JP6898073B2 - Substrate processing equipment and substrate processing method - Google Patents

Description

The present invention relates to a semiconductor substrate, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for FED (Field Emission Display), a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, and the like. The present invention relates to a substrate processing apparatus and a substrate processing method for removing liquid adhering to various substrates (hereinafter, simply referred to as “substrate”) from the substrate.

In the manufacturing process of electronic components such as semiconductor devices and liquid crystal display devices, various wet treatments using liquids are applied to the substrate, and then the substrate is subjected to a drying treatment to remove the liquid adhering to the substrate by the wet treatment. Apply to.

Examples of the wet treatment include a cleaning treatment for removing contaminants on the surface of the substrate. For example, a reaction by-product (etching residue) is present on the surface of a substrate on which a fine pattern having irregularities is formed by a dry etching step. In addition to the etching residue, metal impurities, organic pollutants, and the like may adhere to the surface of the substrate, and in order to remove these substances, a cleaning treatment such as supplying a cleaning liquid to the substrate is performed.

After the cleaning treatment, a rinsing treatment for removing the cleaning liquid with a rinsing liquid and a drying treatment for drying the rinsing liquid are performed. Examples of the rinsing treatment include a rinsing treatment in which a rinsing liquid such as Deionized Water (DIW) is supplied to the surface of the substrate to which the cleaning liquid is attached to remove the cleaning liquid on the surface of the substrate. Then, a drying treatment is performed to dry the substrate by removing the rinsing liquid.

In recent years, as the pattern formed on the substrate has become finer, the aspect ratio (ratio of height to width in the convex portion of the pattern) in the convex portion of the pattern having irregularities has increased. For this reason, during the drying process, the surface tension acting on the interface between the liquid such as the cleaning liquid or rinsing liquid that has entered the concave portion of the pattern and the gas in contact with the liquid attracts the adjacent convex portions in the pattern and collapses. There is a problem of so-called pattern collapse.

As a drying technique for the purpose of preventing the collapse of a pattern that is troubled by such surface tension, for example, in Patent Document 1 below, a solution is brought into contact with a substrate on which a structure (pattern) is formed, and the solution is applied. A method is disclosed in which a solid is changed to form a pattern support, and the support is changed from a solid phase to a gas phase and removed without passing through a liquid phase. Further, Patent Document 1 discloses that at least one of a methacrylic resin material, a styrene resin material, and a fluorocarbon material is used as a support material.

Further, in Patent Documents 2 and 3, a solution of a sublimable substance is supplied on a substrate, the solvent in the solution is dried, and the substrate is filled with a solid phase sublimable substance to sublimate the sublimable substance. The drying technique is disclosed. According to these patent documents, since surface tension does not act on the interface between the solid and the gas in contact with the solid, it is possible to suppress the collapse of the pattern due to the surface tension.

Further, in Patent Document 4, a melt of tert-butanol (t-butanol) is supplied to a substrate to which a liquid is attached, and t-butanol is coagulated on the substrate to form a coagulated body, and then t-butanol is used. A drying technique for sublimating and removing is disclosed.

Japanese Unexamined Patent Publication No. 2013-16699 Japanese Unexamined Patent Publication No. 2012-243869 Japanese Unexamined Patent Publication No. 2013-258272 Japanese Unexamined Patent Publication No. 2015-12069

However, in the drying technique disclosed in Patent Document 1, the pattern collapses on a substrate having a fine and high aspect ratio (that is, the height of the convex pattern is higher than the width of the convex pattern). There is a problem that it cannot be sufficiently prevented.

Further, in the drying technique disclosed in Patent Documents 2 and 3, a solution in which a sublimable substance is dissolved in a solvent is supplied to the substrate, and then the solvent is selectively removed on the substrate to remove the sublimable substance on the substrate. It is necessary to deposit with.

For example, in Patent Document 3, 1,2,3-benzotriazole is used as a sublimable substance. The melting point of this substance is 95 ° C. After supplying a solution in which 1 g of 1,2,3-benzotriazole is dissolved in 20 ml of IPA (isopropyl alcohol), the substrate is heated at 50 ° C. or lower to evaporate the IPA. The sublimable substance is deposited on the surface of the substrate. At this time, if the recesses of the pattern of the substrate are not deposited in a state of being filled with the sublimable substance, there is a problem that surface tension acts on the pattern of the substrate and the collapse of the pattern cannot be prevented. This problem becomes even more pronounced as the pattern becomes finer.

Further, in the drying technique disclosed in Patent Document 4, a melt of t-butanol is supplied to the substrate to solidify t-butanol. Therefore, as in Patent Documents 2 and 3, a sublimable substance by removing a solvent is used. The above problem can be solved in that precipitation is not performed. However, even if the sublimation drying technique using t-butanol is used, it may not be possible to sufficiently prevent the collapse of the fine and high aspect ratio pattern.

The present invention has been made in view of the above problems, and provides a substrate processing apparatus and a substrate processing method capable of removing liquid adhering to the surface of a substrate while preventing the pattern formed on the surface of the substrate from collapsing. The purpose is to provide.

In order to solve the above-mentioned problems, the substrate processing apparatus according to the present invention uses a supply means for supplying a processing liquid containing a sublimable substance in a molten state to a pattern-forming surface of the substrate, and the processing liquid to form the pattern. A coagulation means for coagulating on a surface to form a coagulant and a sublimation means for sublimating the coagulant to remove it from the pattern-forming surface, and the sublimating substance contains a fluorocarbon compound. It is a feature.

According to the above configuration, for example, when a liquid is present on the pattern forming surface of the substrate, the liquid can be removed while preventing the pattern from collapsing by the principle of freeze-drying (or sublimation drying). Specifically, the supply means replaces the liquid with the treatment liquid by supplying the treatment liquid to the pattern forming surface of the substrate. Next, the coagulation means coagulates the treatment liquid to form a coagulant. Further, the sublimation means sublimates the solidified body to remove the solidified body from the pattern forming surface. The sublimation of the coagulated product is due to the fact that it is composed of a fluorocarbon compound as a sublimating substance. Since the sublimable substance containing the fluorocarbon compound changes its state from a solid to a gas without passing through a liquid, it does not exert surface tension on the pattern formed on the substrate. As a result, it is possible to prevent the pattern formed on the substrate from collapsing. Moreover, since the fluorocarbon compound, which is a sublimable substance, further suppresses the collapse of the pattern as compared with the conventional sublimable substance such as t-butanol, a fine and high aspect ratio pattern can be obtained. It is also effective for the formed substrate.

Here, the "melted state" means a state in which the sublimable substance has fluidity and is in a liquid state when it is completely or partially melted. Further, the "sublimable substance" means that a single substance, a compound or a mixture has a property of undergoing a phase transition from a solid to a gas or a gas to a solid without passing through a liquid, and the "sublimable substance" is the same. It means a substance having such sublimation property. Further, the "pattern forming surface" means a surface on which an uneven pattern is formed in an arbitrary region on the substrate regardless of whether it is a flat surface, a curved surface, or an uneven shape. The "coagulant" is a solidified liquid-state treatment liquid. For example, when the liquid existing on the substrate is mixed with the treatment liquid and coagulated by the coagulation means, the "coagulant" is used. The liquid may also be included.

In the above configuration, the fluorocarbon compound is preferably at least one of the following compounds (A) to (E).
Compound (A): A fluoroalkane having 3 to 6 carbon atoms, or at least one selected from the group consisting of a halogen group excluding a fluorine group, a hydroxyl group, an oxygen atom, a carboxyl group and a perfluoroalkyl group is bonded to the fluoroalkane. What I did;
Compound (B): Fluorocycloalkane having 3 to 6 carbon atoms, or at least one selected from the group consisting of a halogen group excluding a fluorine group, a hydroxyl group, an oxygen atom, a carboxyl group and a perfluoroalkyl group in the fluorocycloalkane. Combined;
Compound (C): Fluorobicycloalkane having 10 carbon atoms, or the fluorobicycloalkane may have a halogen group other than a fluorine group, a cycloalkyl group which may have a halogen atom, and a cycloalkyl which may have a halogen atom. At least one bonded from the group consisting of alkyl groups having a group;
Compound (D): Fluorotetracyanoquinodimethane or a product in which at least one halogen group other than a fluorine group is bonded to the fluorotetracyanoquinodimethane;
Compound (E): Fluorocyclotriphosphazene, or a compound in which at least one selected from the group consisting of a halogen group excluding a fluorine group, a phenoxy group and an alkoxy group is bonded to the fluorocyclotriphosphazene.

Further, in the above configuration, the compound (A) is preferably tetradecafluorohexane.

Further, in the above-mentioned constitution, the compound (B) is 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1,2,3,4,5-pentane. Fluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorocyclohexane, dodecafluorocyclohexane, 1,1,4-trifluorocyclohexane, 2-fluorocyclohexanol, 4,4- From the group consisting of difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid and 1,2,2,3,3,4,5,5,6,6-undecafluoro-1- (nonafluorobutyl) cyclohexane It is preferably at least one selected.

Further, in the above-mentioned composition, the compound (C) is 2- [difluoro (undecafluorocyclohexyl) methyl] -1,1,2,3,3,4,4a, 5,5,6. , 6,7,7,8,8,8a-Heptadecafluorodecahydronaphthalene is preferred.

Further, in the above configuration, the compound (D) is preferably tetrafluorotetracyanoquinodimethane.

Further, in the above composition, the compound (E) is preferably hexafluorocyclotriphosphazene.

Further, in the above configuration, the supply means supplies the treatment liquid to the pattern forming surface of the substrate under atmospheric pressure, and the coagulation means supplies the treatment liquid under atmospheric pressure. It is preferable that the substance is cooled below the freezing point of the sublimable substance. As a result, at least in the supply means and the solidification means, it is not necessary to have a pressure-resistant configuration, and the cost of the device can be reduced.

Further, in the above configuration, it is preferable that the fluorocarbon compound as the sublimating substance has sublimation property under atmospheric pressure, and the sublimation means sublimates the sublimating substance under atmospheric pressure. .. As a result, by using a fluorocarbon compound which is a sublimable substance having sublimation property under atmospheric pressure, it is not necessary to have a pressure-resistant configuration at least in the sublimation means, and the equipment cost is reduced. It can be reduced.

Further, in the above configuration, the coagulation means and the sublimation means direct an inert gas inert to at least the sublimation substance toward the pattern forming surface at a temperature equal to or lower than the freezing point of the sublimation substance. It can be used as a common gas supply means for supplying gas.

According to the above configuration, since the gas supply means supplies an inert gas having a temperature below the freezing point of the sublimable substance toward the pattern forming surface as the coagulation means, the sublimable substance is cooled and solidified. It becomes possible to make it. Further, the gas supply means can sublimate the coagulated body by supplying the inert gas to the coagulated body formed on the pattern forming surface, and can function as the sublimation means. Further, since the gas supply means can be used in combination with the solidification means and the sublimation means, the number of parts can be reduced and the equipment cost can be reduced. Since the inert gas is inactive with respect to the sublimable substance, the sublimable substance is not denatured.

Further, in the above configuration, at least one of the coagulation means and the sublimation means directs the refrigerant toward the back surface opposite to the pattern forming surface of the substrate at a temperature equal to or lower than the freezing point of the sublimable substance. Can be supplied.

According to the above configuration, in the coagulation means, the sublimable substance is cooled and solidified by supplying a refrigerant below the freezing point of the sublimable substance toward the back surface opposite to the pattern forming surface of the substrate. It becomes possible to make it. Further, in the sublimation means, the solidified body can be sublimated by supplying the refrigerant toward the back surface of the substrate. Further, when both the coagulation means and the sublimation means are configured so that the refrigerant can be supplied to the back surface of the substrate, the number of parts can be reduced and the equipment cost can be reduced.

Further, in the above configuration, the sublimation means is preferably a decompression means for depressurizing the pattern forming surface on which the solidified body is formed in an environment lower than atmospheric pressure.

By using the depressurizing means as the sublimation means, the pattern forming surface of the substrate can be placed in an environment lower than the atmospheric pressure, and the sublimable substance in the solidified body can be sublimated. Here, when the sublimable substance is sublimated and vaporized from the coagulated body, the coagulated body is deprived of heat as sublimation heat. Therefore, the solidified body is cooled. Therefore, even in a temperature environment slightly higher than the melting point of the sublimable substance, the solidified body can be maintained at a temperature lower than the melting point of the sublimable substance without separately cooling. As a result, the coagulated body can be sublimated while preventing the sublimating substance from melting in the coagulated body. Further, since it is not necessary to provide a separate cooling mechanism, the device cost and the processing cost can be reduced.

Further, in the above configuration, it is preferable to use the depressurizing means as the coagulation means. According to this configuration, since the decompression means used as the sublimation means is also used as the coagulation means, the number of parts can be reduced and the equipment cost can be reduced.

Further, in the above configuration, it is preferable that the supply means has a treatment liquid temperature adjusting unit that adjusts the temperature of the treatment liquid to a temperature equal to or higher than the melting point of the sublimable substance and lower than the boiling point. According to the above configuration, the supply means is further provided with a treatment liquid temperature adjusting unit, so that the temperature of the treatment liquid can be adjusted to a temperature equal to or higher than the melting point of the sublimable substance and lower than the boiling point. By setting the temperature of the treatment liquid to be equal to or higher than the melting point of the sublimable substance, it is possible to satisfactorily dry the liquid on the substrate while further preventing the pattern formed on the substrate from collapsing.

Further, in the above configuration, the supply means shall perform cleaning or rinsing on the pattern-forming surface of the substrate by supplying the treatment liquid as a cleaning liquid or a rinsing liquid to the pattern-forming surface of the substrate. Is preferable. According to the above configuration, the supply means uses the treatment liquid containing the sublimable substance in the molten state as the cleaning liquid and / or the rinsing liquid, and supplies the treatment liquid to the pattern forming surface of the substrate to perform the cleaning step and / or. The rinsing process can be performed. As a result, the contamination existing on the pattern-forming surface of the substrate is compared with the case where the treatment liquid is supplied after the cleaning step and / or the rinsing step, the cleaning liquid or the rinsing liquid is replaced with the treatment liquid, and freeze-drying (or sublimation drying) is performed. The number of processes can be reduced while removing substances, and the processing efficiency can be improved.

Further, in the above configuration, it is preferable to provide at least a water-repellent treatment means for treating the pattern-forming surface with water-repellent treatment before supplying the treatment liquid to the pattern-forming surface of the substrate. When the solidified body sublimates, the solidified body may exert stress on the pattern of the substrate. At this time, if the degree of sublimation of the solidified body is non-uniform, non-uniform stress is also applied to the pattern, and as a result, the pattern may collapse. Since hydroxyl groups are present on the surface of a normal pattern, when the patterns come into contact with each other due to the collapse of the pattern, the hydroxyl groups are hydrogen-bonded to each other, resulting in a state in which the patterns are attached to each other. However, in the above configuration, since the water-repellent treatment means preliminarily treats the pattern-forming surface of the substrate with water-repellent treatment, even if the patterns try to come into contact with each other, they repel each other due to repulsive force, and as a result, the patterns collapse. Can be prevented. As a result, the collapse rate of the pattern can be suppressed as compared with the case where the water repellent treatment is not performed.

