing liquid on the substrate. By evaporating the solvent, a cured film is formed on the substrate. The cured film contains a main sublimable substance and a sub-sublimable substance. Therefore, the cured film sublimates. By sublimation of the cured film, the substrate is dried.

Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime. Therefore, the substrate is properly dried. Specifically, the substrate is dried in a state where the pattern formed on the substrate is well protected.

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

The above-mentioned substrate processing apparatus preferably includes a temperature control part for adjusting the above-mentioned processing liquid on the substrate to a first temperature. The processing liquid on the substrate is well maintained at the first temperature. Therefore, the solvent evaporates smoothly from the processing liquid on the substrate. Therefore, the cured film is formed more appropriately. As a result, the cured film better protects the pattern formed on the substrate from the influence of the processing liquid. The substrate is dried in a state where the pattern formed on the substrate is better protected. That is, the substrate is dried more appropriately.

The present invention is a treatment liquid for drying a substrate on which a pattern is formed. The treatment liquid contains a main sublimable substance, a secondary sublimable substance and a solvent. The main sublimable substance is cyclohexanone oxime, and the secondary sublimable substance is cyclohexanone oxime. The active substance is at least one of camphor and acetone oxime.

The treatment liquid is used to dry the patterned substrate. The treatment liquid is specifically a drying auxiliary liquid. The treatment liquid contains a main sublimable substance, a sub-sublimable substance and a solvent.

Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime. Therefore, it is easier to properly dry the substrate using the treatment liquid. Specifically, using a treatment liquid makes it easier to protect the pattern on the substrate and allow the substrate to dry. As such, the treatment liquid is useful for drying the substrate.

As mentioned above, the substrate is properly dried using the processing liquid. [Effects of the invention]

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

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

<1. First Embodiment> ＜1-1.Substrate＞ The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL (Electroluminescence), a substrate for an FPD (Flat Panel Display), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, or an optical disk. Cover substrate, solar cell substrate. The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in plan view.

FIG. 1 is a diagram schematically showing a part of the substrate W. As shown in FIG. The substrate W has the pattern WP. The pattern WP is formed on the surface of the substrate W.

The pattern WP has a concavo-convex shape, for example. The pattern WP has a plurality of convex portions T, for example. The convex portion T is a part of the substrate W. The convex part T is a structure. The convex portion T includes, for example, at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN), and a polycrystalline silicon film. The convex portion T protrudes upward from the surface of the substrate W, for example. The plurality of convex portions T are separated from each other. The plurality of convex portions T are arranged mutually in the horizontal direction, for example. The convex portion T defines the concave portion A. The concave portion A is a space. The concave portion A is located between two adjacent convex portions T. The concave portion A is adjacent to the side of the convex portion T. Each convex part T has a first side part and a second side part. The second side is the opposite side to the first side. The recessed portion A is in contact with the first side portion of the convex portion T and the second side portion of the convex portion T, for example. The recessed portion A is open upward, for example.

The convex portion T has a height HP. Specifically, the convex portion T has a base end Tp and a front end Td. The base end Tp corresponds to the proximal end of the convex portion T. The front end Td corresponds to the distal end of the convex portion T. The height HP corresponds to the distance between the base end Tp and the front end Td. In this specification, the height HP is appropriately referred to as the height HP of the pattern WP.

<1-2. Treatment liquid (drying auxiliary liquid)> In this specification, the processing liquid used for drying the substrate W is simply referred to as "processing liquid". The treatment liquid has the function of assisting drying of the substrate W. The treatment liquid may in other words be called a drying auxiliary liquid.

The treatment liquid contains a main sublimable substance and a sub-sublimable substance. The main sublimable substance consists of, for example, one compound. The sub-sublimable substance consists of, for example, one compound. Alternatively, the sub-sublimable substance contains, for example, two types of compounds. In other words, the sub-sublimable substance includes, for example, a first sub-sublimable substance and a second sub-sublimable substance.

The compounds contained in the sub-sublimable substance do not overlap with the compounds contained in the main sublimable substance. Specifically, the main sublimable substance does not contain the compound contained in the sub-sublimable substance. Sub-sublimable substances do not contain compounds contained in main sublimable substances. Sub-sublimable substances only include compounds that are different from the main sublimable substances.

The main sublimable substance and the sub-sublimable substance respectively have sublimation properties. The so-called "sublimation property" refers to the property of a single substance, compound or mixture to transfer from a solid phase to a gas or from a gas phase to a solid without passing through a liquid.

It is preferred that the main sublimable substance and the sub-sublimable substance each have a vapor pressure of 0.1 Pa or more at normal temperature. Here, normal temperature includes room temperature. Normal temperature is, for example, a temperature in the range of 5°C or more and 35°C or less. Normal temperature is, for example, a temperature in the range of 10°C or more and 30°C or less. The value of vapor pressure in this specification is expressed as absolute pressure based on absolute vacuum.

The vapor pressure of the main sublimable substance at normal temperature is not less than 0.1 Pa. Mainly sublimable substances do not include compounds with a vapor pressure lower than 0.1 Pa at normal temperature. The vapor pressure of parasublimable substances at room temperature is not less than 0.1 Pa. Parasublimable substances do not include compounds with a vapor pressure lower than 0.1 Pa at normal temperature.

In this specification, the melting point (°C) of the main sublimable substance is called the melting point PA. The melting point of a sub-sublimable substance is called the melting point PB. The melting point of the first sublimable substance is called melting point PB1. The melting point of the second sublimable substance is called melting point PB2. The melting point PB includes, for example, melting point PB1 and melting point PB2. The melting point PA is, for example, higher than normal temperature. The melting point PB is, for example, higher than normal temperature. The melting point PB1 is, for example, higher than normal temperature. The melting point PB2 is, for example, higher than normal temperature.

The main sublimable substance is, for example, cyclohexanone oxime. The main sublimable substance is, for example, only cyclohexanone oxime.

The vapor pressure of cyclohexanone oxime at room temperature is above 0.1 Pa. The melting point of cyclohexanone oxime is higher than normal temperature.

The sub-sublimable substance is, for example, at least one of camphor and acetone oxime. The sub-sublimable substance is, for example, camphor. The sub-sublimable substance is, for example, acetone oxime. Examples of sub-sublimable substances include camphor and acetone oxime. The first sublimable substance is, for example, camphor. The second sublimable substance is, for example, acetone oxime.

The vapor pressure of camphor at room temperature is above 0.1 Pa. The vapor pressure of acetone oxime at room temperature is above 0.1 Pa. The melting point of camphor is higher than normal temperature. The melting point of acetone oxime is higher than normal temperature.

The treatment liquid contains a solvent. The solvent dissolves the main sublimable substance and the sub-sublimable substance. The main sublimable substances and sub-sublimable substances in the treatment liquid are dissolved in the solvent. That is, the treatment liquid contains a solvent, a main sublimable substance dissolved in the solvent, and a secondary sublimable substance dissolved in the solvent. The main sublimable substance and the sub-sublimable substance respectively correspond to the solute of the treatment liquid.

Solvents have relatively high vapor pressure at room temperature. The vapor pressure of the solvent at normal temperature is preferably higher than the vapor pressure of the main sublimable substance at normal temperature. The vapor pressure of the solvent at normal temperature is preferably higher than the vapor pressure of the sub-sublimable substance at normal temperature.

In this specification, the melting point of the solvent is called the melting point PC. The melting point PC is preferably lower than the melting point PA and the melting point PB. The melting point PC is preferably lower than the melting point PB1 and the melting point PB2. The melting point PC is, for example, lower than normal temperature.

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

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

Isopropyl alcohol can dissolve cyclohexanone oxime, camphor and acetone oxime well.

The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of cyclohexanone oxime at room temperature. The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of camphor at room temperature. The vapor pressure of isopropyl alcohol at room temperature is higher than the vapor pressure of acetone oxime at room temperature.

The melting point of isopropyl alcohol is lower than the melting point of cyclohexanone oxime. The melting point of isopropyl alcohol is lower than the melting point of camphor. The melting point of isopropyl alcohol is lower than the melting point of acetone oxime. The melting point of isopropyl alcohol is lower than normal temperature.

The treatment liquid is composed of only a main sublimable substance, a secondary sublimable substance and a solvent, for example. The treatment liquid consists of only cyclohexanone oxime, camphor, and isopropyl alcohol, for example. The treatment liquid consists of only cyclohexanone oxime, acetone oxime, and isopropyl alcohol, for example. The treatment liquid consists of only cyclohexanone oxime, camphor, acetone oxime, and isopropyl alcohol, for example.

Here, the preparation of the main sublimable substance, the sub-sublimable substance and the solvent in the treatment liquid will be described. The volume QA is set to the volume of the main sublimable substance contained in the treatment liquid. Let the volume QB be the volume of the sub-sublimable substance contained in the treatment liquid. Volume QB is less than volume QA. For example, the volume QB is 0.5% or more and 20% or less of the volume QA.

Let the volume QB1 be the volume of the first sublimable substance contained in the treatment liquid. Let the volume QB2 be the volume of the second sublimable substance contained in the treatment liquid. Volume QB is, for example, the sum of volume QB1 and volume QB2.

The volume QC is the volume of the solvent contained in the treatment liquid. Volume QC is greater than volume QA. The volume QC is, for example, sufficiently larger than the volume QA.

<1-3. Overview of substrate processing equipment> FIG. 2 is a plan view showing the inside of the substrate processing apparatus 1 according to the first embodiment. The substrate processing apparatus 1 processes the substrate W. The processing in the substrate processing apparatus 1 includes drying processing.

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

In this specification, for the sake of convenience, the direction in which the carrying part 3 and the processing block 7 are arranged is called the "front and rear direction X". The front and rear direction X is horizontal. The direction from the processing block 7 toward the carrying unit 3 in the front-rear direction X is called "front". The direction opposite to the front is called "rear". The horizontal direction orthogonal to the front-rear direction X is called "width direction Y". One direction of "width direction Y" is appropriately called "right". The direction opposite to the right is called "left". The direction perpendicular to the horizontal direction is called "vertical direction Z". In each figure, for reference, front, back, right, left, upper, and lower are shown appropriately.

The carrying unit 3 includes a plurality of (for example, four) carrier placing units 4 . Each carrier placing part 4 places one carrier C respectively. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), or OC (Open Cassette).

The transfer unit 3 is provided with a transport mechanism 5 . The conveyance mechanism 5 is arranged behind the carrier placement part 4 . The transport mechanism 5 transports the substrate W. The transport mechanism 5 can enter and exit the carrier C placed on the carrier placement portion 4 . The conveying mechanism 5 includes a robot 5a and a robot driving part 5b. The robot arm 5a supports the substrate W. The robot driving part 5b is connected to the robot 5a. The robot driving part 5b moves the robot 5a. The robot driving part 5b moves the robot 5a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example. The robot driving part 5b rotates the robot 5a in a horizontal plane, for example.

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

The processing block 7 includes a plurality of processing units 11 . The processing unit 11 is arranged on the side of the transport mechanism 8 . Each processing unit 11 processes the substrate W.

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

The transport mechanism 8 can enter and exit each processing unit 11 . The transport mechanism 8 can deliver the substrate W to the substrate holding part 13 . The transport mechanism 8 can obtain the substrate W from the substrate holding part 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 can communicate with the transport mechanisms 5 and 8 and the processing unit 11 . The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11 .

The control unit 10 is implemented by a central processing unit (CPU) that performs various processes, a RAM (Random-Access Memory) that is a working area for arithmetic processing, a storage medium such as a fixed disk, and the like. The control unit 10 has various information stored in the storage medium in advance. The information held by the control unit 10 is, for example, conveyance condition information for controlling the conveyance mechanisms 5 and 8 . The information possessed by the control unit 10 is, for example, processing condition information used to control the processing unit 11 . Processing condition information is also called a processing plan.

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

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

The transport mechanism 8 distributes the substrate W to the processing unit 11 . Specifically, the transport mechanism 8 transports the substrate W from the transport mechanism 5 to the substrate holding portion 13 of each processing unit 11 .

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

After the substrate W is processed by the processing unit 11 , the transport mechanism 8 collects the substrate W from each processing unit 11 . Specifically, the transport mechanism 8 receives the substrate W from each substrate holding unit 13 . Then, the conveyance mechanism 8 delivers the substrate W to the conveyance mechanism 5 .

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

<1-4. Structure of processing unit 11> FIG. 4 is a diagram showing the structure of the processing unit 11. Each processing unit 11 has the same structure. The processing unit 11 is classified as monolithic. That is, each processing unit 11 processes only one substrate W at a time.

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

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

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

Here, normal pressure includes standard atmospheric pressure (1 atmosphere, 101325 Pa). Normal pressure is, for example, the air pressure within the range of 0.7 atmospheric pressure or more and 1.3 atmospheric pressure or less. In this manual, pressure values are expressed as absolute pressure based on absolute vacuum.

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

The substrate holding portion 13 is located below the substrate W held by the substrate holding portion 13 . The substrate holding portion 13 is in contact with at least one of the lower surface of the substrate W and the peripheral edge portion of the substrate W. The lower surface of the substrate W is also called the back surface of the substrate W. The substrate holding portion 13 is not in contact with the upper surface of the substrate W.

The processing unit 11 includes a rotation drive unit 14 . At least a part of the rotation driving part 14 is provided 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 portion 13 rotates integrally with the substrate holding portion 13 . The substrate W held by the substrate holding portion 13 rotates around the rotation axis B. The rotation axis B passes through the center of the substrate W and extends in the vertical direction Z, for example.

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

The supply part 15 includes a first supply part 15a, a second supply part 15b, a third supply part 15c, a fourth supply part 15d, and a fifth supply part 15e. The first supply part 15a supplies the processing liquid. The second supply part 15b supplies the chemical solution. The third supply part 15c supplies flushing liquid. The fourth supply part 15d supplies replacement liquid. The fifth supply part 15e supplies dry gas.

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

As mentioned above, the inside of the housing 12 is at normal temperature and pressure. Therefore, the treatment liquid should be used in a normal temperature environment. The treatment fluid is used in a normal pressure environment.

