TW202129750A - Substrate processing method and substrate processing device - Google Patents

Abstract

This substrate processing method comprises: a pre-drying processing liquid supply step in which a pre-drying processing liquid, which is a solution obtained by dissolving a sublimable substance in a solvent, is supplied onto an upper surface of a substrate on which a pattern is formed, and a liquid film of the pre-drying processing liquid is formed on the upper surface of the substrate; a deposition step in which, by causing the solvent to be evaporated from the liquid film, a solid of the sublimable substance is deposited on the upper surface of the substrate; a concentration determination step in which, before the deposition of the solid of the sublimable substance in the deposition step, it is determined, on the basis of a film thickness reduction speed which is the speed at which the thickness of the liquid film is reduced by evaporation of the solvent, whether the concentration of the sublimable substance in the liquid film is within a reference concentration range; and a sublimation step in which, if it is determined in the concentration determination step that the concentration of the sublimable substance in the liquid film is within the reference concentration range, the solid of the sublimable substance is sublimated after completion of the deposition step.

Description

Substrate processing method

The present invention relates to a substrate processing method and substrate processing apparatus for processing substrates. The substrates include, for example, semiconductor wafers, liquid crystal display devices, or organic EL (electroluminescence, electroluminescence) display devices, such as FPD (Flat Panel Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, and optical disks. Cover substrates, ceramic substrates, solar cell substrates, etc.

In the manufacturing process of semiconductor devices, FPDs, etc., substrates such as semiconductor wafers or glass substrates for FPDs are treated as needed. Such processing includes supplying a processing liquid such as a chemical liquid or a rinse liquid to the substrate. After supplying the processing liquid, the processing liquid is removed from the substrate, and the substrate is dried. In a single-chip substrate processing apparatus that processes substrates one by one, spin drying is performed, that is, the substrate is dried by removing liquid on the substrate by high-speed rotation of the substrate.

When a pattern is formed on the surface of the substrate, when the substrate is dried, the force generated by the surface tension of the treatment liquid attached to the substrate may be applied to the pattern, which may cause the pattern to collapse. As a countermeasure, the following method is adopted: a liquid with a low surface tension such as IPA (isopropyl alcohol) is supplied to the substrate, or a hydrophobizing agent that makes the contact angle of the liquid with respect to the pattern close to 90 degrees is supplied to the substrate. However, even if IPA or a hydrophobizing agent is used, the damage to the pattern is not zero. Therefore, depending on the strength of the pattern, even if such countermeasures are taken, the damage of the pattern may not be sufficiently prevented.

In recent years, sublimation drying has attracted people's attention as a technique to prevent patterns from deteriorating. For example, Patent Document 1 discloses a substrate processing method and a substrate processing apparatus that perform sublimation drying. In the sublimation drying described in Patent Document 1, a solution of a sublimable substance is supplied to the upper surface of a substrate, and DIW (deionized water) on the substrate is replaced with a solution of the sublimable substance. Thereafter, the solvent of the sublimable substance is evaporated, and the sublimable substance is precipitated. Thereby, a film containing a solid sublimable substance is formed on the upper surface of the substrate. After that, the substrate is heated. Thereby, the sublimable substance on the substrate is sublimated and removed from the substrate. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-243869

[The problem to be solved by the invention]

Generally speaking, sublimation drying has a lower rate of pattern collapse than previous drying methods, such as spin drying using high-speed rotation of the substrate to remove liquid or IPA drying using IPA. However, if the strength of the pattern is extremely low, even if the sublimation drying is performed, it may not be possible to sufficiently prevent the pattern from breaking down. According to the research conducted by the inventors of the present case, one of the reasons is the thickness of the film containing the solid sublimable substance.

The thickness of the solid of the sublimation substance corresponds to the thickness of the solution of the sublimation substance when the saturated concentration of the sublimation substance is reached. As long as the concentration of the sublimable substance in the solution of the sublimable substance can be known before the saturation concentration of the sublimable substance is reached, the thickness of the solid of the sublimable substance can be predicted, and the formation of the solid of the sublimable substance of inappropriate thickness can be avoided.