In the substrate processing method of the present invention, in order to solve the above-mentioned problems, a supply step of supplying a treatment liquid containing a sublimable substance in a molten state to the pattern-forming surface of the substrate, and the treatment liquid being applied to the pattern-forming surface The sublimating substance includes a fluorocarbon compound, which comprises a coagulation step of coagulating on the above to form a coagulated body and a sublimation step of sublimating the coagulated body to remove it from the pattern forming surface.

According to the above configuration, for example, when a liquid is present on the pattern forming surface of the substrate, the liquid can be removed while preventing the pattern from collapsing by the principle of freeze-drying (or sublimation drying). Specifically, in the supply step, the treatment liquid is replaced with the treatment liquid by supplying the treatment liquid to the pattern forming surface of the substrate. Next, in the coagulation step, the treatment liquid is coagulated to form a coagulated body. Further, in the sublimation step, the solidified body is removed from the pattern forming surface by sublimating the solidified body. The sublimation of the coagulated product is due to the fact that it is composed of a fluorocarbon compound as a sublimating substance. Since the sublimable substance containing the fluorocarbon compound changes its state from a solid to a gas without passing through a liquid, it does not exert surface tension on the pattern formed on the substrate. As a result, it is possible to prevent the pattern formed on the substrate from collapsing. Moreover, since the fluorocarbon compound, which is a sublimable substance, further suppresses the collapse of the pattern as compared with the conventional sublimable substance such as t-butanol, a fine and high aspect ratio pattern can be obtained. It is also effective for the formed substrate.

In the above configuration, the fluorocarbon compound is preferably at least one of the following compounds (A) to (E).
Compound (A): A fluoroalkane having 3 to 6 carbon atoms, or at least one selected from the group consisting of a halogen group excluding a fluorine group, a hydroxyl group, an oxygen atom, a carboxyl group and a perfluoroalkyl group is bonded to the fluoroalkane. What I did;
Compound (B): Fluorocycloalkane having 3 to 6 carbon atoms, or at least one selected from the group consisting of a halogen group excluding a fluorine group, a hydroxyl group, an oxygen atom, a carboxyl group and a perfluoroalkyl group in the fluorocycloalkane. Combined;
Compound (C): Fluorobicycloalkane having 10 carbon atoms, or the fluorobicycloalkane may have a halogen group other than a fluorine group, a cycloalkyl group which may have a halogen atom, and a cycloalkyl which may have a halogen atom. At least one bonded from the group consisting of alkyl groups having a group;
Compound (D): Fluorotetracyanoquinodimethane or a product in which at least one halogen group other than a fluorine group is bonded to the fluorotetracyanoquinodimethane;
Compound (E): Fluorocyclotriphosphazene, or a compound in which at least one selected from the group consisting of a halogen group excluding a fluorine group, a phenoxy group and an alkoxy group is bonded to the fluorocyclotriphosphazene.

In the above configuration, the compound (A) is preferably tetradecafluorohexane.

Further, in the above-mentioned constitution, the compound (B) is 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1,1,2,2,3,3. , 4-Heptafluorocyclopentane, fluorocyclohexane, dodecafluorocyclohexane, 1,1,4-trifluorocyclohexane, 2-fluorocyclohexanol, 4,4-difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid and 1,2 , 2,3,3,4,4,5,5,6,6-undecafluoro-1- (nonafluorobutyl) cyclohexane is preferably at least one selected from the group.

Further, in the above-mentioned composition, the compound (C) is 2- [difluoro (undecafluorocyclohexyl) methyl] -1,1,2,3,3,4,4a, 5,5,6. , 6,7,7,8,8,8a-Heptadecafluorodecahydronaphthalene is preferred.

Further, in the above configuration, the compound (D) is preferably tetrafluorotetracyanoquinodimethane.

Further, in the above composition, the compound (E) is preferably hexafluorocyclotriphosphazene.

The present invention exerts the following effects by the means described above.
That is, according to the present invention, for example, when a liquid is present on the pattern-forming surface of the substrate, the liquid is replaced with a treatment liquid containing a fluorocarbon compound as a sublimable substance, and then the fluorocarbon. The compound is coagulated to form a coagulated product, and then the coagulated product is sublimated. Therefore, surface tension is not applied to the pattern formed on the substrate, and the pattern can be prevented from collapsing. Moreover, since the fluorocarbon compound which is a sublimable substance further suppresses the collapse of the pattern as compared with the conventional sublimable substance such as t-butanol, the substrate processing apparatus of the present invention has a pattern. It is extremely suitable for drying the liquid on the substrate on which the above is formed.

It is explanatory drawing which shows the outline of the substrate processing apparatus which concerns on 1st Embodiment of this invention. It is a schematic plan view which shows the substrate processing apparatus. It is explanatory drawing which shows the schematic structure of the control unit in the said substrate processing apparatus. FIG. 4A is a block diagram showing a schematic configuration of a drying auxiliary liquid storage unit in the substrate processing apparatus, and FIG. 4B is an explanatory diagram showing a specific configuration of the drying auxiliary liquid storage unit. .. It is a block diagram which shows the schematic structure of the gas tank in the said substrate processing apparatus. It is a flowchart which shows the substrate processing method using the said substrate processing apparatus. It is a figure which shows the state of the substrate in each step of the substrate processing method. It is a flowchart which shows the substrate processing method which concerns on 2nd Embodiment of this invention. It is a figure which shows the state of the substrate in each step of the substrate processing method which concerns on the 2nd Embodiment. It is explanatory drawing which shows the outline of the substrate processing apparatus which concerns on 3rd Embodiment of this invention. It is a schematic plan view which shows the substrate processing apparatus. It is a flowchart which shows the substrate processing method using the said substrate processing apparatus. It is a figure which shows the state of the substrate in each step of the substrate processing method which concerns on the 3rd Embodiment. It is a figure which shows the state of the substrate in each step of the substrate processing method which concerns on 4th Embodiment. 6 is an SEM image showing a pattern-forming surface of an untreated silicon substrate used in Examples and Comparative Examples of the present invention. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Example 1 of the present invention. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Example 2 of the present invention. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Example 3 of the present invention. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Comparative Example 1. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Example 4 of the present invention. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Example 5 of the present invention. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Comparative Example 2. 6 is an SEM image showing another pattern-forming surface of the silicon substrate subjected to the substrate treatment according to Comparative Example 2. 6 is an SEM image showing a pattern-forming surface of a silicon substrate subjected to substrate treatment according to Example 6 of the present invention. 6 is an SEM image showing a pattern forming surface when the silicon substrate used in Example 6 is subjected to a substrate treatment without performing a water repellent treatment step.

(First Embodiment)
The first embodiment of the present invention will be described below.
FIG. 1 is an explanatory diagram showing an outline of the substrate processing apparatus 1 according to the present embodiment. FIG. 2 is a schematic plan view showing the internal configuration of the substrate processing device 1. In each figure, the XYZ orthogonal coordinate axes are appropriately displayed in order to clarify the directional relationship of the illustrated ones. In FIGS. 1 and 2, the XY plane represents a horizontal plane, and the 10Z direction represents a vertically upward direction.

The substrate processing device 1 can be used, for example, for processing various substrates. The "substrate" includes a semiconductor substrate, a glass substrate for a photomask, a glass substrate for a liquid crystal display, a glass substrate for a plasma display, a substrate for a FED (Field Emission Display), an optical disk substrate, a magnetic disk substrate, and a magneto-optical disk. Refers to various substrates such as substrates. In the present embodiment, a case where the substrate processing apparatus 1 is used for processing a semiconductor substrate (hereinafter, referred to as “substrate W”) will be described as an example.

Further, as the substrate W, an example is a substrate W in which a circuit pattern or the like (hereinafter referred to as “pattern”) is formed only on one main surface. Here, the pattern-forming surface (main surface) on which the pattern is formed is referred to as "front surface", and the main surface on which the pattern is not formed on the opposite side is referred to as "back surface". Further, the surface of the substrate facing downward is referred to as "lower surface", and the surface of the substrate facing upward is referred to as "upper surface". In the following, the upper surface will be described as the surface.

The substrate processing apparatus 1 is a single-wafer type substrate processing apparatus used for a cleaning treatment (including a rinsing treatment) for removing contaminants such as particles adhering to the substrate W and a drying treatment after the cleaning treatment. Is. Although FIGS. 1 and 2 show only the parts used for the drying treatment and do not show the cleaning nozzles and the like used for the cleaning treatment, the substrate processing apparatus 1 may include the nozzles and the like. ..

<1-1 Configuration of board processing equipment>
First, the configuration of the substrate processing apparatus 1 will be described with reference to FIGS. 1 and 2.
The substrate processing device 1 is held by a chamber 11 which is a container for accommodating the substrate W, a substrate holding means 51 for holding the substrate W, a control unit 13 for controlling each part of the substrate processing device 1, and a substrate holding means 51. The processing liquid supply means (supply means) 21 for supplying the treatment liquid as the drying auxiliary liquid to the substrate W, the IPA supply means 31 for supplying IPA to the substrate W held by the substrate holding means 51, and the substrate holding means 51. IPA or drying that is supplied to the gas supply means 41 (coagulation means, sublimation means) that supplies gas to the substrate W held by the substrate W and is supplied to the substrate W held by the substrate holding means 51 and discharged to the outside of the circumferential portion of the substrate W. At least a shatterproof cup 12 for collecting auxiliary liquid and the like, a swivel drive unit 14 for independently swiveling and driving each arm described later in each part of the substrate processing device 1, and a decompression means 71 for depressurizing the inside of the chamber 11 are provided. .. Further, the substrate processing device 1 includes a substrate loading / unloading means, a chuck pin opening / closing mechanism, and a wet cleaning means (none of which is shown). Each part of the substrate processing apparatus 1 will be described below.

The substrate holding means 51 includes a rotation driving unit 52, a spin base 53, and a chuck pin 54. The spin base 53 has a plane size slightly larger than that of the substrate W. A plurality of chuck pins 54 for gripping the peripheral edge of the substrate W are erected in the vicinity of the peripheral edge of the spin base 53. The number of chuck pins 54 to be installed is not particularly limited, but it is preferable to provide at least three chuck pins 54 in order to reliably hold the circular substrate W. In this embodiment, three spin bases 53 are arranged at equal intervals along the peripheral edge of the spin base 53 (see FIG. 2). Each chuck pin 54 includes a substrate support pin that supports the peripheral edge of the substrate W from below, and a substrate holding pin that presses the outer peripheral end surface of the substrate W supported by the substrate support pin to hold the substrate W.

Each chuck pin 54 can be switched between a pressing state in which the substrate holding pin presses the outer peripheral end surface of the substrate W and a released state in which the substrate holding pin separates from the outer peripheral end surface of the substrate W, so that the entire device can be switched. The state switching is executed according to the operation command from the control unit 13 to be controlled.

More specifically, when the substrate W is carried in and out of the spin base 53, each chuck pin 54 is released, and when the substrate W is subjected to the substrate treatment from the cleaning treatment to the sublimation treatment described later. , Each chuck pin 54 is put into a pressed state. When the chuck pin 54 is in the pressed state, the chuck pin 54 grips the peripheral edge portion of the substrate W, and the substrate W is held in a horizontal posture (XY surface) at a predetermined distance from the spin base 53. As a result, the substrate W is held horizontally with its surface Wf facing upward.

As described above, in the present embodiment, the substrate W is held by the spin base 53 and the chuck pin 54, but the substrate holding method is not limited to this. For example, the back surface Wb of the substrate W may be held by a suction method such as a spin chuck.

The spin base 53 is connected to the rotation drive unit 52. The rotation drive unit 52 rotates around the axis Al along the Z direction according to the operation command of the control unit 13. The rotation drive unit 52 is composed of a known belt, a motor, and a rotation shaft. When the rotation drive unit 52 rotates around the shaft Al, the substrate W held by the chuck pin 54 above the spin base 53 rotates around the shaft Al together with the spin base 53.

Next, the processing liquid supply means 21 (supply means) will be described.
The processing liquid supply means 21 is a unit that supplies the drying auxiliary liquid to the pattern forming surface of the substrate W, and as shown in FIG. 1, the nozzle 22, the arm 23, the swivel shaft 24, the pipe 25, and the valve 26. And at least a treatment liquid storage unit 27.

As shown in FIGS. 4A and 4B, the treatment liquid storage unit 27 includes a treatment liquid storage tank 271, a stirring unit 277 that agitates the drying auxiliary liquid in the treatment liquid storage tank 271, and a treatment liquid. At least a pressurizing unit 274 that pressurizes the storage tank 271 and sends out the drying auxiliary liquid, and a temperature adjusting unit 272 that heats the drying auxiliary liquid in the processing liquid storage tank 271 are provided. Note that FIG. 4A is a block diagram showing a schematic configuration of the treatment liquid storage unit 27, and FIG. 4B is an explanatory diagram showing a specific configuration of the treatment liquid storage unit 27.

The stirring unit 277 includes a rotating unit 279 that agitates the drying auxiliary liquid in the processing liquid storage tank 271 and a stirring control unit 278 that controls the rotation of the rotating unit 279. The stirring control unit 278 is electrically connected to the control unit 13. The rotating unit 279 is provided with a propeller-shaped stirring blade at the tip of the rotating shaft (the lower end of the rotating unit 279 in FIG. 5), the control unit 13 issues an operation command to the stirring control unit 278, and the rotating unit 279 sends an operation command. By rotating, the stirring blade stirs the drying auxiliary liquid, and the concentration and temperature of the drying auxiliary substance and the like in the drying auxiliary liquid are made uniform.

Further, the method for making the concentration and temperature of the drying auxiliary liquid in the treatment liquid storage tank 271 uniform is not limited to the above-mentioned method, and known methods such as a method of providing a separate circulation pump to circulate the drying auxiliary liquid are known. The method can be used.

The pressurizing unit 274 is composed of a nitrogen gas tank 275, which is a supply source of the gas for pressurizing the inside of the processing liquid storage tank 271, a pump 276 for pressurizing the nitrogen gas, and a pipe 273. The nitrogen gas tank 275 is connected to the treatment liquid storage tank 271 by a pipe 273, and a pump 276 is inserted in the pipe 273.

The temperature adjusting unit 272 is electrically connected to the control unit 13 and heats the drying auxiliary liquid stored in the processing liquid storage tank 271 according to the operation command of the control unit 13 to adjust the temperature. The temperature may be adjusted so that the temperature of the drying auxiliary liquid is equal to or higher than the melting point of the drying auxiliary substance (sublimable substance, which will be described in detail later) contained in the drying auxiliary liquid. As a result, the thawed state of the drying aid can be maintained. The upper limit of the temperature adjustment is preferably a temperature lower than the boiling point. Further, the temperature adjusting unit 272 is not particularly limited, and for example, a known temperature adjusting mechanism such as a resistance heating heater, a Perche element, or a pipe through which temperature-controlled water is passed can be used. In the present embodiment, the temperature adjusting unit 272 has an arbitrary configuration. For example, when the installation environment of the substrate processing apparatus 1 is an environment higher than the melting point of the sublimable substance, the molten state of the sublimable substance can be maintained, so that heating of the drying auxiliary liquid becomes unnecessary. .. As a result, the temperature adjusting unit 272 can be omitted.