The chemical liquid supplied from the second supply part 15b is, for example, an etching liquid. The etching liquid contains, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

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

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

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

The first supply part 15a includes a nozzle 16a. Similarly, the second to fifth supply parts 15b to 15e are respectively provided with nozzles 16b to 16e. The nozzles 16a-16e are respectively arranged inside the housing 12. The nozzle 16a sprays the processing liquid. The nozzle 16b sprays the chemical liquid. The nozzle 16c sprays the flushing liquid. The nozzle 16d sprays the replacement liquid. The nozzle 16e sprays dry gas.

The first supply part 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided in the pipe 17a. When the valve 18a is opened, the nozzle 16a sprays the processing liquid. When the valve 18a is closed, the nozzle 16a does not eject the processing liquid. Similarly, the second to fifth supply parts 15b to 15e respectively include pipes 17b to 17e and valves 18b to 18e. The pipes 17b-17e are connected to the nozzles 16b-16e respectively. Valves 18b to 18e are respectively provided in pipes 17b to 17e. Valves 18b-18e control the ejection of chemical liquid, flushing liquid, replacement liquid and drying gas respectively.

At least part of the piping 17a may be provided outside the housing 12. The pipes 17b-17e can be arranged similarly to the pipe 17a. The valve 18a may be provided outside the housing 12. Valves 18b-18e may be configured similarly to valve 18a.

The substrate processing apparatus 1 includes a first supply source 19a. The first supply source 19a is connected to the first supply part 15a. The first supply source 19a communicates with the first supply part 15a. The first supply source 19a is connected to the pipe 17a, for example. The first supply source 19a supplies the processing liquid to the first supply part 15a.

The second supply part 15b is connected to the second supply source 19b. The second supply part 15b communicates with the second supply source 19b. The second supply source 19b is connected to the pipe 17b, for example. The second supply source 19b supplies the chemical solution to the second supply part 15b. Similarly, the third to fifth supply parts 15c to 15e are respectively connected to the third to fifth supply sources 19c to 19e. The third to fifth supply parts 15c to 15e are respectively connected to the third to fifth supply sources 19c to 19e. The third to fifth supply sources 19c to 19e are connected to pipes 17c to 17e, for example. The third supply source 19c supplies the flushing liquid to the third supply part 15c. The fourth supply source 19d supplies the replacement liquid to the fourth supply part 15d. The fifth supply source 19e supplies the dry gas to the fifth supply part 15e.

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

The first supply source 19a can supply the processing liquid to the plurality of processing units 11. Alternatively, the first supply source 19a may supply the 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 19 b does not need to be an element of the substrate processing apparatus 1 . For example, the second supply source 19b may be a physical device provided outside the substrate processing apparatus 1 . Similarly, the third to fifth supply sources 19c to 19e may respectively be elements of the substrate processing apparatus 1 . Alternatively, the third to fifth supply sources 19c to 19e may not be components of the substrate processing apparatus 1, respectively.

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

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

<1-5. Structure of the first supply source 19a> Refer to Figure 4. The first supply source 19a further generates a processing liquid.

A structural example of the first supply source 19a is shown below. The first supply source 19a is divided into a production unit 21 and a pressure feeding unit 31. The generation unit 21 generates a treatment liquid. The pressure feeding unit 31 feeds the processing liquid to the first supply part 15a.

The generation unit 21 includes a tank 22 and supply parts 23a, 23b, 23c, and 23d. The supply part 23a supplies the main sublimable substance to the tank 22. The supply parts 23b and 23c respectively supply the sub-sublimable substance to the tank 22. Specifically, the supply part 23b supplies the 1st sublimable substance to the tank 22. The supply part 23c supplies the second sublimable substance to the tank 22. The supply part 23d supplies the solvent to the tank 22. The main sublimable material, the secondary sublimable material and the solvent are mixed in the tank 22 . The main sublimable substance, the sub-sublimable substance and the solvent become the treatment liquid g in the tank 22 .

The tank 22 is placed in a normal temperature environment. The tank 22 is installed in a normal pressure environment. Therefore, the treatment liquid g is generated in a normal temperature environment. The treatment liquid g is generated in a normal pressure environment.

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

The supply part 23a includes, for example, a pipe 24a and a valve 25a. The pipe 24a is connected to the tank 22. The pipe 24a communicates with the tank 22. The valve 25a is provided in the pipe 24a. When the valve 25a is opened, the supply part 23a supplies the main sublimable substance to the tank 22. When the valve 25a is closed, the supply part 23a does not supply the main sublimable substance to the tank 22. Similarly, supply parts 23b-23d are equipped with pipes 24b-24d and valves 25b-25d, respectively. The pipes 24b to 24d are connected to the tank 22 respectively. Valves 25b to 25d are respectively provided in pipes 24b to 24d. The valves 25b and 25c respectively control the supply of the sub-sublimable material to the tank 22. Specifically, the valve 25b controls the supply of the first sublimable substance to the tank 22. The valve 25c controls the supply of the second sublimable substance to the tank 22. Valve 25d controls the supply of solvent to tank 22.

Furthermore, the valve 25a adjusts the amount of the main sublimable substance supplied to the tank 22. The amount of the main sublimable substance supplied to the tank 22 is equivalent to the volume of the main sublimable substance used to generate the treatment liquid g. More specifically, the amount of the main sublimable material supplied to the tank 22 is equivalent to the volume of the main sublimable material used to generate the treatment liquid g. The amount of the main sublimable substance supplied to the tank 22 corresponds to the above-mentioned volume QA. Therefore, the valve 25a adjusts the volume QA.

Similarly, the valves 25b and 25c adjust the amount of the sub-sublimable substance supplied to the tank 22. The amount of the sub-sublimable material supplied to the tank 22 is equivalent to the volume of the sub-sublimable material used to generate the treatment liquid g. The amount of the sub-sublimable substance supplied to the tank 22 corresponds to the above-mentioned volume QB. Therefore, the valves 25b, 25c adjust the volume QB.

The valve 25b adjusts the amount of the first sublimable substance supplied to the tank 22. The amount of the first sublimable substance supplied to the tank 22 is equivalent to the volume of the first sublimable substance used to generate the treatment liquid g. The amount of the first sublimable substance supplied to the tank 22 corresponds to the above-mentioned volume QB1. Therefore, the valve 25b adjusts the volume QB1.

The valve 25c adjusts the amount of the second sublimable substance supplied to the tank 22. The amount of the second sublimable substance supplied to the tank 22 is equivalent to the volume of the second sublimable substance used to generate the treatment liquid g. The amount of the second sublimable substance supplied to the tank 22 corresponds to the above-mentioned volume QB2. Therefore, valve 25c adjusts volume QB2.

Valve 25d adjusts the amount of solvent supplied to tank 22. The amount of solvent supplied to the tank 22 corresponds to the volume of the solvent used to generate the treatment liquid g. The amount of solvent supplied to tank 22 corresponds to the above-mentioned volume QC. Therefore, valve 25d adjusts volume QC.

The valves 25a - 25d may each include a flow regulating valve, for example. For example, the valves 25a to 25d may each include a flow control valve and an on-off valve.

The supply part 23a is connected to the supply source 26a. The supply part 23a communicates with the supply source 26a. For example, the supply source 26a is connected to the pipe 24a. The supply source 26a supplies the main sublimable substance to the supply part 23a. Similarly, supply parts 23b-23d are respectively connected to supply sources 26b-26d. The supply parts 23b to 23d are respectively connected to the supply sources 26b to 26d. For example, supply sources 26b to 26d are connected to pipes 24b to 24d, respectively. The supply sources 26b and 26c transport the sub-sublimable substance to the supply parts 23b and 23c respectively. Specifically, the supply source 26b transports the first sublimable substance to the supply part 23b. The supply source 26c supplies the second sublimable substance to the supply part 23c. The supply source 26d supplies the solvent to the supply part 23d.

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

The pressure feeding unit 31 further includes a pump 34 and a filter 35 . The pump 34 is provided in the pipe 32 . When the pump 34 is operated, the pump 34 transports the processing liquid g from the tank 22 to the first supply part 15a. When the pump 34 operates, the pump 34 pressure-feeds the processing liquid g from the tank 22 to the first supply part 15a. When the operation of the pump 34 is stopped, the pump 34 does not transport the processing liquid g from the tank 22 to the first supply part 15a. When the pump 34 stops operating, the pump 34 does not pressure-feed the processing liquid g from the tank 22 to the first supply part 15a. The filter 35 is provided in the pipe 32 . The treatment liquid g passes through the filter 35 . The filter 35 filters the treatment liquid g. The filter 35 removes foreign matter from the treatment liquid g.

Refer to Figure 3. The control unit 10 can communicate with the first supply source 19a. The control unit 10 controls the first supply source 19a. The control part 10 controls the generation unit 21. The control part 10 controls the supply parts 23a-23d. The control part 10 controls the valves 25a-25d. 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. The processing liquid condition information includes information on the conditions of the processing liquid. The processing liquid condition information includes, for example, objects related to preparation of the processing liquid g. The target related to the preparation of the treatment liquid g is, for example, specifying the respective values of the volumes QA, QB, and QC. Objectives related to the preparation of the treatment liquid g include, for example, specifying the ratio of the volumes QA, QB, and QC. The processing liquid condition information is stored in the storage medium of the control unit 10 in advance.

<1-6. Operation example of first supply source 19a and processing unit 11> FIG. 5 is a flowchart showing the procedure of the substrate processing method according to the first embodiment. The substrate processing method includes step S1 and steps S11-S18. Step S1 is executed by the first supply source 19a. Steps S11-S18 are essentially executed by the processing unit 11. Step S1 is executed synchronously with steps S11-S18. The first supply source 19a and the processing unit 11 operate according to the control of the control unit 10.

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

Step S1: Treatment liquid generation process In the processing liquid generating step, the processing liquid g is generated.

The control unit 10 controls the generation unit 21 based on the processing liquid condition information. The generation unit 21 generates the treatment liquid g. Specifically, the control unit 10 controls the supply units 23a to 23d based on the target regarding the preparation of the processing liquid g. The supply part 23a supplies the main sublimable substance to the tank 22. The supply parts 23b and 23c supply the sub-sublimable substance to the tank 22. The supply part 23b supplies the 1st secondary sublimable substance to the tank 22. The supply part 23c supplies the second sublimable substance to the tank 22. The supply part 23d supplies the solvent to the tank 22. The treatment liquid g is generated in the tank 22 . The treatment liquid g contains a main sublimable substance, a sub-sublimable substance and a solvent. The actual preparation of the main sublimable substance, the sub-sublimable substance and the solvent in the treatment liquid g and the target adaptation related to the preparation of the treatment liquid g. That is, the processing liquid g is matched with the processing liquid condition information. The treatment liquid g is stored in the tank 22 .

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

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

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

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

Thereafter, the second supply part 15b stops supplying the chemical solution to the substrate W. Specifically, the valve 18b is closed. The nozzle 16b stops spraying the chemical liquid.

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

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

Thereafter, the third supply part 15c stops supplying the rinse liquid to the substrate W. Specifically, valve 18c is closed. The nozzle 16c stops spraying the flushing fluid.

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

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

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

Step S15: Treatment liquid supply process In the processing liquid supply 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 part 15a. The first supply part 15a supplies the processing liquid g to the substrate W held by the substrate holding part 13. Specifically, the pump 34 transports the processing liquid g from the tank 22 to the first supply part 15a. The pump 34 pressure-feeds the processing liquid g from the tank 22 to the first supply part 15a. Open valve 18a. The nozzle 16a sprays the processing liquid g. The processing liquid g is supplied to the upper surface of the substrate W. The processing liquid g removes the replacement liquid from the substrate W. The replacement liquid on the substrate W is replaced with the processing liquid g.

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

FIG. 6 is a diagram schematically showing the substrate W in the processing liquid supply step. When the substrate W is held by the substrate holding part 13, the pattern WP is located on the upper surface of the substrate W. When the substrate W is held by the substrate holding portion 13, the pattern WP faces upward.

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

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

The liquid film G has an upper surface G1. The upper surface G1 is located higher than the entire pattern WP. The upper surface G1 does not intersect the pattern WP. The upper surface G1 is located higher than the entire convex portion T. The upper surface G1 does not intersect the convex portion T.

Furthermore, 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 recessed portion A.

Gas J exists above the liquid film G. The pattern WP is not connected to the gas J. The pattern WP is not exposed to the gas J. The convex portion T is not in contact with the gas J. The convex portion T is not exposed to the gas J.

Gas J is in contact with liquid film G. 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 WP does not intersect the gas-liquid interface between the liquid film G and the gas J. The convex portion T does not intersect with the gas-liquid interface between the liquid film G and the gas J.

In the process of supplying the processing liquid, the height position of the upper surface G1 can be further adjusted. For example, the height position of the upper surface G1 can be adjusted while supplying the processing liquid g to the substrate W from the nozzle 16a. 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 can also be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface G1 can also 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 HG of the liquid film G. The thickness HG of the liquid film G is equivalent to the thickness of the processing liquid g on the substrate W. The thickness HG of the liquid film G is, for example, the distance in the vertical direction Z between the base end Tp of the convex portion T and the upper surface G1.

Step S16: Cured film forming process In the cured film forming process, the solvent evaporates from the treatment 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 main sublimable substance and a sub-sublimable substance.

FIG. 7 is a diagram schematically showing the substrate W in the cured film forming step. As mentioned above, solvents have relatively high vapor pressures. At normal temperature, the solvent has a higher vapor pressure than the main sublimable substance and the secondary sublimable substance. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W. The solvent changes smoothly from liquid to gas.

When the solvent evaporates from the processing liquid g on the substrate W, the solvent is removed from the processing liquid g on the substrate W. As the solvent evaporates from the treatment 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 concentration of the main sublimable substance in the liquid film G increases. As the amount of solvent contained in the liquid film G decreases, the concentration of the parasublimable substance in the liquid film G also increases.