Generally, in order to determine the concentration of a substance in a liquid, it is necessary to contact the device for concentration measurement with the liquid. Since the solution of the sublimable substance formed on the substrate is relatively thin, it is difficult to make the device for concentration measurement contact the liquid film without contacting the upper surface of the substrate. Therefore, there is a risk that the pattern may be damaged and collapsed due to the contact of the machine for measuring the concentration.

Therefore, one of the objectives of the present invention is to provide a substrate processing method and a substrate processing apparatus that can reduce the collapse rate of the pattern that occurs when sublimable substances are removed from the upper surface of the substrate by sublimation. [Technical means to solve the problem]

An embodiment of the present invention provides a substrate processing method comprising: a pre-drying treatment liquid supply process, which is a solution obtained by dissolving a sublimable substance in a solvent, that is, a pre-drying treatment liquid, which is supplied onto a patterned substrate The liquid film of the pre-drying treatment liquid is formed on the upper surface of the substrate; the precipitation process involves evaporating the solvent from the liquid film so that the solid of the sublimable substance is deposited on the substrate. Precipitation on the upper surface; concentration determination process, which is based on the rate at which the thickness of the liquid film decreases by the evaporation of the solvent, that is, the rate at which the film thickness decreases, to determine the liquid Whether the concentration of the sublimable substance in the film is within the reference concentration range; and the sublimation process, which is when the concentration of the sublimable substance in the liquid film is determined to be within the reference concentration range in the above concentration determination process, After the above precipitation process is completed, the solid of the above sublimable substance is sublimated.

According to this method, a solution in which a sublimable substance is dissolved in a solvent is supplied to the upper surface of the substrate. Thereby, a liquid film of the treatment liquid before drying is formed on the upper surface of the substrate. Thereafter, the solvent is evaporated from the liquid film of the pre-drying treatment liquid. The concentration of sublimable substances in the liquid film of the treatment solution before drying rises with the evaporation of the solvent. If the concentration of the sublimation substance reaches the saturation concentration of the sublimation substance, the solid of the sublimation substance will precipitate in the liquid film of the treatment solution before drying.

The inventors of the present case discovered that there is a correlation between the rate of film thickness reduction and the concentration of sublimable substances in the liquid film. Therefore, if the concentration of the sublimable substance in the liquid film is within the reference concentration range based on the rate of decrease in the thickness of the liquid film of the pre-drying treatment solution in the precipitation process, it is before the solid of the sublimable substance precipitates. , Before the concentration of the sublimation substance reaches the saturation concentration of the sublimation substance, it can be determined whether the concentration of the sublimation substance in the liquid film is within the reference concentration range. When it is determined that the concentration of the sublimable substance in the liquid film is within the reference concentration range, a solid of the sublimable substance with an appropriate thickness is formed. In addition, since the solid of the sublimable substance is sublimated after the precipitation process is completed, a substrate with a reduced pattern collapse rate can be obtained.

On the other hand, when it is judged that the concentration of the sublimable substance in the liquid film is not within the reference concentration range, if the substrate processing is interrupted, the sublimation of the sublimable substance with an inappropriate thickness can be prevented beforehand. Thereby, the increase in the collapse rate of the pattern can be suppressed.

In one embodiment of the present invention, the concentration determination process includes the following process: by comparing the pre-measured reference data with the film thickness reduction rate measured in the precipitation process, inferring the film thickness in the liquid film The concentration of sublimable substances. Therefore, in the precipitation process, the concentration of the sublimable substance in the liquid film can be easily estimated.

In one embodiment of the present invention, the substrate processing method further includes a pre-drying treatment liquid removal process, and the pre-drying treatment liquid removal process is performed in the concentration determination process to determine that the concentration of the sublimable substance in the liquid film is not the above When the concentration is within the reference concentration range, the pre-drying treatment liquid is removed from the upper surface of the substrate by supplying a removing liquid to the upper surface of the substrate before the solid of the sublimable substance precipitates in the precipitation process.