Return to FIG. The treatment liquid storage unit 27 (more specifically, the treatment liquid storage tank 271) is connected to the nozzle 22 via a pipe 25, and a valve 26 is inserted in the middle of the path of the pipe 25.

A barometric pressure sensor (not shown) is provided in the processing liquid storage tank 271 and is electrically connected to the control unit 13. The control unit 13 maintains the pressure in the processing liquid storage tank 271 at a predetermined pressure higher than the atmospheric pressure by controlling the operation of the pump 276 based on the value detected by the pressure sensor. On the other hand, the valve 26 is also electrically connected to the control unit 13 and is normally closed. The opening and closing of the valve 26 is also controlled by the operation command of the control unit 13. Then, when the control unit 13 issues an operation command to the processing liquid supply means 21 and opens the valve 26, the drying auxiliary liquid is pressure-fed from the pressurized processing liquid storage tank 271 and the nozzle 22 is passed through the pipe 25. Is discharged from. Thereby, the drying auxiliary liquid can be supplied to the surface Wf of the substrate W. The treatment liquid storage tank 271 is preferably airtight because the drying auxiliary liquid is pressure-fed using the pressure of nitrogen gas as described above.

The nozzle 22 is attached to the tip of the horizontally extended arm 23 and is arranged above the spin base 53. The rear end portion of the arm 23 is rotatably supported around the shaft J1 by a swivel shaft 24 extending in the Z direction, and the swivel shaft 24 is fixed in the chamber 11. The arm 23 is connected to the swivel drive unit 14 via the swivel shaft 24. The swivel drive unit 14 is electrically connected to the control unit 13 and rotates the arm 23 around the shaft J1 in response to an operation command from the control unit 13. As the arm 23 rotates, the nozzle 22 also moves.

As shown by the solid line in FIG. 2, the nozzle 22 is usually arranged at the retracted position P1 outside the peripheral edge of the substrate W and outside the shatterproof cup 12. When the arm 23 rotates according to the operation command of the control unit 13, the nozzle 22 moves along the path of the arrow AR1 and is arranged at a position above the central portion (axis A1 or its vicinity) of the surface Wf of the substrate W.

Return to FIG. Next, the IPA supply means 31 will be described. The IPA supply means 31 is a unit that supplies IPA (isopropyl alcohol) to the substrate W, and includes a nozzle 32, an arm 33, a swivel shaft 34, a pipe 35, a valve 36, and an IPA tank 37. Be prepared.

The IPA tank 37 is connected to the nozzle 32 via a pipe 35, and a valve 36 is inserted in the middle of the path of the pipe 35. IPA is stored in the IPA tank 37, the IPA in the IPA tank 37 is pressurized by a pump (not shown), and the IPA is sent from the pipe 35 toward the nozzle 32.

The valve 36 is electrically connected to the control unit 13 and is normally closed. The opening and closing of the valve 36 is controlled by the operation command of the control unit 13. When the valve 36 is opened by the operation command of the control unit 13, IPA is supplied from the nozzle 32 to the surface Wf of the substrate W through the pipe 35.

The nozzle 32 is attached to the tip of a horizontally extended arm 33 and is arranged above the spin base 53. The rear end portion of the arm 33 is rotatably supported around the shaft J2 by a swivel shaft 34 extending in the Z direction, and the swivel shaft 34 is fixed in the chamber 11. The arm 33 is connected to the swivel drive unit 14 via the swivel shaft 34. The swivel drive unit 14 is electrically connected to the control unit 13 and rotates the arm 33 around the shaft J2 in response to an operation command from the control unit 13. As the arm 33 rotates, the nozzle 32 also moves.

As shown by a solid line in FIG. 2, the nozzle 32 is usually arranged at the retracted position P2 outside the peripheral edge of the substrate W and outside the shatterproof cup 12. When the arm 33 rotates according to the operation command of the control unit 13, the nozzle 32 moves along the path of the arrow AR2 and is arranged at a position above the central portion (axis A1 or its vicinity) of the surface Wf of the substrate W.

In the present embodiment, IPA is used in the IPA supply means 31, but the present invention may be any liquid as long as it is soluble in a drying auxiliary substance and deionized water (DIW: Deionized Water). Not limited to. As an alternative to IPA in this embodiment, methanol, ethanol, acetone, benzene, carbon tetrachloride, chloroform, hexane, decalin, tetralin, acetic acid, cyclohexanol, ether, hydrofluoro ether, etc. are used. Can be mentioned.

Return to FIG. Next, the gas supply means 41 will be described. The gas supply means 41 is a unit that supplies gas to the substrate W, and includes a nozzle 42, an arm 43, a swivel shaft 44, a pipe 45, a valve 46, and a gas tank 47.

FIG. 5 is a block diagram showing a schematic configuration of the gas tank 47. The gas tank 47 includes a gas storage unit 471 for storing gas and a gas temperature adjusting unit 472 for adjusting the temperature of the gas stored in the gas storage unit 471. The gas temperature adjusting unit 472 is electrically connected to the control unit 13, and heats or cools the gas stored in the gas storage unit 471 according to the operation command of the control unit 13 to adjust the temperature. The temperature may be adjusted so that the gas stored in the gas storage unit 471 has a low temperature equal to or lower than the freezing point of the drying auxiliary substance.

The gas temperature adjusting unit 472 is not particularly limited, and for example, a known temperature adjusting mechanism such as a Perche element or a pipe through which temperature-controlled water is passed can be used.

Return to FIG. The gas tank 47 (more specifically, the gas storage unit 471) is connected to the nozzle 42 via a pipe 45, and a valve 46 is inserted in the middle of the path of the pipe 45. The gas in the gas tank 47 is pressurized by a pressurizing means (not shown) and sent to the pipe 45. Since the pressurizing means can be realized by compressing and storing the gas in the gas tank 47 in addition to pressurizing by a pump or the like, any pressurizing means may be used.

The valve 46 is electrically connected to the control unit 13 and is normally closed. The opening and closing of the valve 46 is controlled by the operation command of the control unit 13. When the valve 46 is opened by the operation command of the control unit 13, gas is supplied from the nozzle 42 to the surface Wf of the substrate W through the pipe 45.

The nozzle 42 is attached to the tip of a horizontally extended arm 43 and is arranged above the spin base 53. The rear end portion of the arm 43 is rotatably supported around the shaft J3 by a swivel shaft 44 extending in the Z direction, and the swivel shaft 44 is fixed in the chamber 11. The arm 43 is connected to the swivel drive unit 14 via the swivel shaft 44. The swivel drive unit 14 is electrically connected to the control unit 13 and rotates the arm 43 around the shaft J3 in response to an operation command from the control unit 13. As the arm 43 rotates, the nozzle 42 also moves.

As shown by a solid line in FIG. 2, the nozzle 42 is usually arranged at the retracted position P3 outside the peripheral edge of the substrate W and outside the shatterproof cup 12. When the arm 43 is rotated by the operation command of the control unit 13, the nozzle 42 moves along the path of the arrow AR3 and is arranged at a position above the central portion (axis A1 or its vicinity) of the surface Wf of the substrate W. The state in which the nozzle 42 is arranged above the central portion of the surface Wf is shown by a dotted line in FIG.

In the gas storage unit 471, at least an inert gas that is inactive with respect to the drying auxiliary substance, more specifically, nitrogen gas is stored. Further, the stored nitrogen gas is adjusted to a temperature equal to or lower than the freezing point of the drying auxiliary substance in the gas temperature adjusting unit 472. The temperature of the nitrogen gas is not particularly limited as long as it is a temperature equal to or lower than the freezing point of the drying auxiliary substance, but is usually set within the range of 0 degrees Celsius or more and 15 degrees Celsius or less. By setting the temperature of the nitrogen gas to 0 degrees Celsius or higher, it is possible to prevent the water vapor existing inside the chamber 11 from solidifying and adhering to the surface Wf of the substrate W, thereby preventing an adverse effect on the substrate W. be able to.

The nitrogen gas used in the first embodiment is preferably a dry gas having a dew point of 0 degrees Celsius or less. When the nitrogen gas is sprayed onto the coagulant in an atmospheric pressure environment, the drying aid in the coagulant sublimates into the nitrogen gas. Since the nitrogen gas continues to be supplied to the coagulant, the partial pressure of the gaseous drying aid generated by sublimation in the nitrogen gas is higher than the saturated vapor pressure of the gaseous drying aid at the temperature of the nitrogen gas. It is kept low and at least on the surface of the solidified material is filled with a gaseous drying aid in an atmosphere present below its saturated vapor pressure.

Further, in the present embodiment, nitrogen gas is used as the gas supplied by the gas supply means 41, but the embodiment of the present invention is not limited to this as long as it is a gas inactive with respect to the drying auxiliary substance. In the first embodiment, examples of the gas as an alternative to the nitrogen gas include argon gas, helium gas or air (a gas having a nitrogen gas concentration of 80% and an oxygen gas concentration of 20%). Alternatively, it may be a mixed gas in which these plurality of types of gases are mixed.

Return to FIG. The decompression means 71 is a means for decompressing the inside of the chamber 11 to an environment lower than the atmospheric pressure, and includes an exhaust pump 72, a pipe 73, and a valve 74. The exhaust pump 72 is a known pump that is connected to the chamber 11 via a pipe 73 and applies pressure to the gas. The exhaust pump 72 is electrically connected to the control unit 13 and is normally in a stopped state. The drive of the exhaust pump 72 is controlled by the operation command of the control unit 13. A valve 74 is inserted into the pipe 73. The valve 74 is electrically connected to the control unit 13 and is normally closed. The opening and closing of the valve 74 is controlled by the operation command of the control unit 13.

When the exhaust pump 72 is driven by the operation command of the control unit 13 and the valve 74 is opened, the gas existing inside the chamber 11 is exhausted to the outside of the chamber 11 through the pipe 73 by the exhaust pump 72. ..

The shatterproof cup 12 is provided so as to surround the spin base 53. The shatterproof cup 12 is connected to an elevating drive mechanism (not shown) and can be elevated in the Z direction. When supplying the drying auxiliary liquid or IPA to the substrate W, the shatterproof cup 12 is positioned at a predetermined position as shown in FIG. 1 by the elevating drive mechanism, and the substrate W held by the chuck pin 54 is moved from the side position. surround. As a result, it is possible to collect the drying auxiliary liquid and the liquid such as IPA scattered from the substrate W and the spin base 53.

FIG. 3 is a schematic view showing the configuration of the control unit 13. The control unit 13 is electrically connected to each part of the substrate processing device 1 (see FIG. 1) and controls the operation of each part. The control unit 13 is composed of a computer having an arithmetic processing unit 15 and a memory 17. As the arithmetic processing unit 15, a CPU that performs various arithmetic processes is used. Further, the memory 17 includes a ROM which is a read-only memory for storing a basic program, a RAM which is a read / write memory for storing various information, and a magnetic disk for storing control software, data, and the like. In the magnetic disk, the substrate processing conditions according to the substrate W are stored in advance as the substrate processing program 19 (also called Lempi), and the CPU reads the contents into the RAM, and the substrate processing program 19 read into the RAM. The CPU controls each part of the substrate processing device 1 according to the contents.

<1-2 Drying aid>
Next, the drying auxiliary liquid used in this embodiment will be described below.
The drying auxiliary liquid of the present embodiment is a treatment liquid containing a drying auxiliary substance (sublimable substance) in a molten state, and is the drying treatment in the drying treatment for removing the liquid existing on the pattern forming surface of the substrate. It fulfills the function of assisting.

The sublimable substance has a property of undergoing a phase transition from a solid to a gas or from a gas to a solid without passing through a liquid, and specifically, a fluorocarbon compound is used. A fluorocarbon compound is a compound in which a fluorine group is bonded to a carbon compound as a substituent. In the present embodiment, the fluorocarbon compound is preferably at least one of the following compounds (A) to (E). These compounds can be used alone or in combination of two or more.

Compound (A): Fluoroalkane having 3 to 6 carbon atoms or a substance having a substituent bonded to the fluoroalkane Compound (B): Fluorocycloalkane having 3 to 6 carbon atoms or a substituent bonded to the fluorocycloalkane. Compound (C): Fluorobicycloalkane having 10 carbon atoms or a substance in which a substituent is bonded to the fluorobicycloalkane Compound (D): Fluorotetracyanoquinodimethane or a substituent on the fluorotetracyanoquinodimethane Compound (E): Fluorocyclotriphosphazene or a substance in which a substituent is bonded to the fluorocyclotriphosphazene.

[Compound (A)]
Examples of the compound (A) include fluoroalkanes having 3 to 6 carbon atoms represented by the following general formula (1).

More specifically, the fluoroalkanes having 3 carbon atoms include, for example, CF ₃ CF ₂ CF ₃ , CHF ₂ CF ₂ CF ₃ , CH ₂ FCF ₂ CF ₃ , CH ₃ CF ₂ CH ₃ , CHF ₂ CF ₂ CH. _{3, CH 2 FCF 2 CH 3} , CH 2 FCF 2 CH 2 F, CHF 2 CF 2 CHF 2, CF 3 CHFCF 3, CH 2 FCHFCF 3, CHF 2 CHFCF 3, CH 2 FCHFCH 2 F, CHF 2 CHFCHF 2, CH ₃ CHFCH ₃ , CH ₂ FCHFCH ₃ , CHF ₂ CHFCH ₃ , CF ₃ CH ₂ CF ₃ , CH ₂ FCH ₂ CF ₃ , CHF ₂ CH ₂ CF ₃ , CH ₂ FCH ₂ CH ₂ F, CH ₂ FCH ₂ CHF ₂ , CHF ₂ CH ₂ CHF ₂ , CH ₃ CH ₂ CH ₂ F, CH ₃ CH ₂ CHF _{2 and the} like.

Examples of fluoroalkanes having 4 carbon atoms include CF ₃ (CF ₂ ) ₂ CF ₃ , CF ₃ (CF ₂ ) ₂ CH ₂ F, CF ₃ CF ₂ CH ₂ CF ₃ , CHF ₂ (CF ₂ ) _2. CHF ₂ , CHF ₂ CHFCF ₂ CHF ₂ , CF ₃ CH ₂ CF ₂ CHF ₂ , CF ₃ CHFCH ₂ CF ₃ , CHF ₂ CHF CHFCHF ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CF ₂ CH ₂ CH _{3 3} CHFCF ₂ CH ₃ , CHF ₂ CH ₂ CF ₂ CH _{3 and the} like can be mentioned.