Soon, the main sublimable material and the secondary sublimable material in the liquid film G begin to precipitate on the substrate W. That is, the main sublimable substance changes from the solute in the treatment liquid g to the main sublimable substance in the solid phase. The parasublimable substance changes from the solute in the treatment liquid g into a solid phase parasublimable substance. The main sublimable substance in the solid phase and the sub-sublimable substance in the solid phase form a cured film K. The main sublimable substance in the solid phase and the sub-sublimable substance in the solid phase form the cured film K. Cured film K does not contain solvents. The cured film K is solid. The cured film K is formed on the substrate W.

The liquid film G gradually decreases through the evaporation of the solvent and the precipitation of the main sublimable substances and the secondary sublimable substances. Due to the precipitation of the main sublimable substance and the sub-sublimable substance, the liquid film G gradually changes into the solidified film K. Due to the precipitation of the main sublimable material and the secondary sublimable material, the cured film K gradually increases. The cured film K gradually grows.

First, the upper part of the liquid film G changes to the solidified film K. The cured film K is located above the liquid film G. The cured film K covers the upper surface G1 of the liquid film G.

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

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

Cured film K has an upper surface K1. The upper surface K1 is connected to the gas J. The height position of the upper surface K1 when the liquid film G starts to change into the solidified film K is called the initial height position of the upper surface K1. The initial height position of the upper surface K1 is substantially equal to the height position of the upper surface G1 just before the liquid film G begins to change into the solidified film K.

The cured film K has a thickness HK. The thickness HK of the cured film K is, for example, the distance in the vertical direction Z between the upper surface G1 of the liquid film G and the upper surface K1 of the cured film K.

As the cured film K increases, the liquid film G decreases. As the thickness HK of the cured film K increases, the thickness HG of the liquid film G decreases. As the thickness HK of the cured film K increases, the height position of the upper surface G1 becomes lower. When the liquid film G does not exert significant force on the convex portion T, the liquid film G gradually decreases. When the solvent does not exert significant force on the convex portion T, the solvent is gradually removed from the substrate W.

Furthermore, the cured film K may be formed before the processing liquid supply process is completed. Part of the period during which the cured film forming step is performed may overlap with part of the period during which the processing liquid supply step is performed.

FIG. 8 is a diagram schematically showing the substrate W in the cured film forming step. FIG. 8 schematically shows the substrate W at the end of the cured film formation process, for example. Only the cured film K exists on the substrate W. At the end of the cured film forming process, the liquid film G completely disappears from the substrate W. The liquid film G does not remain in the recessed portion A. All the solvent disappeared from the substrate W. The solvent will not remain in the recessed portion A.

The cured film K extends to the base end Tp of the substrate W. The recessed portion A is filled with the cured film K. The entire recessed portion A is filled only with the cured film K. After all the liquid film G disappears from the substrate W, the thickness HK of the cured film K is, for example, the distance in the vertical direction Z between the base end Tp of the protrusion T and the upper surface K1 of the cured film K.

The cured film K is in contact with the pattern WP. The cured film K supports the pattern WP. Cured film K protection pattern WP. For example, the cured film K prevents the pattern WP from collapsing.

The cured film K is in contact with the convex portion T. The cured film K is in contact with both the first side portion of the convex portion T and the second side portion of the convex portion T. The cured film K supports the convex portion T. The cured film K forms the convex portion T from each of the first side portion and the second side portion of the convex portion T. The cured film K protects the convex portion T. For example, the cured film K prevents the convex portion T from collapsing. For example, the cured film K prevents the convex portion T from inclining toward the first side. For example, the cured film K prevents the convex portion T from inclining toward the second side.

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

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

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

FIG. 9 is a diagram schematically showing the substrate W in the sublimation process. As the cured film K sublimates, the cured film K gradually decreases. As the cured film K sublimates, the height position of the surface K1 above the cured film K becomes lower. As the cured film K sublimates, the thickness HK of the cured film K gradually decreases. As the cured film K sublimates, the cured film K gradually becomes thinner.

Furthermore, sublimating substances have sublimation properties. Therefore, the sublimation of the cured film K can also start before the liquid film G disappears from the substrate W. Part of the period during which the sublimation process is performed may overlap with part of the period during which the cured film forming process is performed.

The pattern WP begins to be exposed in the gas J. The convex portion T begins to be exposed in the gas J.

When the cured film K sublimates, the cured film K does not become liquid. Therefore, in the sublimation process, the liquid does not exist on the substrate W. In the sublimation process, there is no liquid in the recessed portion A. In the sublimation process, no gas-liquid interface is generated near the pattern WP.

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

FIG. 10 is a diagram schematically showing the substrate W in the sublimation process. FIG. 10 schematically shows the substrate W at the end of the sublimation process, for example. At the end of the sublimation process, the cured film K completely disappears from the substrate W. There is no liquid on the substrate W. The entire pattern WP is exposed to the gas J. The entire convex portion T is exposed to the gas J. The entire recessed portion A is filled with gas J alone. The substrate W is dried.

The processes in the above-mentioned processing liquid supply process, cured film formation process, and sublimation process are examples of drying processes. The processing in the above-mentioned processing liquid supply process, cured film formation process, and sublimation process corresponds to the use example of the processing liquid g. The treatment liquid g should be used in normal temperature environment. The treatment liquid g is used in a normal pressure environment.

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

<1-7. Technical significance of treatment liquid g> The technical significance of the treatment liquid g is explained through Experimental Examples 1, 2, 3 and Comparative Examples.

The only difference between Experimental Examples 1-3 and Comparative Examples lies in the sub-sublimable substance. Conditions other than the sub-sublimable substance are common between Experimental Examples 1-3 and Comparative Examples.

The conditions of Experimental Example 1 will be described. In Experimental Example 1, the substrate W was processed in the processing liquid supply process, the cured film forming process, and the sublimation process. More specifically, the substrate W is processed in a chemical solution supply process, a rinse liquid supply process, a replacement liquid supply process, a processing liquid supply process, a cured film forming process, and a sublimation process.

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

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

The processing liquid g used in the processing liquid supply step contains a main sublimable substance, a secondary sublimable substance and a solvent. The main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is camphor. The solvent is isopropyl alcohol (IPA).

The volume ratio of the cyclohexanone oxime contained in the treatment liquid g and the isopropyl alcohol contained in the treatment liquid g is as follows. Cyclohexanone oxime: isopropyl alcohol = 1:40 (volume ratio)

In other words, the ratio of volume QA to volume QC is as follows. QA: QC=1:40 (volume ratio)

The volume ratio of the cyclohexanone oxime contained in the treatment liquid g and the camphor contained in the treatment liquid g is as follows. Cyclohexanone oxime: camphor = 100:5 (volume ratio)

In other words, the volume ratio of the volume QA to the volume QB is as follows. QA:QB=100:5 (volume ratio)

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

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

The conditions of Experimental Example 2 will be described. In Experimental Example 2, the sub-sublimable substance is acetone oxime.

The volume ratio of cyclohexanone oxime contained in the treatment liquid g and acetone oxime contained in the treatment liquid g is as follows. Cyclohexanone oxime: acetone oxime = 100:5 (volume ratio)

The conditions of Experimental Example 3 will be explained. In Experimental Example 3, the sub-sublimable substances are camphor and acetone oxime. Specifically, the sub-sublimable substance includes a first sub-sublimable substance and a second sub-sublimable substance. The first sublimable substance is camphor. The second sublimable substance is acetone oxime. The volume ratios of cyclohexanone oxime contained in the treatment liquid g, camphor contained in the treatment liquid g, and acetone oxime contained in the treatment liquid g are as follows. Cyclohexanone oxime: camphor: acetone oxime = 100: 2.5: 2.5 (volume ratio)

In other words, in Experimental Example 3, the ratio of volume QA, volume QB1, and volume QB2 is as follows. QA: QB1: QB2=100:2.5:2.5 (volume ratio)

Explain the conditions of the comparative example. In the comparative example, the processing liquid g used in the processing liquid supply process contains a main sublimable substance and a solvent. That is, the treatment liquid g does not contain a sub-sublimable substance. Specifically, the treatment liquid g contains cyclohexanone oxime and isopropyl alcohol. Treatment solution g does not contain camphor. Treatment solution g does not contain acetone oxime.

Each substrate W processed in Experimental Examples 1-3 and Comparative Examples was evaluated based on the collapse rate. The collapse rate is the probability that the pattern WP on the substrate W will collapse when the substrate W is processed. In other words, the collapse rate is the probability that the convex portion T on the substrate W collapses when the substrate W is processed.

Example collapse rate. The collapse rate includes, for example, the average collapse rate Da (%), the maximum collapse rate Db (%), and the minimum collapse rate Dc (%). The average collapse rate Da is the average of multiple local collapse rates di. The maximum collapse rate Db is the maximum value of multiple local collapse rates di. The minimum collapse rate Dc is the minimum value of multiple local collapse rates di. Each local collapse rate di (%) is the collapse rate of each local area Ei. i is any natural number from 1 to NE. NE is the number of local areas Ei. The number NE is a natural number above 2. Each local area Ei is a minute area of the substrate W. Each local area Ei is magnified to 50,000 times by, for example, a scanning electron microscope. The observer observes the pattern WP (convex portion T) of each local area Ei. The observer evaluates the convex portion T of each local area Ei one by one. The observer determines the convex portion T of each local area Ei one by one. Specifically, the observer determines whether the convex portion T collapsed for each convex portion T. Here, let the number of evaluated convex portions T in each local area Ei be NPi. Let the number of determined convex portions T in each local area Ei be NPi. Let the number of convex portions T determined to have collapsed in each local area Ei be NTi. The number NTi is less than the number NPi. The local collapse rate di is the ratio of the coefficient NTi to the number NPi. The local collapse rate di is defined by, for example, the following equation. di＝NTi/NPi﹡100 (%)

FIG. 11 is a table showing the collapse rate of the treated substrate W in Experimental Examples 1-3 and Comparative Examples. FIG. 12 is a graph showing the collapse rate of the treated substrate W in Experimental Examples 1-3 and Comparative Examples.

The average collapse rates Da of Experimental Examples 1-3 are respectively lower than the average collapse rates Da of Comparative Examples (=1.07%). The maximum collapse rates Db of Experimental Examples 1-3 are respectively lower than the maximum collapse rate Db of Comparative Examples (=2.87%). The minimum collapse rates Dc of Experimental Examples 1-3 are respectively lower than the minimum collapse rates Dc of Comparative Examples (=0.30%).

The maximum collapse rate Db (=0.75%) of Experimental Example 2 is lower than the average collapse rate Da of Comparative Example.

The maximum collapse rate Db (=0.20%) of Experimental Example 3 is lower than the average collapse rate Da of Comparative Example. The maximum collapse rate Db (=0.20%) of Experimental Example 3 is lower than the minimum collapse rate Dc of Comparative Example.

The average collapse rate Da (=0.03%) of Experimental Example 3 is lower than the minimum collapse rate Dc of Comparative Example.

The average collapse rate Da of Experimental Example 3 is lower than the average collapse rate Da of Experimental Examples 1 and 2. The maximum collapse rate Db of Experimental Example 3 is lower than the maximum collapse rate Db of Experimental Examples 1 and 2. The minimum collapse rate Dc of Experimental Example 3 is lower than the minimum collapse rate Dc of Experimental Examples 1 and 2.

The difference between the maximum collapse rate Db and the minimum collapse rate Dc is called difference F. The difference F in Experimental Example 1 is 1.98%. The difference F in Experimental Example 2 is 0.72%. The difference F in Experimental Example 3 is 0.20%. The difference F in the comparative example is 2.57%. The difference F between Experimental Examples 1-3 is smaller than the difference F between Comparative Examples.

The difference F in Experimental Example 3 is smaller than the difference F between Experimental Examples 1 and 2.

When the cases of Experimental Examples 1 to 3 are not distinguished, they are collectively referred to as Experimental Examples.

To sum up, for example, the collapse of the partial pattern WP in the experimental example is less than that in the comparative example. For example, the collapse of part of the pattern WP in the experimental example is less than that in the comparative example. In the experimental example, the pattern WP was protected more appropriately than in the comparative example. In the experimental example, the substrate W is dried while the pattern WP is well protected. In the experimental example, the substrate W was processed more appropriately than in the comparative example.

＜1-8. Collapse mechanism of pattern WP＞ The present inventors speculate as follows about the collapse mechanism of the pattern WP in the comparative example.

Figures 13, 14, 15, 16, and 17 are diagrams respectively illustrating the collapse mechanism of the pattern WP. 13 to 16 are diagrams schematically showing the substrate W in the cured film forming step. FIG. 17 is a diagram schematically showing the substrate W in the sublimation process.

Refer to Figure 13. The treatment liquid g contains a main sublimable substance. The treatment liquid g does not contain sub-sublimable substances.

In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of crystal nuclei mA. Crystallization nuclei mA are generated in the treatment liquid g. The crystal nucleus mA contains a main sublimable substance. The crystallization nucleus mA is derived from the main sublimation substance. In this specification, the crystallization nucleus mA of the main sublimable substance is called the main crystallization nucleus mA.

The main crystallization nucleus mA is solid. The main crystal nuclei mA are microparticles.

Refer to Figure 14. The main crystal nucleus mA grows on the substrate W to become crystal MA. The main crystal nucleus mA changes into crystalline MA in the treatment liquid g. Crystalline MA contains a main sublimable substance. In this specification, the crystalline MA of the main sublimable substance is called main crystalline MA.

The main crystalline MA is solid. The main crystal MA has a particle size larger than the main crystal nucleus mA. The main crystal MA constitutes the cured film K. In other words, the cured film K contains the main crystal MA. However, the cured film K does not contain a sub-sublimable substance.

By growing the main crystal nucleus mA into the main crystal MA, the main crystal nucleus mA disappears. In Figure 14, the main crystallization nucleus mA that disappears is represented by a dotted line.

The main crystalline MA grows. The main crystal MA becomes larger. When the main crystal MA grows, the main crystal MA absorbs the main crystal nucleus mA other than the main crystal nucleus mA which is the basis of the main crystal MA. As a result, the number of main crystals MA is smaller than the number of main crystal nuclei mA. The number of main crystal MA is less than the number of main crystal nuclei mA produced. In Figure 14, the main crystal nucleus mA absorbed by the main crystal MA is represented by a dotted line.