Examples of fluoroalkanes having 5 carbon atoms include CF ₃ (CF ₂ ) ₃ CF ₃ , CF ₃ CF ₂ CF ₂ CHFCF ₃ , CHF ₂ (CF ₂ ) ₃ CF ₃ , CHF ₂ (CF ₂ ) ₃ CHF ₂ , CF ₃ CH (CF ₃ ) CH ₂ CF ₃ , CF ₃ CHFCF ₂ CH ₂ CF ₃ , CF ₃ CF (CF ₃ ) CH ₂ CHF ₂ , CHF ₂ CHFCF ₂ CHFC _{CHF 2} , CF ₃ CH ₂ CF ₂ CH ₂ CF ₃ , CHF ₂ (CF ₂ ) ₂ CHFCH ₃ , CHF ₂ CH ₂ CF ₂ CH ₂ CHF ₂ , CF ₃ (CH ₂ ) ₃ CF ₃ , CF ₃ CHFCHFCF ₂ CF _{3 and the} like.

Examples of fluoroalkanes having 6 carbon atoms include CF ₃ (CF ₂ ) ₄ CF ₃ , CF ₃ (CF ₂ ) ₄ CHF ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ F, CF ₃ CH (CF ₃ ) CHFCF. ₂ CF ₃ , CHF ₂ (CF ₂ ) ₄ CHF ₂ , CF ₃ CF ₂ CH ₂ CH (CF ₃ ) CF ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ CF ₂ CF ₃ , CF ₃ CH ₂ (CF ₂ ) ₂ CH ₂ CF ₃ , CF ₃ (CF ₂ ) ₃ CH ₂ CF ₃ , CF ₃ CH (CF ₃ ) (CH ₂ ) ₂ CF ₃ , CHF ₂ CF ₂ (CH ₂ ) ₂ CF ₂ CHF ₂ , CF ₃ ( CF ₂ ) ₂ (CH ₂ ) ₂ CH _{3 and the} like can be mentioned.

Further, as the compound (A), a compound in which a substituent is bonded to the fluoroalkane having 3 to 6 carbon atoms can be mentioned. The substituent is at least selected from the group consisting of a halogen group excluding a fluorine group (specifically, a chlorine group, a bromine group, an iodine group), a hydroxyl group, an oxygen atom, an alkyl group, a carboxyl group and a perfluoroalkyl group. One type can be mentioned.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like.

The perfluoroalkyl group is not particularly limited, and examples thereof include a saturated perfluoroalkyl group and an unsaturated perfluoroalkyl group. Further, the perfluoroalkyl group may have either a linear structure or a branched structure. More specifically, the perfluoroalkyl group includes, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, a perfluoro-n-butyl group, and a perfluoro-. sec-butyl group, perfluoro-tert-butyl group, perfluoro-n-amyl group, perfluoro-sec-amyl group, perfluoro-tert-amyl group, perfluoroisoamyl group, perfluoro-n-hexyl group, Perfluoroisohexyl group, perfluoroneohexyl group, perfluoro-n-heptyl group, perfluoroisoheptyl group, perfluoroneoheptyl group, perfluoro-n-octyl group, perfluoroisooctyl group, perfluoroneooctyl group Group, perfluoro-n-nonyl group, perfluoroneononyl group, perfluoroisononyl group, perfluoro-n-decyl group, perfluoroisodecyl group, perfluoroneodecyl group, perfluoro-sec-decyl group, Examples thereof include a perfluoro-tert-decyl group.

[Compound (B)]
Examples of the compound (B) include fluorocycloalkanes having 3 to 6 carbon atoms represented by the following general formula (2).

More specifically, examples of the fluorocycloalkane having 3 to 6 carbon atoms include monofluorocyclohexane, dodecafluorocyclohexane, 1,1,4-trifluorocyclohexane, 1,1,2,2-tetrafluorocyclobutane, and the like. 1,1,2,2,3-pentafluorocyclobutane, 1,2,2,3,3,4-hexafluorocyclobutane, 1,1,2,2,3,3-hexafluorocyclobutane, 1,1, 2,2,3,3-hexafluorocyclobutane, 1,1,2,2,3,4-hexafluorocyclobutane, 1,1,2,2,3,3-hexafluorocyclopentane, 1,1,2 , 2,3,4-hexafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3,4,5-heptafluorocyclopentane, 1,1,2,2,3,3,4,4-octafluorocyclopentane, 1,1,2,2,3,3,4,5-octafluorocyclopentane, 1,1,2,2 3,3,4,5-Octafluorocyclopentane, 1,1,2,2,3,4,5,6-octafluorocyclohexane, 1,1,2,2,3,3,4,5-octa Fluorocyclohexane, 1,1,2,2,3,3,4,4-octafluorocyclocyclohexane, 1,1,2,2,3,3,4,5-octafluorocyclocyclohexane, 1,1,2 , 2,3,4,4,5,6-nonafluorocyclohexane, 1,1,2,2,3,3,4,5-nonafluorocyclocyclohexane, 1,1,2,2,3 3,4,5,6-Nonafluorocyclocyclohexane, 1,1,2,2,3,3,4,5,6-decafluorocyclohexane, 1,1,2,2,3,3,4 , 4,5,6-decafluorocyclohexane, 1,1,2,2,3,3,4,5,5-decafluorocyclocyclohexane, 1,1,2,2,3,3,4 Examples thereof include 4,5,6-decafluorocyclocyclohexane, perfluorocyclopropane, perfluorocyclobutane, perfluorocyclopentane, and perfluorocyclohexane.

Further, as the compound (B), a compound in which a substituent is bonded to the fluorocycloalkane having 3 to 6 carbon atoms can be mentioned. The substituent is at least selected from the group consisting of a halogen group excluding a fluorine group (specifically, a chlorine group, a bromine group, an iodine group), a hydroxyl group, an oxygen atom, an alkyl group, a carboxyl group and a perfluoroalkyl group. One type can be mentioned. The alkyl group and the perfluoroalkyl group are not particularly limited, and examples thereof include the same as those described in the compound (A).

Specific examples of the compound (B) in which a substituent is bonded to the fluorocycloalkane having 3 to 6 carbon atoms include, for example, 1,2,2,3,3-tetrafluoro-1-trifluoromethylcyclobutane, 1, 2,4,4-Tetrafluoro-1-trifluoromethylcyclobutane, 2,2,3,3-7 tetrafluoro-1-trifluoromethylcyclobutane, 1,2,2-trifluoro-1-trimethylcyclobutane, 1 , 4,4,5,5-pentafluoro-1,2,2,3,3-pentamethylcyclopentane, 1,2,5,5-tetraflu-1,2-dimethylcyclopentane, 3,3,4 , 4,5,5,6,6-octaflu-1,2-dimethylcyclohexane, 1,1,2,2-tetrachloro-3,3,4,5-tetrafluorocyclobutane, 2-fluorocyclohexanol, 4 , 4-Difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid, 1,2,2,3,3,4,5,5,6,6-undecafluoro-1- (nonafluorobutyl) cyclohexane, Perfluoromethylcyclopropane, perfluorodimethylcyclopropane, perfluorotrimethylcyclopropane, perfluoromethylcyclobutane, perfluorodimethylcyclobutane, perfluorotrimethylcyclobutane, perfluoromethylcyclopentane, perfluorodimethylcyclopentane, perfluorotrimethylcyclopentane , Perfluoromethylcyclohexane, perfluorodimethylcyclohexane, perfluorotrimethylcyclohexane and the like.

[Compound (C)]
Examples of the fluorobicycloalkane having 10 carbon atoms in the compound (C) include fluorobicyclo [4.4.0] decane, fluorobicyclo [3.3.2] decane, and perfluorobicyclo [4.4.0]. Decane, perfluorobicyclo [3.3.2] decane and the like can be mentioned.

Further, as the compound (C), a compound (C) in which a substituent is bonded to the fluorobicycloalkane having 10 carbon atoms can be mentioned. As the substituent, a halogen group other than a fluorine group (specifically, a chlorine group, a bromine group, an iodine group), a cycloalkyl group which may have a halogen atom, or a cyclo which may have a halogen atom. An alkyl group having an alkyl group can be mentioned.

In the cycloalkyl group which may have a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The cycloalkyl group which may have a halogen atom includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a perfluorocyclopropyl group, a perfluorocyclobutyl group, a perfluorocyclopentyl group and a perfluorocyclohexyl. Examples include a group, a perfluorocycloheptyl group and the like.

Among the alkyl groups having a cycloalkyl group which may have a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, among the alkyl groups having a cycloalkyl group which may have a halogen atom, the cycloalkyl group which may have a halogen atom includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. , Perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocycloheptyl group and the like. Specific examples of the alkyl group having a cycloalkyl group which may have a halogen atom include a difluoro (undecafluorocyclohexyl) methyl group and the like.

Specific examples of the compound (C) in which a substituent is bonded to the fluorobicycloalkane having 10 carbon atoms include, for example, 2- [difluoro (undecafluorocyclohexyl) methyl] -1,1,2,3,3,4. , 4,4a, 5,5,6,6,7,7,8,8,8a-Heptadecafluorodecahydronaphthalene and the like.

[Compound (D)]
Examples of the fluorotetracyanoquinodimethane in the compound (D) include tetrafluorotetracyanoquinodimethane.

Further, as the compound (D), at least one halogen group (specifically, a chlorine group, a bromine group, an iodine group) other than a fluorine group is bonded to the fluorotetracyanoquinodimethane.

[Compound (E)]
Examples of the fluorocyclotriphosphazene in the compound (E) include hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, decafluorocyclopentaphosphazene, and dodecafluorocyclohexaphosphazene.

Further, as the compound (E), a compound in which a substituent is bonded to the fluorocyclotriphosphazene can also be mentioned. Examples of the substituent include a halogen group (chlorine group, bromine group, iodine group) excluding a fluorine group, a phenoxy group, an alkoxy group (−OR group) and the like. Examples of R in the alkoxy group include an alkyl group, a fluoroalkyl group, an aromatic group and the like. Further, examples of the R include an alkyl group such as a methyl group and an ethyl group, a fluoroalkyl group such as a trifluoromethyl group, and an aromatic group such as a phenyl group.

Specific examples of the compound (E) in which the substituent is bonded to the fluorocyclotriphosphazene include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, and hexa. Examples thereof include phenoxycyclotriphosphazene.

The drying auxiliary liquid may consist only of a sublimating substance in a melted state, but may further contain an organic solvent. In this case, the content of the sublimating substance is preferably 60% by mass or more, more preferably 95% by mass or more, based on the total mass of the drying auxiliary liquid. The organic solvent is not particularly limited as long as it is compatible with the sublimable substance in the molten state. Specifically, for example, alcohols and the like can be mentioned.

<1-3 Substrate processing method>
Next, the substrate processing method using the substrate processing apparatus 1 of the present embodiment will be described below with reference to FIGS. 6 and 7. FIG. 6 is a flowchart showing the operation of the substrate processing device 1 according to the first embodiment. FIG. 7 is a schematic view showing the state of the substrate W in each step of FIG. An uneven pattern Wp is formed on the substrate W by the previous step. The pattern Wp includes a convex portion Wp1 and a concave portion Wp2. In the present embodiment, the convex portion Wp1 has a height in the range of 100 to 600 nm and a width in the range of 10 to 50 nm. Further, the shortest distance (the shortest width of the concave portion Wp2) between the two adjacent convex portions Wp1 is in the range of 10 to 50 nm. The aspect ratio of the convex portion Wp1, that is, the value obtained by dividing the height by the width (height / width) is 10 to 20.

Unless otherwise specified, each of FIGS. 7 (a) to 7 (e) is processed in an atmospheric pressure environment. Here, the atmospheric pressure environment refers to an environment of 0.7 atm or more and 1.3 atm or less, centered on the standard atmospheric pressure (1 atm, 1013 hPa). In particular, when the substrate processing apparatus 1 is arranged in a clean room where the pressure is positive, the environment of the surface Wf of the substrate W becomes higher than 1 atm.

See FIG. First, the operator instructs the board processing program 19 according to the predetermined board W to be executed. After that, in preparation for carrying the substrate W into the substrate processing device 1, the control unit 13 issues an operation command and performs the following operations.

That is, the rotation of the rotation drive unit 52 is stopped, and the chuck pin 54 is positioned at a position suitable for delivery of the substrate W. Further, the valves 26, 36, 46 and 74 are opened, and the nozzles 22, 32 and 42 are positioned at the retracted positions Pl, P2 and P3, respectively. Then, the chuck pin 54 is opened by an opening / closing mechanism (not shown).

When the unprocessed substrate W is carried into the substrate processing apparatus 1 by a substrate loading / unloading mechanism (not shown) and placed on the chuck pin 54, the chuck pin 54 is closed by an opening / closing mechanism (not shown).

After the untreated substrate W is held by the substrate holding means 51, the substrate is subjected to the cleaning step S11 by a wet cleaning means (not shown). The cleaning step S11 includes a rinsing process for removing the cleaning liquid after supplying the cleaning liquid to the surface Wf of the substrate W for cleaning. The cleaning liquid is not particularly limited, and examples thereof include SC-1 (liquid containing ammonia, hydrogen peroxide solution, and water) and SC-2 (liquid containing hydrochloric acid, hydrogen peroxide solution, and water). The rinsing liquid is not particularly limited, and examples thereof include DIW and the like. The supply amounts of the cleaning liquid and the rinsing liquid are not particularly limited, and can be appropriately set according to the cleaning range and the like. Further, the cleaning time is not particularly limited and can be set as needed.

In the present embodiment, SC-1 is supplied to the surface Wf of the substrate W to clean the surface Wf by a wet cleaning means, and then DIW is further supplied to the surface Wf to obtain SC-1. Remove.

FIG. 7A shows the state of the substrate W at the end of the cleaning step S11. As shown in FIG. 7A, the DIW supplied in the cleaning step S11 (shown by “60” in the drawing) is attached to the surface Wf of the substrate W on which the pattern Wp is formed. ..

Return to FIG. Next, the IPA rinsing step S12 for supplying IPA to the surface Wf of the substrate W to which the DIW 60 is attached is performed. First, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis A1 at a constant speed.

Next, the control unit 13 issues an operation command to the swivel drive unit 14, and positions the nozzle 32 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 36 to open the valve 36. As a result, the IPA is supplied from the IPA tank 37 to the surface Wf of the substrate W via the pipe 35 and the nozzle 32.

The IPA supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral portion of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the surface Wf of the substrate W Spreads over the entire surface. As a result, the DIW adhering to the surface Wf of the substrate W is removed by the supply of IPA, and the entire surface Wf of the substrate W is covered with IPA. The rotation speed of the substrate W is preferably set so that the film thickness of the film made of IPA is higher than the height of the convex portion Wp1 on the entire surface of the surface Wf. Further, the supply amount of IPA is not particularly limited and can be set as appropriate.

After the completion of the IPA rinsing step S12, the control unit 13 issues an operation command to the valve 36 to close the valve 36. Further, the control unit 13 issues an operation command to the swivel drive unit 14 to position the nozzle 32 at the retracted position P2.

FIG. 7B shows the state of the substrate W at the end of the IPA rinsing step S12. As shown in FIG. 7B, the IPA supplied in the IPA rinsing step S12 (shown by “61” in the figure) adheres to the surface Wf of the substrate W on which the pattern Wp is formed. DIW60 is replaced by IPA61 and removed from the surface Wf of the substrate W.