Furthermore, part of the main crystal MA can also absorb other main crystal MA. Here, the other main crystal MA is adjacent to a part of the main crystal MA, for example. The growth of other main crystalline MAs is, for example, slower than that of some main crystalline MAs. The other main crystal MA is, for example, smaller than a part of the main crystal MA. As a result, the number of main crystal MA further decreases.

Refer to Figure 15. The main crystal MA is further grown on the substrate W. The particle size of the main crystal MA becomes excessively large on the substrate W.

Soon, the main crystals MA come into contact with each other on the substrate W. For example, two adjacent main crystals MA are in contact with each other.

After the main crystal MA comes into contact with each other, a minute space L may be formed. The minute space L is, for example, a crystal grain boundary. The minute space L is, for example, a crack. The minute space L is, for example, a gap.

There is no main crystal MA in the tiny space L. The cured film K does not exist in the small space L.

The minute space L is located inside the cured film K, for example. The minute space L is located below the cured film K, for example.

The micro space L is located around the main crystal MA, for example. The minute space L is in contact with the main crystal MA, for example.

The tiny space L is located between the plurality of main crystals MA. The micro space L is located, for example, below two main crystals MA that are in contact with each other. The micro space L is located around the pattern WP, for example. The minute space L is in contact with the pattern WP, for example. The minute space L is located around the convex portion T, for example. The minute space L is in contact with the convex portion T, for example. The minute space L relates to the recessed portion A, for example. The minute space L is formed in the recessed portion A, for example.

As described above, the particle size of the main crystal MA is too large. Furthermore, the number of main crystal MA is small. Therefore, the minute interval L is too large. For example, the minute space L is larger than one recess A. For example, the length of the tiny space L in the vertical direction Z is greater than the height HP of the pattern WP.

As a result, the main crystal MA does not exist in at least one recessed portion A. A recessed portion A in which the main crystal MA does not exist is generated. The cured film K is not formed in at least one recessed portion A. The recessed portion A where the cured film K is not formed is generated.

Specifically, the plurality of recessed portions A are classified into the first recessed portion A1 and the second recessed portion A2. The first recessed portion A1 is the recessed portion A in which the cured film K is substantially present. The second recessed portion A2 is a recessed portion A in which the cured film K does not substantially exist. When the cured film K does not contain a sub-sublimable substance, the recessed portion A includes the second recessed portion A2 in addition to the first recessed portion A1. When the cured film K does not contain a sub-sublimable substance, the second concave portion A2 is generated.

The plurality of convex portions T are classified into a first convex portion T1 and a second convex portion T2. The first convex portion T1 is a convex portion T that is not in contact with the second concave portion A2. That is, the first convex portion T1 is in contact with the first recessed portion A1. Both the first side portion of the first convex portion T1 and the second side portion of the first convex portion T1 are in contact with the first recessed portion A1. For example, the first recessed portion A1 is in contact with both the first side portion of the first convex portion T1 and the second side portion of the first convex portion T1. The second convex part T2 is the convex part T in contact with the second concave part A2. At least one of the first side portion of the second convex portion T2 and the second side portion of the second convex portion T2 is in contact with the second recessed portion A2. For example, the second concave portion A2 is in contact with one of the first side portion of the second convex portion T2 and the second side portion of the second convex portion T2. Alternatively, the second recessed portion A2 is in contact with both the first side portion of the second convex portion T2 and the second side portion of the second convex portion T2. When the cured film K does not contain a sub-sublimable substance, the convex portion T includes the second convex portion T2 in addition to the first convex portion T1. When the cured film K does not contain a sub-sublimable substance, the second convex portion T2 is generated.

The position of the micro space L is locally distributed. The positions of the second recessed portions A2 are locally distributed. The positions of the second protrusions T2 are locally distributed.

The treatment liquid g remains in the tiny space L. The processing liquid g remains in a part of the concave portion A. The processing liquid g remains in the second concave portion A2. Specifically, a part of the treatment liquid g remains in the micro space L without turning into the cured film K. A part of the processing liquid g remains in the concave portion A. A part of the processing liquid g remains in the second concave portion A2.

Refer to Figure 16. The treatment liquid g in the tiny space L gradually decreases. The treatment liquid g in the tiny space L gradually disappears. Gas J enters the tiny space L. The processing liquid g and the gas J exist in the small space L. The treatment liquid g and gas J in the tiny space L form a gas-liquid interface R. The gas-liquid interface R is located in the tiny space L. The gas-liquid interface R is located, for example, in the second recessed portion A2.

The gas-liquid interface R located in the second concave portion A2 intersects the second convex portion T2. Therefore, the processing liquid g exerts a significant force on the second convex portion T2. Specifically, the second convex portion T2 receives the surface tension of the processing liquid g.

The cured film K does not exist in the 2nd recessed part A2. There is substantially no cured film K in the second recessed portion A2. Therefore, the cured film K does not support at least one of the first side portion of the second convex portion T2 and the second side portion of the second convex portion T2. Therefore, when the second convex part T2 is subjected to the surface tension of the processing liquid g, the second convex part T2 is extremely easy to collapse.

Refer to Figure 17. In the sublimation process, the cured film K is sublimated. By sublimation of the cured film K, the substrate W is dried. The second convex portion T2 is in a collapsed state.

In summary, when the cured film K does not contain a sub-sublimable substance, the main crystal MA contained in the cured film K is too large. Therefore, an excessively large minute space L may be formed between the main crystals MA. In this case, a part of the convex portion T corresponds to the second convex portion T2. The second convex portion T2 is not properly supported by the cured film K. The position of the micro space L is locally distributed. The positions of the second protrusions T2 are locally distributed. If the gas-liquid interface R intersects the second convex part T2, the second convex part T2 collapses. If the processing liquid g remaining in the micro space L forms a gas-liquid interface R intersecting the second convex portion T2, the second convex portion T2 will collapse. That is, partial collapse of the pattern WP occurs.

Based on the above mechanism, the present inventors speculated that collapse of the pattern WP occurred in the comparative example.

Furthermore, in the above-mentioned mechanism, the reduction of the processing liquid g in the micro space L occurs during the cured film formation process. The generation of the gas-liquid interface R in the micro space L occurs during the cured film formation process. The collapse of the pattern WP (convex portion T) occurs in the cured film forming process. But it is not limited to this. The reduction of the processing liquid g in the micro space L can occur in at least any one of the cured film formation process and the sublimation process. The generation of the gas-liquid interface R in the micro space L can occur in at least any one of the cured film formation process and the sublimation process. The collapse of the pattern WP (convex portion T) can occur in at least any one of the cured film formation process and the sublimation process. Under these circumstances, the second convex portion T2 is also very likely to collapse.

＜1-9. Protection mechanism of pattern WP＞ The inventors of the present invention studied the protection mechanism of the pattern WP in the experimental example. Below, the four mechanisms for protecting pattern WP are explained. The present inventors speculate that at least one of the four mechanisms played a role in the experimental examples.

<1-9-1. The first example of the protection mechanism of pattern WP> 18(a)-18(d) are diagrams respectively illustrating the first example of the protection mechanism of the pattern WP. 18(a) to 18(d) are diagrams schematically showing the substrate W in the cured film forming step.

Refer to Figure 18(a). The treatment liquid g contains a main sublimable substance. The treatment liquid g contains a sub-sublimable substance.

In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of main crystal nuclei mA and a plurality of auxiliary crystal nuclei mB. The main crystal nucleus mA and the auxiliary crystal nucleus mB are respectively generated in the treatment liquid g. The main crystal nucleus mA contains a main sublimable substance. The main crystallization nucleus mA is derived from the main sublimable substance. The secondary crystal core mB contains a secondary sublimable substance. The secondary crystallization nucleus mB is derived from a secondary sublimable substance. The main crystal nucleus mA and the subsidiary crystal nucleus mB are respectively solid. The main crystal nucleus mA and the subsidiary crystal nucleus mB are microparticles respectively.

The secondary crystal nucleus mB is generated, for example, at a position between a plurality of main crystal nuclei mA. The secondary crystal nucleus mB is generated substantially simultaneously with the main crystal nucleus mA, for example.

Refer to Figure 18(b). The main crystal nucleus mA grows on the substrate W to become the main crystal MA. The main crystal nucleus mA changes into the main crystal MA in the treatment liquid g. The main crystal MA contains a main sublimable substance. The main crystalline MA is solid. The main crystal MA is larger than the main crystal nucleus mA.

The secondary crystal nuclei mB grow on the substrate W to form the secondary crystal MB. The secondary crystal nucleus mB changes into the secondary crystal MB in the treatment liquid g. Sub-crystalline MB contains a sub-sublimable substance. The secondary crystalline MB is solid. The accessory crystal MB is larger than the accessory crystal nucleus mB.

For example, the change from the accessory crystallization nucleus mB to the accessory crystallization MB and the change from the autonomous crystallization nucleus mA to the main crystallization MA occur substantially simultaneously.

The subsidiary crystal MB grows, for example, between the plurality of main crystals MA.

The main crystalline MA grows. The main crystal MA becomes larger. Vice crystal MB grows. The secondary crystal MB becomes larger. The subsidiary crystal MB grows substantially in the same manner as the main crystal MA, for example. For example, the secondary crystal MB grows substantially simultaneously with the main crystal MA. Therefore, the size of the secondary crystal MB is substantially the same as the size of the main crystal MA, for example. The particle size of the secondary crystal MB is, for example, substantially the same as the particle size of the main crystal MA.

The main crystal MA and the sub-crystal MB constitute the cured film K. In other words, the cured film K includes main crystal MA and sub-crystal MB.

When the main crystal MA grows, the main crystal MA absorbs the main crystal nucleus mA other than the main crystal nucleus mA which is the basis of the main crystal MA. As a result, the number of main crystals MA is less than the number of main crystal nuclei mA. The number of main crystal MA is less than the number of main crystal nuclei mA produced.

Furthermore, part of the main crystal MA can also absorb other main crystal MA. As a result, the number of main crystal MA further decreases.

When the sub-crystal MB grows, the sub-crystal MB absorbs sub-crystal nuclei mB other than the sub-crystal nucleus mB which is the basis of the sub-crystal MB. As a result, the number of secondary crystals MB is smaller than the number of secondary crystal nuclei mB. The number of secondary crystal MB is less than the number of secondary crystal nuclei mB produced.

Furthermore, some of the secondary crystals MB can also absorb other secondary crystals MB. As a result, the number of secondary crystals MB further decreases.

Refer to Figure 18(c). The main crystal MA and the sub-crystal MB are further grown on the substrate W respectively. The main crystal MA and the sub-crystal MB respectively become larger on the substrate W. The size of the secondary crystal MB is substantially the same as the size of the main crystal MA.

Soon, the secondary crystal MB comes into contact with the main crystal MA on the substrate W. For example, the main crystal MA and the sub-crystal MB adjacent to each other are in contact with each other.

Here, no absorption occurs between the main crystal MA and the sub-crystal MB. One of the main crystal MA and the sub-crystal MB does not absorb the other of the main crystal MA and the sub-crystal MB.

After the main crystal MA and the sub-crystal MB come into contact with each other, a minute space L may be formed. The minute space L is, for example, a crystal grain boundary. The minute space L is, for example, a crack. The minute space L is, for example, a gap.

There is no main crystal MA in the tiny space L. There is no accessory crystal MB in the tiny space L. The cured film K does not exist in the tiny space L.

The micro space L is located inside the cured film K. The minute space L is located below the cured film K, for example.

The tiny space L is located around the main crystal MA. The tiny space L is connected to the main crystal MA. The tiny space L is located around the sub-crystal MB. The minute space L is in contact with the sub-crystal MB.

The tiny space L is located between the main crystal MA and the sub-crystal MB. The minute space L is located, for example, below the main crystal MA and the sub-crystal MB that are in contact with each other. The micro space L is located around the pattern WP, for example. The minute space L is in contact with the pattern WP, for example. The minute space L is located around the convex portion T, for example. The minute space L is in contact with the convex portion T, for example. The minute space L relates to the recessed portion A, for example. The minute space L is formed in the recessed portion A, for example.

Here, the main crystal MA and the sub-crystal MB are each relatively small. The main crystal MA is not too large. The secondary crystal MB is not too large either.

For example, the particle size of the main crystal MA shown in FIG. 18(c) is smaller than the particle size of the main crystal MA shown in FIG. 15 . Specifically, the size of the main crystal MA when the cured film K contains the sub-sublimable substance is smaller than the size of the main crystal MA when the cured film K does not contain the sub-sublimable substance.

For example, the particle size of the secondary crystal MB shown in FIG. 18(c) is smaller than the particle size of the main crystal MA shown in FIG. 15 . Specifically, the size of the secondary crystal MB when the cured film K contains a sub-sublimable substance is smaller than the size of the main crystal MA when the cured film K does not contain a sub-sublimable substance.

Since the main crystal MA and the sub-crystal MB are respectively relatively small, the micro space L is relatively small. The tiny space L is not too large. The micro space L when the cured film K contains the sub-crystal MB is smaller than the micro space L when the cured film K does not contain the sub-crystal MB. For example, the size of the micro space L shown in FIG. 18(c) is smaller than the size of the micro space L shown in FIG. 15 .

When the main crystal MA and the accessory crystal MB are not distinguished, they are simply called crystal M. When the cured film K contains a sub-sublimable substance, the number of crystals M is the sum of the number of main crystals MA and the number of sub-crystals MB. When the cured film K contains a main sublimable material and a sub-sublimable material, the number of crystals M is equal to the sum of the number of main crystals MA and the number of sub-crystals MB. When the cured film K does not contain a sub-sublimable substance, the number of crystals M is only the number of main crystals MA. When the cured film K contains a main sublimable substance and does not contain a sub-sublimable substance, the number of crystals M is equal to the number of main crystals MA. Therefore, the number of crystals M when the cured film K contains a sub-sublimable substance is larger than the number of crystals M when the cured film K does not contain a sub-sublimable substance. The number of crystals M when the cured film K contains a main sublimable substance and a sub-sublimable substance is greater than the number of crystals M when the cured film K contains a main sublimable substance and does not contain a sub-sublimable substance.

Since the number of crystals M contained in the cured film K is relatively large, the microspace L becomes smaller.

Furthermore, the subsidiary crystal MB grows at a position between the plurality of main crystals MA. Therefore, the sub-crystal MB makes the micro space L smaller more effectively.

For example, the minute space L is smaller than one recess A. For example, the length of the tiny space L in the vertical direction Z is smaller than the height HP of the pattern WP. For example, when the cured film K contains a main sublimable material and a sub-sublimable material, the length of the minute space L in the vertical direction Z is smaller than the height HP of the pattern WP. For example, the length of the tiny space L in the experimental example in the vertical direction Z is smaller than the height HP of the pattern WP.

As a result, the crystal M enters all the recessed portions A. The cured film K is formed in all the recessed parts A.

Therefore, when the cured film K contains a sub-sublimable substance, all the recessed portions A correspond to the first recessed portion A1. When the cured film K contains a sub-sublimable substance, the recessed portion A does not include the second recessed portion A2.

When the cured film K contains a sub-sublimable substance, all the convex portions T correspond to the first convex portion T1. When the cured film K contains a sub-sublimable substance, the convex portion T does not include the second convex portion T2.

The treatment liquid g may remain in the tiny space L. The processing liquid g may remain in a part of the concave portion A. The processing liquid g may remain in part of the first recessed portion A1. Specifically, a part of the treatment liquid g may remain in the micro space L without turning into the cured film K. Part of the treatment liquid g may remain in the recessed portion A. Part of the processing liquid g may remain in the first concave portion A1.

Refer to Figure 18(d). The treatment liquid g in the tiny space L gradually decreases. The treatment liquid g in the tiny space L gradually disappears. Gas J may enter the tiny space L. The processing liquid g and the gas J may exist in the minute space L. The treatment liquid g and gas J in the small space L may form a gas-liquid interface R. The gas-liquid interface R is located in the tiny space L. The gas-liquid interface R may be located in the first recessed portion A1, for example. The gas-liquid interface R sometimes intersects the first convex portion T1.

If the gas-liquid interface R intersects the first convex part T1, the processing liquid g acts significantly on the first convex part T1. Specifically, the first convex portion T1 receives the surface tension of the processing liquid g.

The first side portion of the first convex portion T1 is in contact with the first recessed portion A1. The second side portion of the first convex portion T1 is in contact with the first recessed portion A1. The cured film K exists in the first recessed portion A1. The cured film K substantially exists in the first recessed portion A1. Therefore, the cured film K supports both the first side portion of the first convex portion T1 and the second side portion of the first convex portion T1.

Therefore, even if the first convex part T1 is subjected to the surface tension of the processing liquid g, the first convex part T1 is unlikely to collapse. The cured film K well protects the first convex portion T1 from the influence of the treatment liquid g.

As described above, all the convex portions T correspond to the first convex portion T1. Therefore, the cured film K supports all the convex portions T well. The cured film K protects all the convex portions T well. For example, the cured film K prevents partial collapse of the pattern WP. For example, the cured film K prevents part of the pattern WP from collapsing.

For convenience, refer to Figures 9 and 10. In the sublimation process, the cured film K is sublimated. By sublimation of the cured film K, the substrate W is dried. After the substrate W is dried, the pattern WP does not collapse. After the substrate W is dried, the pattern WP also maintains a proper shape.

In summary, when the cured film K contains a main sublimable substance and a sub-sublimable substance, at least one of the main crystal MA and the sub-crystal MB contained in the cured film K is smaller. Therefore, even if the micro space L is formed between the main crystal MA and the sub crystal MB, the micro space L is small. In this case, the entire convex portion T corresponds to the first convex portion T1. The first convex portion T1 is appropriately supported by the cured film K. It is assumed that even if the gas-liquid interface R intersects the first convex part T1, the first convex part T1 will not collapse. Even if the processing liquid g remaining in the tiny space L forms a gas-liquid interface R intersecting the first convex portion T1, the first convex portion T1 will not collapse. That is, collapse of the pattern WP is suppressed. The collapse of local pattern WP is also suppressed. Therefore, the pattern WP is appropriately protected.

Based on the above mechanism, the inventors speculated that the pattern WP was properly protected in the experimental example.

Furthermore, in the above-mentioned mechanism, the reduction of the processing liquid g in the micro space L occurs during the cured film formation process. The generation of the gas-liquid interface R in the micro space L occurs during the cured film formation process. But it is not limited to this. The reduction of the processing liquid g in the micro space L can occur in at least any one of the cured film formation process and the sublimation process. The generation of the gas-liquid interface R in the micro space L can occur in at least any one of the cured film formation process and the sublimation process. In such cases, the pattern WP is also properly protected.

＜1-9-2. The second example of the protection mechanism of pattern WP＞ The second example of the protection mechanism of pattern WP is explained. In the first example, the formation of the secondary crystal nucleus mB and the formation of the main crystal nucleus mA occur substantially simultaneously. In the first example, the growth of the sub-crystal MB and the growth of the main crystal MA occur substantially simultaneously. In contrast, in the second example, the main crystal nucleus mA is formed earlier than the secondary crystal nucleus mB. In the second example, the growth of the main crystal MA is earlier than the growth of the subsidiary crystal MB.

19(a)-19(d) are diagrams respectively illustrating the second example of the protection mechanism of the pattern WP. 19(a) to 19(d) are diagrams schematically showing the substrate W in the cured film forming step.

Refer to Figure 19(a). The treatment liquid g contains a main sublimable substance and a secondary sublimable substance.

In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of main crystal nuclei mA. However, the processing liquid g on the substrate W has not yet generated secondary crystal nuclei mB.

Refer to Figure 19(b). The main crystal nucleus mA grows on the substrate W to become the main crystal MA.

The treatment liquid g on the substrate W generates a plurality of secondary crystal nuclei mB. The secondary crystallization nucleus mB is generated after the main crystallization nucleus mA. In other words, the main crystal nucleus mA is formed earlier than the subsidiary crystal nucleus mB.

Refer to Figure 19(c). The main crystal MA is further grown on the substrate W.

The secondary crystal nuclei mB grow on the substrate W to form the secondary crystal MB. The change from the secondary crystal nucleus mB to the secondary crystal MB occurs after the change from the primary crystal nucleus mA to the primary crystal MA. For example, when the main crystal MA grows, the subsidiary crystal nucleus mB changes into the subsidiary crystal MB. For example, when the main crystal MA grows, the secondary crystal nucleus mB changes into the secondary crystal MB.

In this way, the main crystal MA grows before the sub-crystal MB. The main crystal MA grows earlier than the accessory crystal MB. Therefore, the size of the main crystal MA is larger than the size of the accessory crystal MB.

Refer to Figure 19(d). The main crystal MA is further grown on the substrate W. The secondary crystal MB also grows further on the substrate W.

The secondary crystal MB grows after the main crystal MA. More specifically, after the main crystal MA starts growing, the sub-crystal MB starts growing. The secondary crystal MB grows later than the main crystal MA. Therefore, the size of the secondary crystal MB is smaller than the size of the main crystal MA.

Soon, the secondary crystal MB comes into contact with the main crystal MA on the substrate W. For example, the main crystal MA and the sub-crystal MB adjacent to each other are in contact with each other. After the main crystal MA and the sub-crystal MB come into contact with each other, a minute space L may be formed.

Here, the secondary crystal MB is not too large. The secondary crystal MB is smaller. Specifically, the size of the accessory crystal MB when the main crystal MA grows earlier than the accessory crystal MB is smaller than the size of the accessory crystal MB when the accessory crystal MB and the accessory crystal MA grow substantially simultaneously. For example, the size of the sub-crystal MB shown in FIG. 19(d) is smaller than the size of the sub-crystal MB shown in FIG. 18(c).

Since the sub-crystal MB is smaller, it is assumed that even if the micro space L is formed, the micro space L is smaller. The tiny space L is not too large. Specifically, the size of the micro space L when the main crystal MA grows earlier than the sub crystal MB is smaller than the size of the micro space L when the sub crystal MB and the main crystal MA grow substantially simultaneously. For example, the size of the micro space L shown in FIG. 19(d) is smaller than the size of the micro space L shown in FIG. 18(c).

Furthermore, the subsidiary crystal MB grows later than the growth of the main crystal MA. Therefore, the sub-crystal MB makes the micro space L smaller more effectively.

Since the minute space L is smaller, the convex portion T is appropriately supported by the cured film K. Specifically, the crystal M enters all the recessed portions A. The cured film K is formed in all the recessed parts A. Therefore, all the recessed portions A correspond to the first recessed portion A1. All convex portions T correspond to the first convex portion T1. Therefore, all the convex portions T are appropriately supported by the cured film K.

Since the convex part T is appropriately supported by the cured film K, the convex part T is unlikely to collapse. It is assumed that even if the gas-liquid interface R intersects the convex part T, the convex part T will not collapse easily. It is assumed that even if a gas-liquid interface R intersecting the convex part T is formed, the convex part T will not collapse easily. Therefore, the pattern WP is properly protected.

＜1-9-3. The third example of the protection mechanism of pattern WP＞ The third example of the protection mechanism of pattern WP is explained. In the third example, the main crystal nucleus mA is formed after the secondary crystal nucleus mB is formed. In the third example, the growth of main crystal MA follows the growth of sub-crystal MB.

Figures 20(a)-20(d) are diagrams respectively illustrating the third example of the protection mechanism of the pattern WP. 20(a) to 20(d) are diagrams schematically showing the substrate W in the cured film forming step.

Refer to Figure 20(a). The treatment liquid g contains a main sublimable substance and a secondary sublimable substance.

In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of secondary crystal nuclei mB. However, the processing liquid g on the substrate W has not yet generated main crystal nuclei mA.

Refer to Figure 20(b). The secondary crystal nuclei mB grow on the substrate W to form the secondary crystal MB.

The treatment liquid g on the substrate W generates a plurality of main crystal nuclei mA. The main crystal nucleus mA is generated after the secondary crystal nucleus mB. In other words, the secondary crystal nucleus mB is formed earlier than the main crystal nucleus mA.

Refer to Figure 20(c). The secondary crystal MB further grows on the substrate W.

The main crystal nucleus mA grows on the substrate W to become the main crystal MA. The change from the autonomous crystallization nucleus mA to the main crystallization MA occurs after the change from the accessory crystallization nucleus mB to the accessory crystallization MB. For example, when the secondary crystal MB grows, the main crystal nucleus mA changes to the main crystal MA. For example, when the secondary crystal MB grows, the main crystal nucleus mA changes to the main crystal MA.

In this way, the secondary crystal MB grows before the main crystal MA. The accessory crystal MB grows earlier than the main crystal MA. Therefore, the size of the accessory crystal MB is larger than the size of the main crystal MA.

Refer to Figure 20(d). The main crystal MA is further grown on the substrate W. The secondary crystal MB also grows further on the substrate W.

The main crystal MA grows after the sub-crystal MB. In other words, after the secondary crystal MB starts growing, the main crystal MA starts growing. The main crystal MA grows later than the accessory crystal MB. Therefore, the size of the main crystal MA is smaller than the size of the accessory crystal MB.

Soon, the secondary crystal MB comes into contact with the main crystal MA on the substrate W. For example, the main crystal MA and the sub-crystal MB adjacent to each other are in contact with each other. After the main crystal MA and the sub-crystal MB come into contact with each other, a minute space L may be formed.

Here, the main crystal MA is not too large. The main crystal MA is smaller. Specifically, the size of the main crystal MA when the secondary crystal MB grows earlier than the main crystal MA is smaller than the size of the main crystal MA when the secondary crystal MB and the main crystal MA grow substantially simultaneously. For example, the size of the main crystal MA shown in FIG. 20(d) is smaller than the size of the main crystal MA shown in FIG. 18(c).

Since the main crystal MA is smaller, it is assumed that even if the micro space L is formed, the micro space L is smaller. The tiny space L is not too large. Specifically, the size of the micro space L when the sub crystal MB grows before the main crystal MA is smaller than the size of the micro space L when the sub crystal MB and the main crystal MA grow substantially simultaneously. For example, the size of the micro space L shown in FIG. 20(d) is smaller than the size of the micro space L shown in FIG. 18(c).

Furthermore, the main crystal MA grows later than the growth of the sub-crystal MB. Therefore, the main crystal MA effectively makes the micro space L smaller.

Since the minute space L is smaller, the convex portion T is appropriately supported by the cured film K. In the third example of the protection mechanism of the pattern WP, similarly to the second example of the protection mechanism of the pattern WP, the pattern WP is appropriately supported by the cured film K.

Since the convex part T is appropriately supported by the cured film K, the convex part T is unlikely to collapse. It is assumed that even if the gas-liquid interface R intersects the convex part T, the convex part T will not collapse easily. It is assumed that even if a gas-liquid interface R intersecting the convex part T is formed, the convex part T will not collapse easily. Therefore, the pattern WP is appropriately protected.

＜1-9-4. The 4th example of the protection mechanism of pattern WP＞ The fourth example of the protection mechanism of pattern WP is explained. In the fourth example, the secondary crystal nucleus mB includes the first secondary crystal nucleus mB1 and the second secondary crystal nucleus mB2. In the fourth example, the secondary crystal MB includes the first secondary crystal MB1 and the second secondary crystal MB2. The fourth example is especially the mechanism in Experimental Example 3.

21(a)-21(c) are diagrams respectively illustrating the fourth example of the protection mechanism of the pattern WP. 21(a) to 21(c) are diagrams schematically showing the substrate W in the cured film forming step.

Refer to Figure 21(a). The treatment liquid g contains a main sublimable substance and a secondary sublimable substance. The sub-sublimable substance includes a first sub-sublimable substance and a second sub-sublimable substance. That is, the treatment liquid g contains a main sublimable substance, a first sublimable substance, and a second sublimable substance.