Return to FIG. Next, a treatment liquid supply step (supply step) S13 for supplying a treatment liquid as a drying auxiliary liquid containing a drying auxiliary substance in a melted state to the surface Wf of the substrate W to which the IPA61 is attached is performed. First, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis Al at a constant speed. At this time, the rotation speed of the substrate W is preferably set so that the film thickness of the liquid film made of the drying auxiliary liquid becomes higher than the height of the convex portion Wp1 on the entire surface of the surface Wf.

Subsequently, the control unit 13 issues an operation command to the swivel drive unit 14, and positions the nozzle 22 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 26 to open the valve 26. As a result, the drying auxiliary liquid is supplied from the processing liquid storage tank 271 to the surface Wf of the substrate W via the pipe 25 and the nozzle 22.

The temperature of the supplied drying auxiliary liquid is set in a range equal to or higher than the melting point of the drying auxiliary substance and lower than the boiling point, at least after being supplied to the surface Wf of the substrate W. For example, when the above 1,1,2,2,3,3,4-heptafluorocyclopentane (boiling point 82.5 degrees Celsius) is used as a drying aid, the range is 35 degrees Celsius or more and 82 degrees Celsius or less. It is preferable to set it. Further, the supply amount of the drying auxiliary liquid is not particularly limited and can be appropriately set.

In this way, by supplying the drying auxiliary liquid in a high temperature state equal to or higher than the melting point, it is possible to form a liquid film of the drying auxiliary liquid on the surface Wf of the substrate W and then form a solidified body. As a result, a film-like solidified body having a uniform layer thickness can be obtained, and the occurrence of uneven drying can be reduced. When the temperature of the substrate W and the ambient temperature in the chamber 11 are equal to or lower than the melting point of the drying auxiliary substance, when the drying auxiliary liquid having a temperature slightly higher than the melting point is supplied to the substrate W, the drying auxiliary liquid comes into contact with the substrate W. After that, it may solidify within a very short time. In such a case, a solidified body having a uniform layer thickness cannot be formed, and it becomes difficult to reduce uneven drying. Therefore, when the temperature of the substrate W and the atmospheric temperature in the chamber 11 are equal to or lower than the melting point of the drying auxiliary substance, it is preferable to adjust the temperature so that the liquid temperature of the drying auxiliary liquid is sufficiently higher than the melting point.

Immediately before supplying to the surface Wf of the substrate W, the liquid temperature of the drying auxiliary liquid is preferably the melting point of the drying auxiliary substance + 10 degrees Celsius or more. If particles or bubbles are present in the drying aid, they can become crystal nuclei when the drying aid is solidified. When a large number of crystal nuclei are present, crystals grow from individual crystal nuclei, resulting in the formation of crystal grains, and grain boundaries are generated at the boundaries where the crystal grains collide with each other. Then, in the presence of grain boundaries, stress acts on the pattern, which may cause the pattern to collapse. However, by setting the liquid temperature of the drying auxiliary liquid to the lower limit value or more, the bubbles existing in the drying auxiliary liquid can be reduced or eliminated. As a result, the occurrence of grain boundaries can be reduced, and the collapse of the pattern can be further reduced.

The drying auxiliary liquid supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the surface Wf of the substrate W Spreads over the entire surface of. As a result, the IPA adhering to the surface Wf of the substrate W is removed by the supply of the drying auxiliary liquid, and the entire surface Wf of the substrate W is covered with the drying auxiliary liquid. After the processing liquid supply step S13 is completed, the control unit 13 issues an operation command to the valve 26 to close the valve 26. Further, the control unit 13 issues an operation command to the swivel drive unit 14 to position the nozzle 22 at the retracted position Pl.

FIG. 7C shows the state of the substrate W at the end of the processing liquid supply step S13. As shown in FIG. 7C, the drying auxiliary liquid supplied in the treatment liquid supply step S13 (shown by “62” in the drawing) is applied to the surface Wf of the substrate W on which the pattern Wp is formed. The IPA 61 is attached and is replaced by the drying auxiliary liquid 62 and removed from the surface Wf of the substrate W.

Return to FIG. Next, a coagulation step S14 is performed in which the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W is coagulated to form a coagulation film of the drying auxiliary substance. First, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is set to such a speed that the drying auxiliary liquid 62 can form a film thickness having a predetermined thickness higher than that of the convex portion Wpl on the entire surface of the surface Wf.

Subsequently, the control unit 13 issues an operation command to the swivel drive unit 14, and positions the nozzle 42 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 46 to open the valve 46. As a result, gas (in this embodiment, nitrogen gas at 7 degrees Celsius) is supplied from the gas tank 47 toward the surface Wf of the substrate W via the pipe 45 and the nozzle 42.

The nitrogen gas supplied toward the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is a drying auxiliary liquid. It diffuses over the entire surface Wf of the substrate W covered with 62. As a result, the liquid film of the drying auxiliary liquid 62 formed on the surface Wf of the substrate W is cooled to a low temperature below the freezing point of the drying auxiliary substance and solidified, and a solidified body is formed.

FIG. 7D shows the state of the substrate W at the end of the solidification step S14. As shown in FIG. 7D, the drying auxiliary liquid 62 supplied in the treatment liquid supply step S13 is cooled and solidified by the supply of nitrogen gas at 7 degrees Celsius, and the coagulated body containing the drying auxiliary substance ( (Shown by "63") is formed in the figure.

Return to FIG. Next, a sublimation step S15 is performed in which the solidified body 63 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W. Also in the sublimation step S15, the supply of gas (nitrogen gas) from the nozzle 42 is continued from the solidification step S14.

Here, the partial pressure of the vapor of the drying auxiliary substance in the nitrogen gas is set lower than the saturated vapor pressure of the drying auxiliary substance at the supply temperature of the nitrogen gas. Therefore, when such nitrogen gas is supplied to the surface Wf of the substrate W and comes into contact with the solidified body 63, the drying auxiliary substance is sublimated into the nitrogen gas from the solidified body 63. Further, since the nitrogen gas has a temperature lower than the melting point of the drying auxiliary substance, the coagulant 63 can be sublimated while preventing the coagulant 63 from melting.

As a result, the sublimation of the drying auxiliary substance in the solid state prevents surface tension from acting on the pattern Wp when removing substances such as IPA existing on the surface Wf of the substrate W, and suppresses the occurrence of pattern collapse. However, the surface Wf of the substrate W can be satisfactorily dried.

FIG. 7E shows the state of the substrate W at the end of the sublimation step S15. As shown in FIG. 7 (e), the coagulated body 63 of the drying auxiliary substance formed in the coagulation step S14 is sublimated by the supply of nitrogen gas at 7 degrees Celsius and removed from the surface Wf, and the surface of the substrate W is formed. Drying of Wf is completed.

After the sublimation step S15 is completed, the control unit 13 issues an operation command to the valve 46 to close the valve 46. Further, the control unit 13 issues an operation command to the swivel drive unit 14 to position the nozzle 42 at the retracted position P3.

As a result, a series of substrate drying processes is completed. After the substrate drying treatment as described above, the dried substrate W is carried out from the chamber 11 by a substrate loading / unloading mechanism (not shown).

As described above, in the present embodiment, the drying auxiliary liquid containing the drying auxiliary substance composed of the fluorocarbon compound in a melted state is supplied to the surface Wf of the substrate W to which the IPA is attached, and the drying auxiliary liquid is supplied to the substrate. After solidifying on the surface Wf of W to form a solidified body containing a drying auxiliary substance, the solidified body is sublimated and removed from the surface Wf of the substrate W to dry the substrate W.

Here, by using the fluorocarbon compound as the drying auxiliary substance, there is an effect that the pattern collapse on the substrate can be more reliably suppressed as compared with the conventional substrate drying. The reason may be that the following factors and other causes are acting in combination.

(Factor 1) Since the drying auxiliary substance composed of the fluorocarbon compound is supplied in a molten state, a film-like solidified body having a uniform layer thickness can be formed on the substrate.

(Factor 2) The vapor pressure of the fluorocarbon compound is compared with the conventional drying aids DIW (vapor pressure 2.3 kPa: 20 degrees Celsius) and t-butanol (vapor pressure 4. lcPa: 20 degrees Celsius). Because it is expensive, the sublimation process can be performed at a faster sublimation speed than before.

(Factor 3) Since the fluorocarbon compound does not have an OH group and is less soluble in water than t-butanol, it does not mix with water remaining on the substrate, and between patterns after sublimation. No water remains.

The specific effect of suppressing pattern collapse will be described in Examples described later.

Further, in the present embodiment, in the coagulation step S14 and the sublimation step S15, the nitrogen gas, which is an inert gas inert to the drying auxiliary substance, is used as the drying auxiliary substance by using the common gas supply means 41. Supply at a temperature below the freezing point. As a result, the sublimation step S15 can be started immediately after the solidification step S14, and the processing time associated with operating each part of the substrate processing apparatus 1 and the amount of memory of the substrate processing program 19 of the control unit 13 to be operated. And the number of parts used for processing can be reduced, which has the effect of reducing the equipment cost. In particular, since the decompression means 71 is not used in this embodiment, the decompression means 71 can be omitted.

(Second Embodiment)
A second embodiment according to the present invention will be described below.
This embodiment is different from the first embodiment in that the treatment liquid is used as a cleaning liquid and / or a rinsing liquid, and the processing liquid supply step is performed as a cleaning / rinsing step. With such a configuration, in the present embodiment, the number of steps can be reduced, the processing efficiency can be improved, the collapse of the pattern can be suppressed, and the surface of the substrate W can be satisfactorily dried.

<2-1 Configuration of substrate processing equipment and processing liquid>
As the substrate processing apparatus and the control unit according to the second embodiment, those having basically the same configuration as the substrate processing apparatus 1 and the control unit 13 according to the first embodiment can be used (see FIGS. 1 and 2). ). Therefore, the description will be omitted with the same reference numerals.

In the present embodiment, the treatment liquid supply means 21 is used as a wet cleaning means and a rinsing means. Since the configuration of the treatment liquid supply means 21 as the wet cleaning means and the rinsing means is the same as that of the first embodiment, the description thereof will be omitted. However, in the present embodiment, since the IPA rinsing step is omitted, the IPA supply means 31 can be omitted. Further, since the treatment liquid used in the present embodiment is the same as the treatment liquid according to the first embodiment, the description thereof will be omitted.

<2-2 Substrate processing method>
Next, a substrate processing method according to the second embodiment using the substrate processing apparatus 1 having the same configuration as that of the first embodiment will be described.

Hereinafter, the substrate processing process will be described with reference to FIGS. 1, 2, 8 and 9 as appropriate. FIG. 8 is a flowchart showing the operation of the substrate processing device 1 according to the second embodiment. FIG. 9 is a schematic view showing the state of the substrate W in each step of FIG. In the second embodiment, each step of the solidification step S14 and the sublimation step S15 shown in FIGS. 8 and 9 (c) and 9 (d) is the same as that of the first embodiment. The explanation is omitted.

As shown in FIG. 8, after the untreated substrate W is held by the substrate holding means 51, the substrate W is subjected to the cleaning / rinsing step S16. In this step, the treatment liquid supply means 21 is used as the cleaning / rinsing means.

That is, first, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis Al at a constant speed. At this time, the rotation speed of the substrate W is preferably set so that the film thickness of the liquid film made of the treatment liquid as the cleaning liquid is higher than the height of the convex portion Wp1 on the entire surface of the surface Wf.

Subsequently, the control unit 13 issues an operation command to the swivel drive unit 14, and positions the nozzle 22 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 26 to open the valve 26. As a result, the treatment liquid as the cleaning liquid is supplied from the treatment liquid storage tank 271 to the surface Wf of the substrate W via the pipe 25 and the nozzle 22.

The liquid temperature of the supplied cleaning liquid (more specifically, the liquid temperature after being supplied to the surface Wf of the substrate W) is set in a range equal to or higher than the melting point of the sublimable substance and lower than the boiling point. Further, the supply amount of the cleaning liquid is not particularly limited and can be appropriately set.

When the temperature of the substrate W and the ambient temperature in the chamber 11 are equal to or lower than the melting point of the sublimable substance, if a cleaning liquid having a temperature slightly higher than the melting point is supplied to the substrate W, it takes an extremely short time after the cleaning liquid comes into contact with the substrate W. May solidify in. In such a case, a solidified body having a uniform layer thickness cannot be formed, and it becomes difficult to reduce uneven drying. Therefore, when the temperature of the substrate W and the atmospheric temperature in the chamber 11 are equal to or lower than the melting point of the sublimable substance, it is preferable to adjust the temperature so that the temperature of the cleaning liquid is sufficiently higher than the melting point.

The cleaning liquid supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the entire surface of the surface Wf of the substrate W. Spread to. As a result, the deposits and the like adhering to the surface Wf of the substrate W are removed by the supply of the cleaning liquid, and the entire surface Wf of the substrate W is covered with the cleaning liquid. After the cleaning is completed, the control unit 13 issues an operation command to the valve 26 to close the valve 26. Further, the control unit 13 issues an operation command to the swivel drive unit 14 to position the nozzle 22 at the retracted position Pl.

FIG. 9A shows the state of the substrate W at the end of cleaning. As shown in FIG. 9A, the cleaning liquid supplied in the cleaning (shown by “64” in the drawing) is attached to the surface Wf of the substrate W on which the pattern Wp is formed. The kimono is removed from the surface Wf of the substrate W by the cleaning liquid 64.

Return to FIG. Further, in the cleaning / rinsing step S16, the substrate W is rinsed by rinsing means. The rinsing liquid used in this treatment is a treatment liquid, and the rinsing means is a treatment liquid supply means 21.

First, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis A1 at a constant speed. Next, the control unit 13 issues an operation command to the swivel drive unit 14, and positions the nozzle 32 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 36 to open the valve 36. As a result, the treatment liquid as the rinse liquid is supplied from the treatment liquid storage tank 271 to the surface Wf of the substrate W via the pipe 25 and the nozzle 22.

The rinse liquid supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral portion of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the surface Wf of the substrate W Spreads over the entire surface of. As a result, the cleaning liquid adhering to the surface Wf of the substrate W is removed by the supply of the rinsing liquid, and the entire surface Wf of the substrate W is covered with the rinsing liquid. The rotation speed of the substrate W is preferably set so that the film thickness of the film made of the rinse liquid is higher than the height of the convex portion Wp1 on the entire surface of the surface Wf. Further, the supply amount of the rinsing liquid is not particularly limited and can be appropriately set. Further, the liquid temperature of the rinsing liquid is the same as the liquid temperature of the cleaning liquid described above. Further, the rinse time is not particularly limited and can be set as needed.

After the cleaning / rinsing step S16 is completed, the control unit 13 issues an operation command to the valve 26 to open the valve 26. Further, the control unit 13 issues an operation command to the swivel drive unit 14 to position the nozzle 22 at the retracted position P1.