In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of main crystal nuclei mA and a plurality of auxiliary crystal nuclei mB. The secondary crystal nucleus mB includes a first secondary crystal nucleus mB1 and a second secondary crystal nucleus mB2. The first crystal nucleus mB1 contains the first sublimable substance. The first crystal nucleus mB1 is derived from the first sublimable substance. The second crystal nucleus mB2 contains a second sublimable substance. The second crystal nucleus mB2 is derived from the second sublimable substance.

Refer to Figure 21(b). The main crystal nucleus mA grows on the substrate W to become the main crystal MA. The first secondary crystal nucleus mB1 grows on the substrate W to become the first secondary crystal MB1. The second secondary crystal nucleus mB2 grows on the substrate W to form the second secondary crystal MB2. The first crystal MB1 contains the first sublimable substance. The second crystal MB2 contains a second sublimable substance.

The main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 constitute the cured film K. In other words, the cured film K includes the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2.

Refer to Figure 21(c). The main crystal MA, the first sub-crystal MB1 and the second sub-crystal MB2 are further grown on the substrate W respectively. Soon, the main crystal MA, the first sub-crystal MB1 and the second sub-crystal MB2 come into contact with each other on the substrate W. After the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 come into contact with each other, a minute space L may be formed.

Here, the main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 are not too large. The main crystal MA, the first sub-crystal MB1, and the second sub-crystal MB2 are each smaller. Specifically, the size of the main crystal MA when the cured film K contains the second sublimable substance is smaller than the size of the main crystal MA when the cured film K does not contain the second sublimable substance. The size of the first secondary crystal MB1 when the cured film K contains the second sublimable substance is smaller than the size of the secondary crystal MB when the cured film K does not contain the second sublimable substance. The size of the second crystal MB2 when the cured film K contains the second sublimable substance is smaller than the size of the secondary crystal MB when the cured film K does not contain the second sublimable substance. For example, the size of the main crystal MA shown in FIG. 21(c) is smaller than the size of the main crystal MA shown in FIG. 18(c). For example, the size of the first sub-crystal MB1 shown in Fig. 21(c) is smaller than the size of the sub-crystal MB shown in Fig. 18(c). For example, the size of the second sub-crystal MB2 shown in Fig. 21(c) is smaller than the size of the sub-crystal MB shown in Fig. 18(c).

Since the main crystal MA, the first sub-crystal MB1 and the second sub-crystal MB2 are each smaller, it is assumed that even if the micro space L is formed, the micro space L is also smaller. The tiny space L is not too large. Specifically, the size of the microspace L when the cured film K contains the second sublimable substance is smaller than the size of the microspace L when the cured film K does not contain the second sublimable substance. For example, the size of the micro space L shown in FIG. 21(c) is smaller than the size of the micro space L shown in FIG. 18(c).

Furthermore, the number of crystals M contained in the cured film K is larger. The reason is that the crystal M includes the second sub-crystal MB2 in addition to the main crystal MA and the first sub-crystal MB1.

Since the number of crystals M contained in the cured film K is larger, the microspace L is smaller.

Since the minute space L is even smaller, the convex portion T is appropriately supported by the cured film K. Since the minute space L is even smaller, the convex portion T is appropriately protected by the cured film K.

Since the convex part T is appropriately supported by the cured film K, the convex part T is unlikely to collapse. It is assumed that even if the gas-liquid interface R intersects the convex part T, the convex part T will not collapse easily. It is assumed that even if a gas-liquid interface R intersecting the convex part T is formed, the convex part T will not collapse easily. Therefore, the pattern WP is appropriately protected.

<1-10. Effects of the first embodiment> The substrate processing method is used to process the substrate W on which the pattern WP is formed. The substrate processing method includes a processing liquid supply process, a cured film forming process, and a sublimation process. In the processing liquid supply step, the processing liquid g is supplied to the substrate W. The treatment liquid g contains a main sublimable substance, a sub-sublimable substance and a solvent. In the cured film forming process, the solvent evaporates from the treatment liquid g on the substrate W. In the cured film forming step, the cured film K is formed on the substrate W. The cured film K contains a main sublimable substance and a sub-sublimable substance. In the sublimation process, the cured film K is sublimated. By sublimation of the cured film K, the substrate W is dried. Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime. Therefore, the substrate W is properly dried. Specifically, the substrate W is dried in a state where the pattern WP is well protected. For example, the pattern WP is properly protected as a whole. For example, even partial or partial collapse of the pattern WP is well suppressed.

As described above, according to the substrate processing method of the first embodiment, the substrate W is appropriately dried.

The sub-sublimable substance includes a first sub-sublimable substance and a second sub-sublimable substance. The first sublimable substance is camphor. The second sublimable substance is acetone oxime. Therefore, the pattern WP is better protected. Therefore, the substrate W is dried more appropriately.

The volume QB of the secondary sublimable substance contained in the treatment liquid g is 0.5% or more and 20% or less of the volume QA of the main sublimable substance contained in the treatment liquid g. In this way, the sub-sublimable substance contained in the treatment liquid g is relatively small. Therefore, the sub-sublimable substance has little influence on the thickness HG of the liquid film G. Therefore, the thickness HG can be easily controlled in the processing liquid supply process. For example, in the processing liquid supply process, it is easy to control the height position of the upper surface G1 just before the liquid film G starts to change into the cured film K. Therefore, it is easy to control the thickness HK of the cured film K in the cured film forming process. For example, in the cured film formation process, it is easy to control the initial height position of the surface K1 on the cured film K. As a result, the substrate W is dried more appropriately.

In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of main crystal nuclei mA of the main sublimable substance. In the cured film forming process, the treatment liquid g on the substrate W generates a plurality of secondary crystal nuclei mB of the sub-sublimable material. In the cured film forming process, on the substrate W, the main crystal nucleus mA grows into the main crystal MA of the main sublimable substance. In the cured film forming process, on the substrate W, the secondary crystal nuclei mB grow into the secondary crystal MB of the secondary sublimable material. At least one of the main crystal MA and the sub-crystal MB is relatively small. In other words, at least one of the main crystal MA and the sub-crystal MB does not have an excessively large particle size. Therefore, even if the micro space L is formed between the main crystal MA and the sub crystal MB, the micro space L is relatively small. In other words, the tiny space L is not too large. Therefore, the cured film K can support the pattern WP well. Therefore, the substrate W is dried with the pattern WP well protected.

As described above, according to the substrate processing method of the first embodiment, the substrate W is appropriately dried.

In the cured film forming process, the secondary crystal MB is in contact with the main crystal MA. Therefore, even if the micro space L is formed around the main crystal MA, the sub crystal MB makes the micro space L smaller favorably.

In the cured film forming process, the secondary crystal MB grows at a position between the plurality of main crystals MA. Therefore, the sub-crystal MB effectively makes the micro space L smaller. Therefore, the pattern WP is better protected.

In the cured film forming process, secondary crystal nuclei mB are generated at positions between the plurality of main crystal nuclei mA. Therefore, the subsidiary crystal MB grows favorably at a position between the plurality of main crystals MA.

In the cured film forming process, the main crystal MA grows earlier than the sub-crystal MB, for example. Therefore, the secondary crystal MB is smaller than the main crystal MA. Therefore, the sub-crystal MB makes the micro space L smaller more effectively.

In the cured film forming process, the main crystal nucleus mA is formed earlier than the secondary crystal nucleus mB, for example. Therefore, it is easy for the main crystal MA to grow before the sub-crystal MB.

In the cured film forming process, the secondary crystal MB grows earlier than the main crystal MA, for example. Therefore, the main crystal MA is smaller than the accessory crystal MB. Therefore, the main crystal MA makes the micro space L smaller more effectively.

In the cured film forming process, the secondary crystal nucleus mB is formed earlier than the main crystal nucleus mA, for example. Therefore, it is easy for the secondary crystal MB to grow before the main crystal MA.

The substrate processing apparatus 1 includes a substrate holding part 13 and a first supply part 15a. The substrate holding part 13 holds the substrate W. The first supply part 15a supplies the processing liquid g to the substrate W held by the substrate holding part 13. The treatment liquid g contains a main sublimable substance, a sub-sublimable substance and a solvent. Therefore, when the processing liquid g is supplied to the substrate W, the solvent evaporates from the processing liquid g on the substrate W. By evaporating the solvent, a cured film K is formed on the substrate W. The cured film K contains a main sublimable substance and a sub-sublimable substance. Therefore, the cured film K sublimates. By sublimation of the cured film, the substrate W is dried.

Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime. Therefore, the substrate W is properly dried. Specifically, the substrate W is dried in a state where the pattern WP is well protected.

As described above, according to the substrate processing apparatus 1 of the first embodiment, the substrate W is appropriately dried.

The processing liquid g is used for drying the substrate W on which the pattern WP is formed. The treatment liquid g is specifically a drying auxiliary liquid. The treatment liquid g contains a main sublimable substance, a sub-sublimable substance and a solvent.

Here, the main sublimable substance is cyclohexanone oxime. The sub-sublimable substance is at least one of camphor and acetone oxime. Therefore, it is easier to dry the substrate W appropriately using the processing liquid g. Specifically, using the treatment liquid g makes it easier to protect the pattern WP well and dry the board W. In this way, the processing liquid g is useful for drying the substrate W.

As described above, the substrate W is appropriately dried using the processing liquid g.

<2. Second Embodiment> The second embodiment will be described with reference to the drawings. In addition, the same components as those in the first embodiment are denoted by the same reference numerals, and detailed descriptions are omitted.

<2-1. Structure of the processing unit 11> Regarding the outline of the substrate processing apparatus 1, the second embodiment is substantially the same as the first embodiment. Next, the structure of the processing unit 11 of the second embodiment will be described.

FIG. 22 is a diagram showing the configuration of the processing unit 11 and the first supply source 19a according to the second embodiment.

The substrate processing apparatus 1 includes a temperature control unit 50 . The temperature adjustment part 50 adjusts the temperature of the processing liquid g on the substrate W.

The temperature regulating part 50 includes a first temperature regulating part 51 and a second temperature regulating part 52 . Before the processing liquid g is ejected onto the substrate W, the first temperature regulating part 51 and the second temperature regulating part 52 respectively adjust the temperature of the processing liquid g.

For example, the first temperature control unit 51 is attached to the first supply source 19a. The first temperature adjustment unit 51 adjusts the temperature of the processing liquid g in the first supply source 19a. For example, the first temperature control unit 51 is attached to the tank 22 . The first temperature adjustment unit 51 adjusts the temperature of the processing liquid g stored in the tank 22 .

For example, the second temperature control part 52 is attached to the first supply part 15a. The second temperature adjustment part 52 adjusts the temperature of the processing liquid g in the first supply part 15a. For example, the second temperature control unit 52 is attached to the pipe 17a. The second temperature adjustment unit 52 adjusts the temperature of the processing liquid g flowing through the pipe 17a.

The temperature control part 50 further includes a third temperature control part 53 and a fourth temperature control part 54. The third temperature adjustment part 53 and the fourth temperature adjustment part 54 respectively adjust the temperature of the processing liquid g on the substrate W. After the processing liquid g is ejected onto the substrate W, the third temperature regulating part 53 and the fourth temperature regulating part 54 respectively adjust the temperature of the processing liquid g on the substrate W.

For example, the third temperature control unit 53 is disposed above the substrate W held by the substrate holding unit 13 . The third temperature adjustment unit 53 adjusts the temperature of the substrate W. The third temperature adjustment unit 53 adjusts the temperature of the processing liquid g on the substrate W. The third temperature adjustment part 53 adjusts the temperature of the liquid film G.

For example, the fourth temperature control unit 54 is disposed below the substrate W held by the substrate holding unit 13 . The fourth temperature adjustment unit 54 adjusts the temperature of the substrate W. The fourth temperature regulating unit 54 regulates the temperature of the processing liquid g on the substrate W via the substrate W.

The temperature control part 50 may also be equipped with various devices for heating or cooling the processing liquid g.

For example, the temperature control unit 50 may include a resistance heater. Resistance heaters are also known as electric heaters. Resistive heaters contain electric wires.

For example, the temperature control unit 50 may include a lamp heater. Lamp heaters are also known as light heaters. The lamp heater contains a light source that illuminates the light.

For example, the temperature control unit 50 may include a supply unit for supplying a fluid whose temperature has been adjusted. Fluid is either liquid or gas. The liquid is, for example, water or deionized water. The gas is, for example, an inert gas. For example, the temperature adjustment part 50 may also supply gas with an adjusted temperature toward the upper surface of the substrate W. For example, the temperature adjustment part 50 may also supply gas with an adjusted temperature toward the lower surface of the substrate W. For example, the temperature adjustment part 50 may also supply liquid with an adjusted temperature toward the lower surface of the substrate W.

For example, the temperature control unit 50 may include a heat exchanger.

Although illustration is omitted, the control unit 10 controls the temperature control unit 50 . The control unit 10 controls the first to fourth temperature regulating units 51-54.

The processing liquid condition information held by the control unit 10 stipulates, for example, the first temperature V (° C.). The first temperature V corresponds to the target value of the temperature of the treatment liquid g.

The first temperature V is preferably lower than both the melting point PA of the main sublimable material and the melting point PB of the secondary sublimable material. The first temperature V is preferably lower than the melting point PA of the main sublimable substance, the melting point PB1 of the first sublimable substance, and the melting point PB2 of the second sublimable substance.

The lowest melting point among the melting point PA and the melting point PB is called the lowest melting point PL. The first temperature V is preferably lower than the lowest melting point PL.

The first temperature V is preferably a temperature close to the lowest melting point PL. The first temperature V is preferably as high as possible within the temperature range that does not reach the lowest melting point PL. For example, the difference between the first temperature V and the lowest melting point PL is preferably 10 degrees or less. The difference between the first temperature V and the lowest melting point PL is preferably 5 degrees or less. The difference between the first temperature V and the lowest melting point PL is preferably 1 degree or less.

When the lowest melting point PL is higher than normal temperature, the first temperature V is preferably higher than normal temperature.

The first temperature V is preferably higher than the melting point PC of the solvent.