FIG. 9B shows the state of the substrate W at the end of rinsing in the cleaning / rinsing step S16. As shown in FIG. 9B, the rinsing liquid supplied in the rinsing treatment (shown by “65” in the figure) adheres to the surface Wf of the substrate W on which the pattern Wp is formed. The cleaning liquid 64 is replaced by the rinsing liquid 65 and removed from the surface Wf of the substrate W.

Return to FIG. Next, a coagulation step S14 is performed in which the rinse liquid 65 supplied to the surface Wf of the substrate W is coagulated to form a coagulation film of the sublimable substance. Further, a sublimation step S15 is performed in which the solidified body 63 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W.

As described above, the series of substrate drying treatments in the present embodiment is completed. After the substrate drying treatment as described above, the dried substrate W is carried out from the chamber 11 by a substrate loading / unloading mechanism (not shown).

(Third Embodiment)
A third embodiment according to the present invention will be described below.
This embodiment is different from the first embodiment in that the pattern forming surface of the substrate is previously subjected to a water repellent treatment. When the solidified body sublimates, the solidified body may exert stress on the pattern of the substrate. At this time, if the degree of sublimation of the solidified body is non-uniform, non-uniform stress is also applied to the pattern, and as a result, the pattern may collapse. However, by subjecting the pattern-forming surface to a water-repellent treatment in advance as in the present embodiment, even if the patterns try to come into contact with each other, they repel each other due to the repulsive force, and as a result, the patterns can be prevented from collapsing. As a result, the surface of the substrate W may be dried more satisfactorily as compared with the case where the pattern forming surface of the substrate is not subjected to the water repellent treatment.

<3-1 Configuration of substrate processing equipment and drying aid>
The substrate processing apparatus according to the third embodiment will be described with reference to FIGS. 10 and 11 as appropriate. FIG. 10 is an explanatory diagram showing an outline of the substrate processing apparatus 10 according to the present embodiment. FIG. 11 is a schematic plan view showing the internal configuration of the substrate processing apparatus 10.

The substrate processing apparatus 10 according to the third embodiment has basically the same configuration as the substrate processing apparatus 1 according to the first embodiment, except that the substrate processing apparatus 10 according to the third embodiment includes the water repellent supply means 81 (see FIG. 10). ). Further, the control unit according to the third embodiment has the same configuration as the control unit 13 according to the first embodiment. Therefore, those having the same function are designated by the same reference numerals and the description thereof will be omitted.

The water repellent supply means 81 is a unit that supplies the water repellent agent to the pattern forming surface of the substrate W, and as shown in FIG. 10, the nozzle 82, the arm 83, the swivel shaft 84, the pipe 85, and the valve. At least 86 and a water repellent supply unit 87 are provided.

The water repellent supply unit 87 is connected to the nozzle 82 via a pipe 85, and a valve 86 is inserted in the middle of the path of the pipe 85. A water repellent agent is stored in the water repellent supply unit 87, the water repellent agent in the water repellent supply unit 87 is pressurized by a pump (not shown), and the water repellent agent is sent from the pipe 85 toward the nozzle 82. Be done. When the water repellent is gaseous, the gaseous water repellent is stored in the water repellent supply unit 87, and is gaseous in the water repellent supply 87 by a pressurizing means (not shown). The water repellent is pressurized and sent from the pipe 85 toward the nozzle 83. Since the pressurizing means can be realized by compressing and storing the gas in the gas tank 47 in addition to pressurizing by a pump or the like, any pressurizing means may be used.

The valve 86 is electrically connected to the control unit 13 and is normally closed. The opening and closing of the valve 86 is controlled by the operation command of the control unit 13. When the valve 86 is opened by the operation command of the control unit 13, the water repellent agent is supplied from the nozzle 82 to the surface Wf of the substrate W through the pipe 85.

The nozzle 82 is attached to the tip of the horizontally extended arm 83 and is arranged above the spin base 53. The rear end portion of the arm 83 is rotatably supported around the shaft J4 by a swivel shaft 84 extending in the Z direction, and the swivel shaft 84 is fixed in the chamber 11. The arm 83 is connected to the swivel drive unit 14 via the swivel shaft 84. The swivel drive unit 14 is electrically connected to the control unit 13 and rotates the arm 83 around the shaft J4 in response to an operation command from the control unit 13. As the arm 83 rotates, the nozzle 82 also moves.

As shown by a solid line in FIG. 11, the nozzle 82 is usually arranged at the retracted position P4 outside the peripheral edge of the substrate W and outside the shatterproof cup 12. When the arm 83 is rotated by the operation command of the control unit 13, the nozzle 82 moves along the path of the arrow AR4 and is arranged at a position above the central portion (axis A1 or its vicinity) of the surface Wf of the substrate W.

Since the drying auxiliary liquid used in the present embodiment is the same as the drying auxiliary liquid according to the first embodiment, the description thereof will be omitted.

<3-2 Water repellent>
Next, the water repellent used in this embodiment will be described below.
The water repellent agent of the present embodiment is not particularly limited as long as it can form a water repellent protective film on the surface of the pattern and is compatible with the drying auxiliary liquid. As such a water repellent, for example, when the substrate W is made of a silicon-based material such as silicon oxide, silicon nitride, polycrystalline silicon, or single crystal silicon, a silicon-based water repellent, a non-chloro water repellent, and the like. Examples include metal-based water repellents.

The silicon-based water repellent is not particularly limited, and is, for example, hydrofluoric acid, a silane coupling agent (for example, HMDS (hexamethyldisilazane), alkyldisilazane, TMS (tetramethylsilane), fluorinated alkylchlorosilane, alkyl. Disilazane) and the like. The non-chloro water repellent is not particularly limited, and for example, dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis (dimethylamino) dimethylsilane, N, N-dimethylaminotrimethyl. Examples thereof include silane, N- (trimethylsilyl) dimethylamine, and organosilane compounds. The metal-based water repellent is not particularly limited, and examples thereof include amines having a hydrophobic group and organic silicon compounds. These can be used alone or in combination of two or more. Further, the water repellent may be in the form of a gas as well as in the form of a liquid.

When the water repellent is in liquid form, the water repellent may contain a solvent that may be used for dilution. Examples of such a solvent include HMDS (hexamethyldisilazane) and the like.

<3-3 Substrate processing method>
Next, the substrate processing method according to the third embodiment using the substrate processing apparatus 10 according to the present embodiment will be described.

Hereinafter, the substrate processing process will be described with reference to FIGS. 12 and 13. FIG. 12 is a flowchart showing the operation of the substrate processing apparatus 10 according to the third embodiment. FIG. 13 is a schematic view showing the state of the substrate W in each step of FIG. In the third embodiment, the cleaning step S11, the IPA rinsing step S12, and the treatment liquid supply step shown in FIGS. 12 and 13 (a) to 13 (f) (excluding FIG. 13 (c)) are shown. Since each step of S13, the solidification step S14, and the sublimation step S15 is the same as that of the first embodiment, the description thereof will be omitted.

As shown in FIG. 12, a water repellent treatment step S17 for supplying a water repellent agent to the surface Wf of the substrate W to which the IPA 61 is attached by the IPA rinsing step is performed. First, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis Al at a constant speed. At this time, the rotation speed of the substrate W is preferably set so that the film thickness of the liquid film made of the drying auxiliary liquid becomes higher than the height of the convex portion Wp1 on the entire surface of the surface Wf.

Subsequently, the control unit 13 issues an operation command to the swivel drive unit 14, and positions the nozzle 82 at the center of the surface Wf of the substrate W. Then, the control unit 13 issues an operation command to the valve 86 to open the valve 86. As a result, the water repellent is supplied from the water repellent supply unit 87 to the surface Wf of the substrate W via the pipe 85 and the nozzle 82.

The liquid temperature and the amount of the water repellent to be supplied are not particularly limited and may be set as necessary, but a water repellent having a large contact angle between the base W and water after the water repellent treatment is used. Is preferable.

The water repellent supplied to the surface Wf of the substrate W flows from the vicinity of the center of the surface Wf of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and the surface Wf of the substrate W Spreads over the entire surface of. As a result, the IPA adhering to the surface Wf of the substrate W is removed by the supply of the water repellent, and the entire surface Wf of the substrate W is covered with the water repellent. After the water repellent treatment step S17 is completed, the control unit 13 issues an operation command to the valve 86 to close the valve 86. Further, the control unit 13 issues an operation command to the swivel drive unit 14 to position the nozzle 82 at the retracted position P4.

FIG. 13C shows the state of the substrate W at the end of the water repellent treatment step S17. As shown in FIG. 13C, the water repellent agent supplied in the water repellent treatment step S17 (shown by “66” in the figure) is applied to the surface Wf of the substrate W on which the pattern Wp is formed. The IPA 61 is attached and is replaced by the water repellent 66 and removed from the surface Wf of the substrate W.

Subsequently, a treatment liquid supply step (supply step) S13 for supplying a drying auxiliary liquid containing a sublimating substance in a molten state to the surface Wf of the substrate W to which the water repellent 66 is attached is performed. Each step after the treatment liquid supply step S13 is the same as the substrate treatment method according to the first embodiment.

As described above, the series of substrate drying treatments in the present embodiment is completed. After the substrate drying treatment as described above, the dried substrate W is carried out from the chamber 11 by a substrate loading / unloading mechanism (not shown).

The present embodiment can also be applied to the substrate processing method according to the second embodiment. In this case, the water repellent treatment step S17 can be performed immediately before the cleaning / rinsing step S16. As a result, non-uniform stress is applied to the patterns due to the non-uniform degree of sublimation of the solidified body, and as a result, even if the patterns try to come into contact with each other, the patterns repel each other and collapse. Can be suppressed. As a result, even in the second embodiment, the occurrence of pattern collapse can be further reduced.

(Fourth Embodiment)
The fourth embodiment according to the present invention will be described below. This embodiment is different from the first embodiment and the second embodiment in that the inside of the chamber is depressurized in place of the supply of nitrogen gas in the solidification step S14 and the sublimation step S15. Even with such a configuration, the surface of the substrate W can be satisfactorily dried while suppressing the collapse of the pattern.

<4-1 Overall configuration of substrate processing equipment and drying aid>
Since the substrate processing apparatus and the control unit according to the fourth embodiment have basically the same configuration as the substrate processing apparatus 1 and the control unit 13 according to the first embodiment (see FIGS. 1 and 2). The description will be omitted with the same reference numerals. Further, since the drying auxiliary liquid used in the present embodiment is the same as the drying auxiliary liquid according to the first embodiment, the description thereof will be omitted.

<4-2 Substrate processing method>
Next, the substrate processing method according to the fourth embodiment using the substrate processing apparatus 1 having the same configuration as that of the first embodiment will be described.

Hereinafter, the substrate processing process will be described with reference to FIGS. 1, 2, 6, and 14 as appropriate. FIG. 14 is a schematic view showing the state of the substrate W in each step of FIG. In the fourth embodiment, each step of the cleaning step S11, the IPA rinsing step S12, and the treatment liquid supply step S13 shown in FIGS. 6 and 14 (a) to 14 (c) is the first embodiment. Since it is the same as the form, the description thereof will be omitted.

Here, FIG. 14A shows the state of the substrate W whose surface Wf is covered with the liquid film of DIW60 at the end of the cleaning step S11 in the fourth embodiment, and FIG. 14B shows the state of the substrate W. , The state of the substrate W whose surface Wf is covered with the liquid film of IPA61 at the end of the IPA rinsing step S12 in the fourth embodiment is shown, and FIG. 14 (c) shows the state of the substrate W in the fourth embodiment. The state of the substrate W whose surface Wf is covered with the liquid film of the drying auxiliary liquid 62 in which the drying auxiliary substance (sublimating substance) is melted at the end of the treatment liquid supply step S13 is shown.

Further, each of FIGS. 14 (a) to 14 (e) is processed in an atmospheric pressure environment without any particular instruction. Here, the atmospheric pressure environment refers to an environment of 0.7 atm or more and 1.3 atm or less, centered on the standard atmospheric pressure (1 atm, 1013 hPa). In particular, when the substrate processing apparatus 1 is arranged in a clean room where the pressure is positive, the environment of the surface Wf of the substrate W becomes higher than 1 atm. Further, the processes shown in FIGS. 14 (d) and 14 (e) (details will be described later) are performed in a reduced pressure environment of ^{1.7 Pa (1.7 × 10-5 atm).}

See FIG. After the cleaning step S11, the IPA rinsing step S12, and the treatment liquid supply step S13 are executed, the liquid film of the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W is coagulated to form a coagulated body containing the drying auxiliary substance. The solidification step S14 is performed. Specifically, first, the control unit 13 issues an operation command to the rotation drive unit 52 to rotate the substrate W around the axis A1 at a constant speed. At this time, the rotation speed of the substrate W is preferably set so that the film thickness of the liquid film made of the drying auxiliary liquid becomes higher than the height of the convex portion Wp1 on the entire surface of the surface Wf.

Subsequently, the control unit 13 issues an operation command to the exhaust pump 72 and starts driving the exhaust pump 72. Then, the control unit 13 issues an operation command to the valve 74 to open the valve 74. As a result, the gas inside the chamber 11 is exhausted to the outside of the chamber 11 via the pipe 73. By sealing the inside of the chamber 11 except for the pipe 73, the internal environment of the chamber 11 is depressurized from the atmospheric pressure.

The depressurization is performed from atmospheric pressure (about 1 atm, about 1013 hPa) to about 1.7 × ^10-5 atm (1.7 Pa). In the practice of the present invention, the atmospheric pressure is not limited to the atmospheric pressure, and the atmospheric pressure in the chamber 11 after decompression may be appropriately set according to the pressure resistance of the chamber 11 and the like.

When the inside of the chamber 11 is depressurized, the drying auxiliary substance evaporates from the drying auxiliary liquid 62 supplied to the surface Wf of the substrate W. At this time, since the heat of vaporization is taken from the drying auxiliary liquid 62, the drying auxiliary liquid 62 is cooled and solidified.

FIG. 14D shows the state of the substrate W at the end of the solidification step S14. As shown in FIG. 14D, the drying auxiliary liquid 62 supplied in the treatment liquid supply step S13 is cooled and solidified by the evaporation of the drying auxiliary material due to the decompression in the chamber 11, and the drying auxiliary material is solidified. (Indicated by "63" in the figure) is formed.

At this time, the layer thickness of the solidified body 63 is reduced by the amount of the drying auxiliary substance evaporated from the drying auxiliary liquid 62. Therefore, in the treatment liquid supply step S13 in the present embodiment, the drying auxiliary liquid 62 is formed into a liquid film having a predetermined thickness or more in consideration of the evaporation amount of the drying auxiliary substance in the solidification step S14. , It is preferable to adjust the rotation speed of the substrate W and the like.

Return to FIG. Next, a sublimation step S15 is performed in which the solidified body 63 formed on the surface Wf of the substrate W is sublimated and removed from the surface Wf of the substrate W. In the sublimation step S15 as well, the decompression treatment in the chamber 11 by the decompression means 71 is continued from the solidification step S14.

Due to the reduced pressure treatment, the environment in the chamber 11 becomes a pressure lower than the saturated vapor pressure of the drying auxiliary substance. Therefore, when such a reduced pressure environment is maintained, sublimation of the drying auxiliary substance occurs from the solidified body 63.

Even when the drying auxiliary substance is sublimated from the solidified body 63, the solidified body 63 is cooled because heat is taken from the solidified body 63 as sublimation heat. Therefore, in the fourth embodiment, the sublimation step Sl5 separately cools the solidified body 63 even when the environment in the chamber 11 is a temperature slightly higher than the melting point of the drying auxiliary substance (normal temperature environment). The solidified body 63 can be maintained at a temperature lower than the melting point of the drying auxiliary substance, and the solidified body 63 can be sublimated while preventing the solidified body 63 from melting. As a result, it is not necessary to provide a separate cooling mechanism, and the device cost and the processing cost can be reduced.

As described above, the sublimation of the drying auxiliary substance in the solid state prevents the surface tension from acting on the pattern Wp when the substance such as IPA existing on the surface Wf of the substrate W is removed, and the pattern collapse occurs. The surface Wf of the substrate W can be satisfactorily dried while being suppressed.

FIG. 14E shows the state of the substrate W at the end of the sublimation step S15. As shown in FIG. 14 (e), the coagulated body 63 of the drying auxiliary substance formed in the coagulation step S14 is sublimated by the reduced pressure environment in the chamber 11 and removed from the surface Wf, and the substrate W is removed. Drying of the surface Wf is completed.

After the sublimation step S15 is completed, the control unit 13 issues an operation command to the valve 74 to open the valve 74. Further, the control unit 13 issues an operation command to the exhaust pump 72 to stop the operation of the exhaust pump 72. Then, the control unit 13 issues an operation command to the valve 46, and by opening the valve 46, gas (nitrogen gas) is introduced into the chamber 11 from the gas tank 47 via the pipe 45 and the nozzle 42, and the chamber 11 The inside is restored from the decompression environment to the atmospheric pressure environment. At this time, the nozzle 42 may be located at the retracted position P3 or may be located at the center of the surface Wf of the substrate W.

The method for returning the inside of the chamber 11 to the atmospheric pressure environment after the completion of the sublimation step S15 is not limited to the above, and various known methods may be adopted.

As a result, a series of substrate drying processes is completed. After the substrate drying treatment as described above, the dried substrate W is carried out from the chamber 11 by a substrate loading / unloading mechanism (not shown).

As described above, in the fourth embodiment, the drying auxiliary liquid in which the drying auxiliary substance is melted is supplied to the surface Wf of the substrate W to which the IPA is attached to replace it. Then, the drying auxiliary liquid is solidified on the surface image Wf of the substrate W to form a solidifying film of the drying auxiliary substance, and then the drying auxiliary substance is sublimated and removed from the surface Wf of the substrate W. As a result, the substrate W is dried.

Even if the drying auxiliary liquid is solidified and sublimated by reducing the pressure as in the fourth embodiment, the substrate W can be well dried while preventing the pattern from collapsing. The specific pattern suppressing effect will be described in Examples described later.

Further, in the fourth embodiment, the inside of the chamber 11 is depressurized by using the common depressurizing means 71 in the solidification step S14 and the sublimation step S15. As a result, the sublimation step S15 can be started immediately after the solidification step S14, and the processing time associated with operating each part of the substrate processing apparatus 1 and the amount of memory of the substrate processing program 19 of the control unit 13 to be operated. And the number of parts used for processing can be reduced, which has the effect of reducing the equipment cost. In particular, since low-temperature nitrogen gas is not used in the fourth embodiment, the temperature adjusting unit 272 in the gas supply means 41 may be omitted, and when the inside of the chamber 11 is returned from the reduced pressure environment to the atmospheric pressure environment, it may be omitted. When a means other than the gas supply means 41 is used, the gas supply means 41 may be omitted.

(Modification example)
In the above description, preferred embodiments of the present invention have been described. However, the present invention is not limited to these embodiments, and can be implemented in various other forms. The other main forms are illustrated below.

In the first to fourth embodiments, each step was performed on the substrate W in one chamber 11. However, the practice of the present invention is not limited to this, and a chamber may be prepared for each step.

For example, in each embodiment, the solidification step S14 is executed in the first chamber, a solidifying film is formed on the surface Wf of the substrate W, the substrate W is carried out from the first chamber, and the solidifying film is transferred to another second chamber. The substrate W on which the above is formed may be carried in and the sublimation step S15 may be performed in the second chamber.

Further, in the first to third embodiments, gas supply by the gas supply means 41 was executed in both the solidification step S14 and the sublimation step S15. Further, in the fourth embodiment, in both the solidification step S14 and the sublimation step S15, the decompression treatment in the chamber 11 was executed by the decompression means 71. However, the implementation of the present invention is not limited to this, and after gas supply by the gas supply means 41 is executed in the solidification step S14 to form the solidified body 63 on the surface Wf, the decompression means 71 is performed in the sublimation step S15. The coagulated body 63 may be sublimated by performing the depressurizing treatment in the chamber 11 according to the above.

In the first to fourth embodiments, in the solidification step S14, the gas supply means 41 supplies a low-temperature gas below the freezing point of the drying auxiliary substance to form the solidified body 63 on the surface Wf. However, the practice of the present invention is not limited to this.

Specifically, instead of the spin base 53 and the chuck pin 54 of FIG. 1 or 10, a spin chuck that directly contacts the central portion of the back surface Wb of the substrate W to attract and hold the substrate W is provided, and the spin chuck is known. The substrate W is cooled from the back surface Wb by cooling by a cooling mechanism (for example, passing through a cold water pipe, using a Perche element, etc.), and the drying auxiliary liquid 62 on the front surface Wf (in the case of the second embodiment, the rinsing liquid 65). ) May be cooled to a low temperature below the freezing point.

Further, in the first to third embodiments, in at least one of the solidification step S14 and the sublimation step S15, instead of the gas supply means 41, the back surface Wb of the substrate W is equal to or less than the freezing point of the drying auxiliary substance. The refrigerant may be supplied at a low temperature of. In this case, the substrate processing devices 1 and 10 are provided with a through hole in the central portion of the spin base 53 of FIG. 1 or FIG. This can be achieved by providing a coagulation means and a sublimation means). The unit includes, for example, a refrigerant storage unit for storing the refrigerant, a refrigerant temperature adjusting unit for adjusting the temperature of the refrigerant stored in the refrigerant storage unit, and a pipe for connecting the refrigerant storage unit to the through hole. , A configuration including a valve provided in the middle of the piping route (neither is shown).

The refrigerant temperature adjusting unit is electrically connected to the control unit 13, and heats or cools the refrigerant stored in the refrigerant storage unit according to an operation command of the control unit 13 to adjust the temperature. The temperature may be adjusted so that the temperature of the refrigerant stored in the refrigerant storage unit is as low as the freezing point of the drying auxiliary substance or lower. The refrigerant temperature adjusting unit is not particularly limited, and for example, a known temperature adjusting mechanism such as a Perche element or a pipe through which temperature-controlled water is passed can be used.

The refrigerant in the refrigerant storage section is pressurized by a pressurizing means (not shown) and sent to the pipe. The pressurizing means can be realized not only by pressurizing with a pump or the like, but also by compressing and storing the gas in the refrigerant storage section.

The valve is electrically connected to the control unit 13 and is normally closed. The opening and closing of the valve is controlled by the operation command of the control unit 13. When the valve is opened by the operation command of the control unit 13, the refrigerant is supplied to the back surface Wb of the substrate W through the through hole through the pipe. As a result, in the coagulation step S14, the drying auxiliary liquid 62 (rinse liquid 65 in the case of the second embodiment) of the surface Wf can be coagulated to form a coagulated body. Further, in the sublimation step S15, the solidified body 63 can be sublimated while preventing the solidified body 63 from melting.

Examples of the refrigerant include a liquid or gas below the freezing point of the drying auxiliary substance. Further, the liquid is not particularly limited, and examples thereof include cold water at 7 degrees Celsius. The gas is not particularly limited, and examples thereof include an inert gas inert to the drying aid, and more specifically, a nitrogen gas at 7 degrees Celsius.

Hereinafter, preferred embodiments of the present invention will be described in detail exemplarily. However, the materials, blending amounts, etc. described in this example are not intended to limit the scope of the present invention to those only unless otherwise specified.

(substrate)
As a substrate, a silicon substrate having a model pattern formed on the surface was prepared. FIG. 9 shows an SEM (Scanning Electron Microscope) image showing a surface on which a model pattern of a silicon substrate is formed. As a model pattern, a pattern in which cylinders having a diameter of 30 nm and a height of 480 nm (aspect ratio of 16) were arranged at intervals of about 30 nm was adopted. In FIG. 9, the white portion is the head of the cylindrical portion (that is, the convex portion of the pattern), and the black portion is the concave portion of the pattern. As shown in FIG. 9, it has been confirmed that white circles having substantially the same size are regularly arranged on the pattern forming surface.

(Example 1)
In this example, the silicon substrate was dried according to the procedure described below, and the effect of suppressing pattern collapse was evaluated. Further, in the processing of the silicon substrate, the substrate processing apparatus described in the first embodiment was used.

<Procedure 1-1 UV irradiation>
First, the surface of the silicon substrate was irradiated with ultraviolet light to make its surface characteristics hydrophilic. This facilitated the entry of the liquid into the recesses of the pattern, and artificially created an environment in which the pattern was prone to collapse after the liquid was supplied.

<Procedure 1-2 Supply process>
Next, in the chamber 11 under atmospheric pressure, a drying auxiliary liquid (liquid temperature 40 ° C.) obtained by melting the sublimable substance was directly supplied to the pattern forming surface of the dried silicon substrate. As a result, a liquid film made of a drying auxiliary liquid was formed on the pattern forming surface of the silicon substrate. As the sublimable substance, 1,1,2,2,3,3,4-heptafluorocyclopentane represented by the following chemical structural formula was used. The compound has a surface tension of 19.6 mN / m in an environment of 25 ° C. and a vapor pressure of 8.2 kPa (62.0 mmHg) in an environment of 20 ° C. Further, the melting point and the freezing point are 20.5 ° C., and the specific gravity is 1.58 in an environment of 25 ° C. Further, since the compound has excellent solubility of, for example, a fluorine-based polymer, it is used as a solvent for various coating agents and as a cleaning agent for oil film stains.

<Procedure 1-3 Coagulation step>
Subsequently, in an atmospheric pressure environment, nitrogen gas at 7 degrees Celsius was supplied onto a liquid film made of a drying auxiliary liquid, and the drying auxiliary liquid was coagulated to form a coagulated body.

<Procedure 1-4 Sublimation process>
Furthermore, under normal temperature and atmospheric pressure environment, nitrogen gas at 7 degrees Celsius is continuously supplied to the coagulant, thereby sublimating the drying auxiliary substance (sublimable substance) while preventing the coagulant from melting. , The solidified body was removed from the pattern forming surface of the silicon substrate. The temperature of nitrogen gas is 7 degrees Celsius, which is lower than the melting point of 1,1,2,2,3,3,4-heptafluorocyclopentane (20.5 degrees Celsius). On the other hand, no separate cooling was performed.

FIG. 16 is an SEM image of the silicon substrate after performing the above steps 1-1 to 1-4. Compared with the pattern forming surface (see FIG. 15) of the silicon substrate before the drying treatment, almost no pattern collapse was observed, and the collapse rate in the displayed region was 0%. As a result, when 1,1,2,2,3,3,4-heptafluorocyclopentane is used as a drying aid, the pattern collapse can be suppressed extremely well, which is effective for sublimation drying. It was shown to be.
The collapse rate is a value calculated by the following formula.
Collapse rate (%) = (number of collapsed convex parts in an arbitrary area) ÷ (total number of convex parts in the area) × 100

(Example 2)
In this embodiment, the temperature of the drying auxiliary liquid supplied to the pattern forming surface of the silicon substrate in the supply step was changed to room temperature (23 ° C.). Except for this, steps 1-1 to 1-4 were carried out in the same manner as in Example 1, and the pattern-forming surface of the silicon substrate was freeze-dried.

FIG. 17 is an SEM image of a silicon substrate after performing steps 1-1 to 1-4 in this embodiment. A slight collapse of the crack-like pattern was observed as compared with the pattern-forming surface of the silicon substrate before the drying treatment (see FIG. 15), but the collapse rate in the displayed area was suppressed to 16%. .. As a result, even when 1,1,2,2,3,3,4-heptafluorocyclopentane as a drying auxiliary substance is used at room temperature, the collapse of the pattern can be satisfactorily suppressed, resulting in sublimation drying. It has been shown to be valid.

(Example 3)
In this embodiment, the temperature of the drying auxiliary liquid supplied to the pattern forming surface of the silicon substrate was changed to 60 ° C. in the supply process. Except for this, steps 1-1 to 1-4 were carried out in the same manner as in Example 1, and the pattern-forming surface of the silicon substrate was freeze-dried.

FIG. 18 is an SEM image of a silicon substrate after performing steps 1-1 to 1-4 in this embodiment. Compared with the pattern forming surface (see FIG. 15) of the silicon substrate before the drying treatment, almost no pattern collapse was observed, and the collapse rate in the displayed region was 0%. As a result, when 1,1,2,2,3,3,4-heptafluorocyclopentane is used as a drying aid, the pattern collapse can be suppressed extremely well, which is effective for sublimation drying. It was shown to be.

(Comparative Example 1)
In this comparative example, t-butanol was used as the drying aid instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Other than that, the silicon substrate was dried in the same manner as in Example 1.

FIG. 19 is an SEM image of a region showing an average pattern collapse rate on a silicon substrate after performing the above procedure. Compared with the pattern forming surface (see FIG. 15) of the silicon substrate before the drying treatment, large white circles were observed in many places, and it was confirmed that the collapse of the pattern could not be reduced. The pattern collapse rate was about 16%.

(Example 4)
In Example 1, the effect of suppressing pattern collapse when the drying auxiliary liquid was directly supplied to the pattern-forming surface of the dried silicon substrate was evaluated. However, in the actual drying treatment of the substrate, after the wet cleaning treatment, the drying treatment is performed on the substrate in which the liquid adheres to the pattern forming surface. Therefore, in the fourth embodiment, the effect of suppressing pattern collapse was evaluated when the dried silicon substrate was subjected to a drying treatment by supplying a drying auxiliary liquid after supplying DIW and IPA. .. As the silicon substrate, the same one as in Example 1 was used. Further, in the drying treatment, the substrate processing apparatus described in the first embodiment was used.

<Procedure 2-1 Ultraviolet light irradiation>
The silicon substrate was irradiated with ultraviolet light in the same manner as in Example 1.

<Procedure 2-2 DIW and IPA supply process>
Next, DIW was supplied to the pattern-forming surface of the dried silicon substrate, and then IPA was further supplied. As a result, the DIW adhering to the pattern forming surface of the silicon substrate was removed, and a liquid film made of IPA was formed.

<Procedure 2-3 Supply process>
Subsequently, in the same manner as in Example 1, the drying auxiliary liquid was supplied onto the pattern-forming surface of the silicon substrate. As a result, the liquid film of IPA formed on the pattern forming surface of the silicon substrate was removed, and a liquid film made of a drying auxiliary liquid was formed. The same drying auxiliary solution as in Example 1 was used.