<2-2. Operation example of first supply source 19a and processing unit 11> For convenience, refer to Figure 5. The substrate processing method of the second embodiment includes steps S1 and S11 to S18 described in the first embodiment. The operations of steps S11 to S14, S17, and S18 are substantially the same between the first embodiment and the second embodiment. Therefore, the description of the operations of steps S11-S14, S17, and S18 is omitted. The operations of steps S1, S15, and S16 will be described.

Step S1: Treatment liquid generation process In the processing liquid generating step, the processing liquid g is generated. Furthermore, in the processing liquid generation process, the processing liquid g is adjusted to the first temperature V.

The control unit 10 controls the first supply source 19a and the temperature control unit 50. The control unit 10 controls the first supply source 19a and the temperature control unit 50 based on the processing liquid condition information. The first supply source 19a generates the processing liquid g. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g in the first supply source 19a to the first temperature V. Thereby, the processing liquid g in the first supply source 19a is maintained at the first temperature V.

Specifically, the generation unit 21 generates the treatment liquid g. The treatment liquid g is stored in the tank 22 . The first temperature adjustment part 51 adjusts the temperature of the processing liquid g in the tank 22 to the first temperature V.

In the second embodiment, the treatment liquid g is generated in the environment of the first temperature V. In the second embodiment, the processing liquid g is stored in an environment of the first temperature V.

Step S15: Treatment liquid supply process In the processing liquid supply step, the processing liquid g is supplied to the substrate W. In the processing liquid supply process, the processing liquid g on the substrate W is maintained at the first temperature V.

The control unit 10 controls the first supply source 19a, the first supply unit 15a, and the temperature control unit 50. The control unit 10 controls the temperature adjustment unit 50 based on the processing liquid condition information. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g in the first supply source 19a to the first temperature V. The first supply source 19a supplies the processing liquid g to the first supply part 15a. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g in the first supply unit 15a to the first temperature V. The first supply part 15a supplies the processing liquid g having the first temperature V to the substrate W held by the substrate holding part 13. Furthermore, the temperature adjustment unit 50 adjusts the temperature of the processing liquid g on the substrate W to the first temperature V. Thereby, the processing liquid g on the substrate W is maintained at the first temperature V.

Specifically, the first temperature adjustment unit 51 adjusts the temperature of the processing liquid g in the tank 22 to the first temperature V. The pressure feeding unit 31 feeds the processing liquid g from the tank 22 to the first supply part 15a. The pressure feeding unit 31 supplies the processing liquid g to the first supply part 15a. The processing liquid g flows through the pipe 17a of the first supply part 15a. The second temperature adjustment unit 52 adjusts the processing liquid g flowing through the pipe 17a to the first temperature V. The nozzle 16a of the first supply part 15a sprays the processing liquid g having the first temperature V. The processing liquid g having the first temperature V is supplied to the upper surface of the substrate W. The third temperature adjustment part 53 and the fourth temperature adjustment part 54 adjust the processing liquid g on the substrate W to the first temperature V respectively.

Step S16: Cured film forming process In the cured film forming process, the processing liquid g on the substrate W is maintained at the first temperature V. That is, the processing liquid g on the substrate W is maintained at the first temperature V from the processing liquid supply process to the cured film forming process. In the cured film forming process, the solvent evaporates from the treatment liquid g on the substrate W. In the cured film forming step, the cured film K is formed on the substrate W. The cured film K contains a main sublimable substance and a sub-sublimable substance.

The control unit 10 controls the temperature adjustment unit 50 . The control unit 10 controls the temperature adjustment unit 50 based on the processing liquid condition information. The temperature adjustment unit 50 adjusts the temperature of the processing liquid g on the substrate W to the first temperature V. Thereby, the processing liquid g on the substrate W is maintained at the first temperature V.

Specifically, the third temperature adjustment part 53 and the fourth temperature adjustment part 54 adjust the processing liquid g on the substrate W to the first temperature V respectively.

While the processing liquid g on the substrate W is maintained at the first temperature V, the solvent evaporates from the processing liquid g on the substrate W. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W.

The first temperature V is a temperature close to the lowest melting point PL. The first temperature V is as high as possible within the temperature range that does not reach the lowest melting point PL. Therefore, the solvent quickly evaporates from the treatment liquid g on the substrate W.

The first temperature V is, for example, a temperature higher than normal temperature. Therefore, the solvent evaporates more quickly from the treatment liquid g on the substrate W.

In the cured film forming step, the cured film K is formed on the substrate W while the processing liquid g on the substrate W is maintained at the first temperature V. The first temperature V is lower than the lowest melting point PL. Therefore, the main sublimable substance of the cured film K does not melt. The main sublimation substance of the cured film K does not become liquid. The sub-sublimable substance of the cured film K does not melt either. The sub-sublimable substance of the cured film K also does not become liquid. Therefore, the cured film K does not melt. The cured film K does not become liquid. Therefore, the cured film K is favorably formed on the substrate W.

The processing in the above-mentioned processing liquid supply process and cured film formation process corresponds to the use example of the processing liquid g. In the second embodiment, the treatment liquid g is used in the environment of the first temperature V.

<2-3. Effects of the second embodiment> The second embodiment also exhibits the same effect as the first embodiment. For example, the treatment liquid g contains a main sublimable substance, a secondary sublimable substance, and a solvent. Therefore, the substrate W is properly dried while the pattern WP is well protected. Furthermore, according to the second embodiment, the following effects are exerted.

From the processing liquid supply process to the cured film formation process, the processing liquid g on the substrate W is maintained at the first temperature V. That is, the temperature of the processing liquid g on the substrate W is kept constant from the processing liquid supply process to the cured film forming process. From the processing liquid supply process to the cured film formation process, the change in the temperature of the processing liquid g on the substrate W is suppressed. Therefore, in the cured film forming step, the solvent evaporates smoothly from the processing liquid g on the substrate W. Therefore, in the cured film forming step, an appropriate cured film K is formed on the substrate W. Therefore, the cured film K well protects the pattern WP from the treatment liquid g.

Specifically, the smoother the solvent evaporates, the smaller the main crystal MA and the sub-crystal MB in the cured film K become. Therefore, even if the micro space L is formed between the main crystal MA and the sub crystal MB, the micro space L is smaller. Therefore, the cured film K supports the pattern WP more favorably. The cured film K better protects the pattern WP from the influence of the treatment liquid g. Therefore, the substrate W is dried in a state where the pattern WP is better protected.

As described above, according to the substrate processing method of the second embodiment, the substrate W is dried more appropriately.

The first temperature V is lower than the lowest melting point PL. Specifically, the first temperature V is lower than both the melting point PA of the main sublimable material and the melting point PB of the secondary sublimable material. Therefore, the main sublimable substance contained in the cured film K easily remains in a solid state. The sub-sublimable substance contained in the cured film K also tends to remain in a solid state. Specifically, the main crystal MA and the sub-crystal MB of the cured film K each tend to maintain a solid state. Therefore, in the cured film forming process, the cured film K is formed more appropriately.

The first temperature V is a temperature close to the lowest melting point PL. Therefore, the solvent quickly evaporates from the treatment liquid g on the substrate W. In other words, the evaporation rate of the solvent is greatly improved. Therefore, in the cured film forming process, a more appropriate cured film K is formed on the substrate W. Therefore, the cured film K better protects the pattern WP from the treatment liquid g.

Specifically, the faster the solvent evaporates, the smaller the main crystal MA and the sub-crystal MB in the cured film K become. Therefore, even if the micro space L is formed between the main crystal MA and the sub crystal MB, the micro space L is smaller. Therefore, the cured film K supports the pattern WP more favorably. The cured film K better protects the pattern WP from the influence of the treatment liquid g. Therefore, the substrate W is dried in a state where the pattern WP is better protected.

The first temperature V is higher than normal temperature, for example. Therefore, the solvent evaporates more quickly from the treatment liquid g on the substrate W. Therefore, the cured film K is formed more appropriately. Therefore, the cured film K better protects the pattern WP from the treatment liquid g.

The first temperature V is, for example, higher than the melting point PC of the solvent. Therefore, the solvent evaporates more quickly from the treatment liquid g on the substrate W. Therefore, the cured film K is formed more appropriately. Therefore, the cured film K better protects the pattern WP from the treatment liquid g.

The above-mentioned substrate processing apparatus 1 includes a temperature control unit 50 . The temperature adjustment unit 50 adjusts the processing liquid g on the substrate W to the first temperature V. Therefore, the processing liquid g on the substrate W is well maintained at the first temperature V. Therefore, the solvent evaporates smoothly from the processing liquid g on the substrate W. Therefore, the cured film K is formed more appropriately. As a result, the cured film K better protects the pattern WP from the influence of the treatment liquid g. The substrate W is dried in a state where the pattern WP is better protected. That is, the substrate W is dried more appropriately.

＜3. Modified implementation＞ The present invention is not limited to the first and second embodiments, but can be implemented in various modifications as described below.

(1) In the first and second embodiments, the main sublimable substance is, for example, cyclohexanone oxime. But it is not limited to this. The main sublimable substance can also be appropriately changed to other compounds. For example, the main sublimable substance may be any one of camphor, acetone oxime, acetophenone oxime, D-camphor, pinacolone oxime, 4-tert-butylphenol, and 4-nitrotoluene.

In this modified embodiment, the main sublimable substance is also a substance different from the sub-sublimable substance. In this modified embodiment, it is also preferred that the main sublimable substance is dissolved in a solvent. In this modified embodiment, it is also preferable that the main sublimable substance has a vapor pressure of 0.1 Pa or more at normal temperature. In this modified embodiment, the melting point PA of the main sublimable substance is preferably higher than the melting point PC of the solvent.

(2) In the first and second embodiments, the sub-sublimable substance is, for example, at least one of camphor and acetone oxime. But it is not limited to this. The sub-sublimable substance can also be appropriately changed to other compounds. For example, the sub-sublimable substance may be at least one of camphor, acetophenone oxime, cyclohexanone oxime, D-camphor, pinacolone oxime, 4-tert-butylphenol, and 4-nitrotoluene.

In this modified embodiment, the secondary sublimable substance is preferably a substance different from the main sublimable substance. In this modified embodiment, it is also preferable that the sub-sublimable substance is dissolved in a solvent. In this modified embodiment, it is also preferable that the sub-sublimable substance has a vapor pressure of 0.1 Pa or more at normal temperature. In this modified embodiment, the melting point PB of the sub-sublimable substance is also preferably higher than the melting point PC of the solvent.

(3) In the first and second embodiments, the sub-sublimable substance contains one or two compounds. But it is not limited to this. The sub-sublimable substance may also contain three or more compounds. For example, the sub-sublimable substance may include a third sub-sublimable substance in addition to the first and second sub-sublimable substances.

(4) In the first and second embodiments, the solvent is, for example, isopropyl alcohol. But it is not limited to this. The solvent can also be appropriately changed to other compounds. In this modified embodiment, the solvent also dissolves the main sublimable substance and the secondary sublimable substance. In this modified embodiment, the melting point PC of the solvent is also preferably lower than the melting point PA of the main sublimable material and the melting point PB of the secondary sublimable material.

(5) In the second embodiment, the temperature control unit 50 includes the first to fourth temperature control units 51 to 54. But it is not limited to this. The temperature control unit 50 may be appropriately changed. For example, any one of the first to fourth temperature regulating parts 51 to 54 may be omitted. Alternatively, any two of the first to fourth temperature regulating parts 51 to 54 may be omitted. Alternatively, any three of the first to fourth temperature regulating parts 51 to 54 may be omitted.

(6) In the first and second embodiments, the processing liquid g is generated before the processing liquid g is supplied to the first supply part 15a. In the first and second embodiments, the first supply source 19 a generates the processing liquid in the tank 22 . But it 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 that supplies the processing liquid g to the first supply part 15a.

FIG. 23 is a diagram showing the structure of the processing unit 11 and the first supply source 19a according to the modified embodiment. In addition, the same components as those in the first embodiment are denoted by the same reference numerals, and detailed descriptions are omitted.

The first supply source 19a includes a first tank 41, a second tank 42, and a third tank 43. The first tank 41 stores the main sublimable substance. For example, the first tank 41 may store the main sublimable substance and the solvent. The second tank 42 stores the sub-sublimable substance. For example, the second tank 42 may store sub-sublimable substances and solvents. The third tank 43 stores solvent. For example, the third tank 43 only stores solvent.

The first supply source 19a includes a mixing unit 44. The mixing part 44 is connected to the first tank 41 , the second tank 42 and the third tank 43 . The mixing part 44 communicates with the first tank 41, the second tank 42, and the third tank 43. The mixing unit 44 generates the processing liquid g.

The mixing part 44 is connected to the first supply part 15a. The mixing part 44 communicates with the 1st supply part 15a. The mixing unit 44 supplies the processing liquid g to the first supply unit 15a.

Specifically, the mixing unit 44 includes pipes 45a, 45b, 45c and a joint 46. The pipe 45a is connected to the first tank 41 . The pipe 45a communicates with the first tank 41 . The pipe 45b is connected to the second tank 42 . The pipe 45b communicates with the second tank 42 . The pipe 45c is connected to the third tank 43. The pipe 45c communicates with the third tank 43. The joint 46 is connected to the pipes 45a, 45b, and 45c. The joint 46 communicates with the pipes 45a, 45b, and 45c. The joint 46 is further connected to the pipe 17a. The joint 46 further communicates with the pipe 17a. The pipes 45a, 45b, and 45c are connected to the pipe 17a via the joint 46. The pipes 45a, 45b, and 45c communicate with the pipe 17a via the joint 46.

The mixing part 44 is equipped with pumps 47a, 47b, and 47c. Pumps 47a, 47b, and 47c are respectively provided in pipes 45a, 45b, and 45c. The pump 47a transports the main sublimable substance from the first tank 41 to the joint 46 via the pipe 45a. The pump 47b transports the sub-sublimable substance from the second tank 42 to the joint 46 via the pipe 45b. The pump 47c sends the solvent from the third tank 43 to the joint 46 via the pipe 45c.