<Procedure 2-4 solidification process>
Subsequently, in an atmospheric pressure environment, nitrogen gas at 7 degrees Celsius was supplied onto a liquid film made of a drying auxiliary liquid, and the drying auxiliary liquid was coagulated to form a coagulated body.

<Procedure 2-5 Sublimation process>
Further, in an environment of normal temperature and atmospheric pressure, nitrogen gas at 7 degrees Celsius is continuously supplied to the coagulated body, whereby the drying auxiliary substance is sublimated while preventing the coagulated body from melting, and the silicon substrate is subjected to. The solidified material was removed from the pattern forming surface. The temperature of nitrogen gas is 7 degrees Celsius, which is lower than the melting point of 1,1,2,2,3,3,4-heptafluorocyclopentane (20.5 degrees Celsius). On the other hand, no separate cooling was performed.

FIG. 20 is an SEM image of the silicon substrate after performing the above steps 2-1 to 2-5. Compared with the pattern forming surface (see FIG. 15) of the silicon substrate before the drying treatment, large white circles were observed at a plurality of places, and the pattern collapse was confirmed. However, the collapse rate in the displayed region is less than 1%, and even for the silicon substrate after the wet cleaning treatment, 1,1,2,2,3,3,4-heptafluoro as a drying auxiliary substance. It was shown that when cyclopentane was used, the occurrence of pattern collapse could be satisfactorily reduced.

(Example 5)
In Example 1 and Example 4, the collapse rate of the pattern was evaluated under normal pressure environment. In Example 5, the effect of suppressing pattern collapse when the drying auxiliary substance was sublimated in a reduced pressure environment was evaluated. As the silicon substrate, the same one as in Example 1 was used. Further, in the drying treatment, the substrate processing apparatus described in the second embodiment was used.

<Procedure 3-1 UV irradiation>
The silicon substrate was irradiated with ultraviolet light in the same manner as in Example 1.

<Procedure 3-2 Supply process>
Next, in the chamber 11 under atmospheric pressure, a drying auxiliary liquid (liquid temperature 40 ° C.) obtained by melting the sublimable substance was directly supplied to the pattern forming surface of the dried silicon substrate. As a result, a liquid film made of a drying auxiliary liquid was formed on the pattern forming surface of the silicon substrate. The same drying auxiliary solution as in Example 1 was used.

<Procedure 3-3 solidification process>
Then, the silicon substrate was placed on the cooling plate under the atmospheric pressure environment, the back surface of the substrate was brought into contact with the cooling plate, and the liquid film of the drying auxiliary liquid was cooled from the surface of the substrate. As a result, a coagulated body composed of a drying auxiliary liquid was formed.

<Procedure 3-4 Sublimation process>
Subsequently, the inside of the chamber 11 containing the silicon substrate was depressurized by the depressurizing means 71, and the atmospheric pressure was set to 1.7 Pa to sublimate the drying auxiliary substance, thereby removing the solidified body from the surface of the silicon substrate.

FIG. 21 is an SEM image of the silicon substrate after performing the above steps 3-1 to 3-4. Compared with the pattern forming surface (see FIG. 15) of the silicon substrate before the drying treatment, large white circles were observed at a plurality of places, and the pattern collapse was slightly confirmed. However, the collapse rate in the indicated area is less than 1%, and even when the sublimation process is performed in a reduced pressure environment, 1,1,2,2,3,3,4-heptafluoro as a drying aid. It was shown that when cyclopentane was used, the occurrence of pattern collapse could be satisfactorily reduced.

(Comparative Example 2)
In this comparative example, t-butanol was used as the drying aid instead of 1,1,2,2,3,3,4-heptafluorocyclopentane. Other than that, the silicon substrate was dried in the same manner as in Example 3.

In this comparative example, the best results were obtained when t-butanol was used as the drying auxiliary liquid and the sublimation step was performed in a reduced pressure environment. When t-butanol was used and the sublimation step was performed in a normal pressure environment, the pattern collapse rate was higher than that in this comparative example, so the description thereof was omitted.

FIG. 22 is an SEM image of a region showing an average pattern collapse rate on a silicon substrate after performing the above procedure. Compared with the pattern forming surface (see FIG. 15) of the silicon substrate before the drying treatment, large white circles were observed in many places, and it was confirmed that the collapse of the pattern could not be reduced. The pattern collapse rate was 34%. Further, FIG. 23 is an SEM image in the region where the pattern collapse rate is the best in the silicon substrate after performing the above procedure. Even in the best area, it was confirmed that the white circles became large in multiple places. The pattern collapse rate in this area was 4%.

(Example 6)
In this example, the silicon substrate was dried according to the procedure described below, and the effect of suppressing pattern collapse was evaluated. Further, in the processing of the silicon substrate, the substrate processing apparatus described in the third embodiment was used. As the silicon substrate, a silicon substrate that was more easily collapsed than the one used in Example 1 and had a fragile pattern formed was used.

<Procedure 4-1 Ultraviolet light irradiation>
The silicon substrate was irradiated with ultraviolet light in the same manner as in Example 1.

<Procedure 4-2 Water repellent treatment process>
Next, the HMDS gas was brought into direct contact with the pattern-forming surface of the dried silicon substrate in the chamber 11 under atmospheric pressure. As a result, the pattern-forming surface of the silicon substrate was water-repellent.

<Procedure 4-3 Supply process>
Subsequently, in the same manner as in Example 1, the drying auxiliary liquid was supplied onto the pattern-forming surface of the silicon substrate. As a result, a liquid film made of a drying auxiliary liquid was formed on the pattern forming surface of the silicon substrate. The same drying auxiliary solution as in Example 1 was used.

<Procedure 4-4 solidification process>
Subsequently, in the same manner as in Example 1, nitrogen gas at 7 degrees Celsius was supplied onto a liquid film composed of a drying auxiliary liquid in an atmospheric pressure environment, and the drying auxiliary liquid was coagulated to form a coagulated body. ..

<Procedure 4-5 Sublimation process>
Subsequently, in the same manner as in Example 1, nitrogen gas at 7 degrees Celsius was continuously supplied to the coagulated body under a normal temperature atmospheric pressure environment, whereby the drying auxiliary substance was prevented while preventing the coagulated body from melting. (Sublimable substance) was sublimated to remove the solidified body from the pattern-forming surface of the silicon substrate.

FIG. 24 is an SEM image of the silicon substrate after performing the above steps 4-1 to 4-5. It was confirmed that the collapse of the pattern was significantly reduced as compared with the pattern forming surface (see FIG. 25) of the silicon substrate when only the water repellent treatment step was not performed. The collapse rate in the displayed region was 1% or less, and it was shown that the occurrence of pattern collapse can be satisfactorily reduced by subjecting the pattern-forming surface of the silicon substrate to a water-repellent treatment step in advance.

(result)
As shown in FIGS. 16 to 23, Examples 1 to 5 using 1,1,2,2,3,3,4-heptafluorocyclopentane, which is a kind of fluorocarbon compound, as a drying auxiliary substance. In some cases, for example, it was confirmed that the occurrence of pattern collapse can be reduced as compared with the cases of Comparative Examples 1 and 2 using the conventional drying auxiliary substance t-butanol.

Further, as shown in FIGS. 16 to 18, in the case of Example 1 in which the liquid temperature of the drying auxiliary liquid is 40 ° C. and Example 3 in which the liquid temperature is 60 ° C., the liquid temperature is 23 ° C. Compared with the case of a certain Example 2, the reduction of the collapse of the pattern was extremely good. As a result, when the drying auxiliary liquid is used at a liquid temperature sufficiently higher than the melting point (20.5 ° C.) of the sublimable substance 1,1,2,2,3,3,4-heptafluorocyclopentane. Was shown to be able to satisfactorily reduce the occurrence of pattern collapse.

Further, as shown in FIG. 24, in the case of Example 6 in which the pattern-forming surface of the silicon substrate is previously subjected to the water-repellent treatment, cracks are found as compared with the case where the water-repellent treatment is not applied (see FIG. 25). It was confirmed that the collapse of the pattern did not occur and the collapse of the pattern was significantly reduced. The collapse rate in the displayed region was 1% or less, and it was shown that the occurrence of pattern collapse can be satisfactorily reduced by subjecting the pattern-forming surface of the silicon substrate to a water-repellent treatment step in advance.

The present invention can be applied to a drying technique for removing a liquid adhering to the surface of a substrate and a substrate processing technique for treating the surface of a substrate by using the drying technique.

1, 10 Board processing device 11 Chamber 12 Scattering prevention cup 13 Control unit 14 Swivel drive unit 15 Arithmetic processing unit 17 Memory 19 Board processing program 21 Processing liquid supply means (supply means)
22 Nozzle 23 Arm 24 Swivel shaft 25 Piping 26 Valve 27 Processing liquid storage 31 IPA supply means 32 Nozzle 33 Arm 34 Swivel shaft 35 Piping 36 Valve 37 IPA tank 41 Gas supply means (coagulation means, sublimation means)
42 Nozzle 43 Arm 44 Swivel shaft 45 Piping 46 Valve 47 Gas tank 51 Board holding means 52 Rotation drive unit 53 Spin base 54 Chuck pin 61 IPA
62 Drying auxiliary liquid 63 Coagulant 71 Depressurizing means 72 Exhaust pump 74 Valve 81 Water repellent supply means 82 Nozzle 83 Arm 84 Swivel shaft 85 Piping 86 Valve 87 Water repellent supply unit 271 Treatment liquid storage tank 272 Temperature control unit 273 Piping 274 Pressurizing part 275 Nitrogen gas tank 276 Pump 277 Stirring part 278 Stirring control part 279 Rotating part 471 Gas storage part 472 Gas temperature adjusting part A1, J1, J2, J3, J4 Axis AR1, AR2, AR3, AR4 Arrows P1, P2, P3 , P4 Retract position S11 Cleaning step S12 IPA rinsing step S13 Treatment liquid supply step (supply step)
S14 Solidification process S15 Sublimation process S16 Cleaning / rinsing process S17 Water repellent treatment process W Substrate Wf (Substrate) Front surface Wb (Substrate) Back surface Wp (Substrate surface) Pattern Wp1 (Pattern) Convex Wp2 (Pattern) Concave

Claims (10)

A supply means for supplying a treatment liquid containing a sublimable substance in a molten state to the pattern forming surface of the substrate,
A coagulation means for forming a coagulated body by coagulating the treatment liquid on the pattern forming surface,
A sublimation means for sublimating the solidified body and removing it from the pattern forming surface,
With
The supply means has a treatment liquid temperature adjusting unit that adjusts the temperature of the treatment liquid to a temperature higher than the melting point of the treatment liquid by 10 ° C. or more and lower than the boiling point of the treatment liquid.
The sublimable substance is observed contains a fluorocarbon compound,
A substrate processing apparatus, wherein the fluorocarbon compound is at least one of the following compounds (A) to (E).
Compound (A): Tetradecafluorohexane;
Compound (B): 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1,2,3,4,5-pentafluorocyclopentane, fluorocyclohexane, dodecafluorocyclohexane, 1,1,4-Trifluorocyclohexane, 2-fluorocyclohexanol, 4,4-difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid and 1,2,2,3,3,4,5,5 At least one selected from the group consisting of 6,6-undecafluoro-1- (nonafluorobutyl) cyclohexane;
Compound (C): 2- [difluoro (Undecafluorocyclohexyl) methyl] -1,1,2,3,3,4,4a, 5,5,6,6,7,7,8,8, 8a-Heptadecafluorodecahydronaphthalene;
Compound (D): Tetrafluorotetracyanoquinodimethane;
Compound (E): Hexafluorocyclotriphosphazene The substrate processing apparatus according to claim 1.
The supply means supplies the treatment liquid to the pattern forming surface of the substrate under atmospheric pressure.
The substrate processing apparatus is characterized in that the coagulation means cools the treatment liquid below the freezing point of the sublimable substance under atmospheric pressure. The substrate processing apparatus according to claim 1 or 2.
The fluorocarbon compound as the sublimable substance has sublimation property under atmospheric pressure and has a sublimation property.
The sublimation means is a substrate processing apparatus, characterized in that the sublimating substance is sublimated under atmospheric pressure. The substrate processing apparatus according to claim 3.
The coagulation means and the sublimation means are common gas supply means for supplying at least an inert gas inert to the sublimation substance toward the pattern forming surface at a temperature equal to or lower than the freezing point of the sublimation substance. A substrate processing device characterized by being present. The substrate processing apparatus according to claim 3.
At least one of the coagulation means and the sublimation means supplies the refrigerant at a temperature equal to or lower than the freezing point of the sublimable substance toward the back surface of the substrate opposite to the pattern forming surface. Sublimation processing equipment. The substrate processing apparatus according to claim 1.
The substrate processing apparatus, wherein the sublimation means is a decompression means for depressurizing the pattern-forming surface on which the solidified body is formed in an environment lower than atmospheric pressure. The substrate processing apparatus according to claim 6.
A substrate processing apparatus characterized in that the decompression means is used as the solidification means. The substrate processing apparatus according to any one of claims 1 to 7.
The substrate processing apparatus is characterized in that the supply means supplies the treatment liquid as a cleaning liquid or a rinsing liquid to the pattern-forming surface of the substrate to clean or rinse the pattern-forming surface. The substrate processing apparatus according to any one of claims 1 to 8.
A substrate treatment apparatus comprising: at least a water-repellent treatment means for treating the pattern-forming surface with water-repellent treatment before supplying the treatment liquid to the pattern-forming surface of the substrate. A supply process for supplying a treatment liquid containing a sublimated substance in a molten state to the pattern forming surface of the substrate, and
A coagulation step of coagulating the treatment liquid on the pattern forming surface to form a coagulated body,
A sublimation step of sublimating the solidified body and removing it from the pattern forming surface,
Including
In the supply step, the temperature of the treatment liquid is adjusted to a temperature higher than the melting point of the treatment liquid by 10 ° C. or more and lower than the boiling point of the treatment liquid, and the treatment liquid is supplied.
The sublimable substance is observed contains a fluorocarbon compound,
A substrate treatment method, wherein the fluorocarbon compound is at least one of the following compounds (A) to (E).
Compound (A): Tetradecafluorohexane;
Compound (B): 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclobutane, 1,2,3,4,5-pentafluorocyclopentane, fluorocyclohexane, dodecafluorocyclohexane, 1,1,4-Trifluorocyclohexane, 2-fluorocyclohexanol, 4,4-difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid and 1,2,2,3,3,4,5,5 At least one selected from the group consisting of 6,6-undecafluoro-1- (nonafluorobutyl) cyclohexane;
Compound (C): 2- [difluoro (Undecafluorocyclohexyl) methyl] -1,1,2,3,3,4,4a, 5,5,6,6,7,7,8,8, 8a-Heptadecafluorodecahydronaphthalene;
Compound (D): Tetrafluorotetracyanoquinodimethane;
Compound (E): Hexafluorocyclotriphosphazene

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