The mixing part 44 is equipped with filters 48a, 48b, and 48c. Filters 48a, 48b, and 48c are provided in pipes 45a, 45b, and 45c, respectively. The main sublimable substance passes through the filter 48a. The filter 48a filters the main sublimable substance. The secondary sublimable substance passes through the filter 48b. The filter 48b filters the sub-sublimable substance. The solvent passes through filter 48c. Filter 48c filters the solvent.

The mixing part 44 is equipped with valves 49a, 49b, and 49c. Valves 49a, 49b, and 49c are provided in pipes 45a, 45b, and 45c, respectively. The valve 49a adjusts the flow rate of the main sublimable substance flowing through the pipe 45a. The valve 49b adjusts the flow rate of the sub-sublimable substance flowing through the pipe 45b. The valve 49c adjusts the flow rate of the solvent flowing through the pipe 45c. The valves 49a, 49b, and 49c may each include a flow regulating valve, for example. The valves 49a, 49b, and 49c may each include a flow control valve and an on-off valve, for example.

An operation example of the first supply source 19a in the modified embodiment will be described. In the processing liquid supply step, the first supply source 19a generates the processing liquid g and transports the processing liquid g to the first supply part 15a. Specifically, valves 49a, 49b, and 49c are opened. The pump 47a transports the main sublimable substance from the first tank 41 to the joint 46. The pump 47a pressure-feeds the main sublimable substance from the first tank 41 to the joint 46. The pump 47b transports the sub-sublimable substance from the second tank 42 to the joint 46. The pump 47b pressure-feeds the sub-sublimable substance from the second tank 42 to the joint 46. The pump 47c delivers the solvent from the third tank 43 to the joint 46. The pump 47c pressure-feeds the solvent from the third tank 43 to the joint 46. The main sublimable substance, the secondary sublimable substance and the solvent are mixed in the joint 46 . The main sublimable substance, the sub-sublimable substance and the solvent become the treatment liquid g in the joint 46 . Furthermore, the processing liquid g flows from the joint 46 to the first supply part 15a. The nozzle 16a sprays the processing liquid g.

According to this modified embodiment, there is no need to store the processing liquid g before supplying the processing liquid g to the first supply part 15a. Therefore, the mixing ratio of the main sublimable substance, the sub-sublimable substance and the solvent in the treatment liquid is controlled with high accuracy. Therefore, the substrate W is dried more appropriately.

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

(7) The substrate processing method of the first and second embodiments includes a chemical solution supply process, a rinse liquid supply process, and a replacement liquid supply process. But it is not limited to this. For example, at least one of the chemical solution supply process, the rinse liquid supply process, and the replacement liquid supply process can be omitted. For example, all of the chemical solution supply process, rinse liquid supply process, and replacement liquid supply process may be omitted.

(8) In the first and second embodiments, when the processing liquid supply step is performed, liquid (eg, replacement liquid) exists on the substrate W. That is, in the processing liquid supply step, the processing liquid g is supplied to the substrate W in a non-dried state. But it is not limited to this. For example, when performing the processing liquid supply process, there may be no liquid (such as replacement liquid) on the substrate W. For example, in the processing liquid supply step, the processing liquid g may be supplied to the substrate W in a dry state.

(9) In the processing liquid supply step of the first and second embodiments, the processing liquid g removes the replacement liquid from the substrate W. But it is not limited to this. For example, in the processing liquid supply process, the substrate W can be cleaned by the processing liquid g. 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. Foreign matter is, for example, resist residue.

(10) In the cured film forming process of the first and second embodiments, dry gas is not supplied to the substrate W. But it is not limited to this. In the cured film forming process, dry gas may be supplied to the substrate W. In the cured film forming process, dry gas may be supplied to the processing liquid g on the substrate W. According to this modified embodiment, in the cured film forming process, the processing liquid g on the substrate W is exposed to the dry gas. Therefore, in the cured film forming process, 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.

(11) In the first and second embodiments, for example, the pattern WP on the substrate W may be formed on the substrate W before the processing unit 11 processes the substrate W. Alternatively, the pattern WP may be formed on the substrate W when the processing unit 11 processes the substrate W. The pattern WP may be formed on the substrate W, for example, in the chemical solution supply process (step S12).

(12) Regarding the first and second embodiments and the modified embodiments described in (1) to (11) above, each configuration may be replaced with the configuration of other modified embodiments or combined with them, etc. Make changes as appropriate.

1:Substrate processing device 3: Transmission Department 4: Vehicle mounting part 5:Transportation mechanism 5a:Manipulator 5b: Robot drive department 7: Processing blocks 8:Transportation mechanism 8a:Manipulator 8b: Robot driving part 10:Control Department 11: Processing unit 12: Shell 13:Substrate holding part 14: Rotary drive part 15: Supply Department 15a: First supply part (processing liquid supply part) 15b: 2nd Supply Department 15c: 3rd Supply Department 15d: 4th Supply Department 15e: 5th Supply Department 16a:Nozzle 16b:Nozzle 16c:Nozzle 16d:Nozzle 16e:Nozzle 17a:Piping 17b:Piping 17c:Piping 17d:Piping 17e:Piping 18a: valve 18b: valve 18c: valve 18d: valve 18e: valve 19a: 1st supply source 19b: 2nd supply source 19c: 3rd supply source 19d: 4th supply source 19e: 5th supply source 21:Generation unit 22:Slot 23a: Supply Department 23b: Supply Department 23c: Supply Department 23d: Supply Department 24a:Piping 24b:Piping 24c:Piping 24d:Piping 25a: valve 25b: valve 25c: valve 25d: valve 26a: Source of supply 26b: Supply source 26c: Source of supply 26d: Supply source 31: Pressure feeding unit 32:Piping 33:Connector 34:Pump 35:Filter 41:Slot 1 42:Slot 2 43:Slot 3 44: Mixing Department 45a:Piping 45b:Piping 45c:Piping 46:Connector 47a:Pump 47b:Pump 47c:pump 48a: filter 48b: filter 48c: filter 49a: valve 49b: valve 49c: valve 50:Temperature control department 51: 1st Temperature Control Department 52: 2nd temperature control section 53: The third temperature control section 54: No. 4 Temperature Control Department A: concave part A1: 1st concave part A2: 2nd concave part B:Rotation axis C:Vehicle g: treatment liquid G: liquid film of treatment liquid G1: Surface above the liquid film HG: thickness of liquid film HK: thickness of cured film HP: height of convex part (height of pattern) J: Gas K: Cured film K1: Surface above the cured film L: small space MA: main crystal MB: Vice crystal MB1: The first crystal MB2: Second crystal mA: main crystal nucleus mB: accessory crystal nucleus mB1: The first crystal nucleus mB2: The second crystal nucleus PA: melting point of main sublimable substance PB: Melting point of sub-sublimable substance PB1: Melting point of the first sublimable substance PB2: The melting point of the second sublimable substance PC: melting point of solvent PL: lowest melting point (the lowest melting point between melting point PA and melting point PB) R: gas-liquid interface T: convex part T1: 1st convex part T2: 2nd convex part Td: front end Tp: base end V: 1st temperature W: substrate WP:Pattern

FIG. 1 is a diagram schematically showing a part of the substrate. FIG. 2 is a plan view showing the inside of the substrate processing apparatus according to the first embodiment. Figure 3 is a control block diagram of the substrate processing device. FIG. 4 is a diagram showing the structure of the processing unit and the first supply source. FIG. 5 is a flowchart showing the procedure of the substrate processing method according to the first embodiment. FIG. 6 is a diagram schematically showing the substrate in the processing liquid supply step. FIG. 7 is a diagram schematically showing a substrate in a cured film forming step. FIG. 8 is a diagram schematically showing a substrate in a cured film forming step. FIG. 9 is a diagram schematically showing the substrate in the sublimation process. FIG. 10 is a diagram schematically showing the substrate in the sublimation process. FIG. 11 is a table showing the collapse rate of the treated substrates in Experimental Examples 1-3 and Comparative Examples. FIG. 12 is a graph showing the collapse rate of the treated substrates in Experimental Examples 1-3 and Comparative Examples. Figure 13 is a diagram illustrating the pattern collapse mechanism. Figure 14 is a diagram illustrating the pattern collapse mechanism. Figure 15 is a diagram illustrating the pattern collapse mechanism. Figure 16 is a diagram illustrating the pattern collapse mechanism. Figure 17 is a diagram illustrating the pattern collapse mechanism. 18(a)-18(d) are diagrams respectively illustrating the first example of the pattern protection mechanism. 19(a)-19(d) are diagrams respectively illustrating the second example of the pattern protection mechanism. 20(a)-20(d) are diagrams respectively illustrating the third example of the pattern protection mechanism. 21(a)-21(c) are diagrams respectively illustrating the fourth example of the pattern protection mechanism. FIG. 22 is a diagram showing the structure of the processing unit and the first supply source according to the second embodiment. FIG. 23 is a diagram showing the structure of the processing unit and the first supply source according to the modified embodiment.

1:Substrate processing device

11: Processing unit

12: Shell

13:Substrate holding part

14: Rotary drive part

15: Supply Department

15a: First supply part (processing liquid supply part)

15b: 2nd Supply Department

15c: 3rd Supply Department

15d: 4th Supply Department

15e: 5th Supply Department

16a:Nozzle

16b:Nozzle

16c:Nozzle

16d:Nozzle

16e:Nozzle

17a:Piping

17b:Piping

17c:Piping

17d:Piping

17e:Piping

18a: valve

18b: valve

18c: valve

18d: valve

18e: valve

19a: 1st supply source

19b: 2nd supply source

19c: 3rd supply source

19d: 4th supply source

19e: 5th supply source

21:Generation unit

22:Slot

23a: Supply Department

23b: Supply Department

23c: Supply Department

23d: Supply Department

24a:Piping

24b:Piping

24c:Piping

24d:Piping

25a: valve

25b: valve

25c: valve

25d: valve

26a: Source of supply

26b: Supply source

26c: Source of supply

26d: Supply source

31: Pressure feeding unit

32:Piping

33:Connector

34:Pump

35:Filter

B:Rotation axis

g: treatment liquid

W: substrate

Claims (15)

A substrate processing method that processes a substrate on which a pattern is formed, including: a processing liquid supply step of supplying a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate; and a cured film forming step , which is to evaporate the above-mentioned solvent from the above-mentioned treatment liquid on the substrate to form a cured film containing the above-mentioned main sublimable substance and the above-mentioned secondary sublimable substance on the substrate; and a sublimation process, which is to sublimate the above-mentioned cured film; the above-mentioned main sublimable substance The sublimable substance is cyclohexanone oxime, and the above-mentioned sub-sublimable substance is at least one of camphor and acetone oxime. The substrate processing method of claim 1, wherein the volume of the secondary sublimable substance contained in the above-mentioned treatment liquid is 0.5% or more and less than 20% of the volume of the above-mentioned main sublimable substance contained in the above-mentioned treatment liquid. A substrate processing method that processes a substrate on which a pattern is formed, including: a processing liquid supply step of supplying a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate; and a cured film forming step , which is to evaporate the above-mentioned solvent from the above-mentioned treatment liquid on the substrate to form a cured film containing the above-mentioned main sublimable substance and the above-mentioned secondary sublimable substance on the substrate; and a sublimation process, which is to sublimate the above-mentioned cured film; in the above-mentioned In the cured film forming process, the above-mentioned treatment liquid on the substrate generates a plurality of main crystal nuclei of the above-mentioned main sublimable substance and the above A plurality of secondary crystal nuclei of the secondary sublimable substance, the above-mentioned main crystal nuclei grow on the substrate to become the main crystal of the above-mentioned main sublimable substance, the above-mentioned secondary crystal nuclei grow on the substrate into the secondary crystals of the above-mentioned secondary sublimable substance, the above-mentioned main The sublimating substance is cyclohexanone oxime. The substrate processing method of claim 3, wherein in the cured film forming step, the secondary crystal grows at a position between a plurality of the main crystals. The substrate processing method according to claim 4, wherein in the cured film forming step, the secondary crystallization nuclei are generated at positions between the plurality of main crystallization nuclei. The substrate processing method of claim 3, wherein in the cured film forming step, the main crystal grows before the secondary crystal. The substrate processing method of claim 6, wherein in the cured film forming step, the main crystal nuclei are formed earlier than the secondary crystal nuclei. The substrate processing method of claim 3, wherein in the cured film forming step, the secondary crystal grows before the main crystal. Such as the substrate processing method of claim 8, wherein In the above-mentioned cured film forming process, the above-mentioned secondary crystal nuclei are formed earlier than the above-mentioned main crystal nuclei. A substrate processing method that processes a substrate on which a pattern is formed, including: a processing liquid supply step of supplying a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate; and a cured film forming step , which is to evaporate the above-mentioned solvent from the above-mentioned treatment liquid on the substrate to form a cured film containing the above-mentioned main sublimable substance and the above-mentioned secondary sublimable substance on the substrate; and a sublimation process, which is to sublime the above-mentioned cured film; During the processing liquid supply step and the cured film forming step, the processing liquid on the substrate is maintained at the first temperature. The substrate processing method of claim 10, wherein the first temperature is lower than both the melting point of the main sublimable material and the melting point of the secondary sublimable material. The substrate processing method of claim 11, wherein the first temperature is a temperature close to the lowest melting point of the melting point of the main sublimable material and the melting point of the secondary sublimable material. A substrate processing apparatus provided with: a substrate holding unit that holds a substrate; and a processing liquid supply unit that supplies a processing liquid containing a primary sublimable substance, a secondary sublimable substance, and a solvent to the substrate held by the substrate holding unit; The main sublimable substance is cyclohexanone oxime, and the secondary sublimable substance is at least one of camphor and acetone oxime. The substrate processing apparatus of Claim 13 is provided with a temperature adjustment part that adjusts the processing liquid on the substrate to a first temperature. A treatment liquid for drying a substrate on which a pattern is formed, and the treatment liquid includes a main sublimable substance, a secondary sublimable substance, and a solvent, where the main sublimable substance is cyclohexanone oxime, and the secondary sublimable substance The substance is at least one of camphor and acetone oxime.