According to this method, when the concentration of the sublimable substance in the liquid film is not within the reference concentration range, the sublimable substance can be removed from the upper surface of the substrate by the removing liquid before the solid of the sublimable substance precipitates. Thereby, it is possible to prevent the formation of a solid of sublimable material of inappropriate thickness on the upper surface of the substrate before it happens. Therefore, the increase in the collapse rate of the pattern can be suppressed. In addition, since the pre-drying treatment liquid on the upper surface of the substrate is removed, the substrate can be reused.

In one embodiment of the present invention, the substrate processing method further includes a solvent evaporation promotion process, and the solvent evaporation promotion process determines that the concentration of the sublimable substance in the liquid film is lower than the reference concentration range in the concentration determination process In the case of the lower limit, the evaporation of the solvent from the liquid film is promoted during the execution of the precipitation process.

According to this method, when it is determined in the concentration determination process that the concentration of the sublimable substance in the liquid film of the treatment solution before drying is lower than the lower limit of the reference concentration range, the evaporation of the solvent from the liquid film of the treatment solution before drying is promoted. If the evaporation of the solvent from the liquid film of the treatment liquid before drying is promoted, the concentration of the sublimable substance in the liquid film of the treatment liquid before drying will increase. Therefore, the concentration of the sublimable substance in the liquid film of the treatment solution before drying can be adjusted to be within the reference concentration range. Therefore, even if the concentration of the sublimable substance in the liquid film of the pre-drying treatment solution is determined to be lower than the lower limit of the reference concentration range in the concentration determination process, a substrate with a reduced pattern collapse rate can be obtained.

In one embodiment of the present invention, the solvent evaporation promotion process includes the following process: by supplying an inert gas to the gas atmosphere in contact with the liquid film, the vapor of the solvent is removed from the gas atmosphere in contact with the liquid film .

According to this method, an inert gas is supplied, and the vapor of the solvent is removed from the gas atmosphere in contact with the liquid film of the pre-drying treatment liquid on the upper surface of the substrate. Therefore, the evaporation of the solvent from the liquid film of the treatment liquid before drying can be promoted.

In one embodiment of the present invention, the above-mentioned substrate processing method further includes: a substrate rotation process, in which the upper surface of the substrate is rotated around a rotation axis in a vertical direction during the deposition process; and a thin-filming process, When it is determined in the above concentration determination process that the concentration of the sublimable substance in the liquid film is higher than the upper limit of the above reference concentration range, before the solid of the sublimable substance precipitates during the execution of the above precipitation process , By increasing the rotation speed of the substrate, the liquid film is thinned.

When the concentration of the sublimable substance in the liquid film of the pre-drying treatment solution is higher than the upper limit of the reference concentration range, the solid thickness of the sublimable substance immediately before sublimation is greater than the intended value. If the thickness of the liquid film of the treatment liquid before drying on the substrate is reduced, the amount of the sublimable substance contained in the liquid film of the treatment liquid before drying is reduced, and therefore, the solid thickness of the sublimation substance is also reduced.

Therefore, when the concentration of the sublimable substance in the liquid film of the pre-drying treatment solution is higher than the upper limit of the reference concentration range, by increasing the rotation speed of the substrate, the centrifugal force acts on the upper surface of the substrate. The liquid film of the treatment liquid before drying can reduce the thickness of the liquid film of the treatment liquid before drying before the solid of the sublimation substance is deposited. Thereby, the solid of the sublimable substance of the intended thickness can be precipitated. Therefore, even if the concentration of the sublimable substance in the liquid film of the pre-drying treatment solution is determined to be higher than the upper limit of the reference concentration range in the concentration determination process, a substrate with a reduced pattern collapse rate can be obtained.

In one embodiment of the present invention, the substrate processing method further includes a solvent evaporation suppression process, wherein the solvent evaporation suppression process determines that the concentration of the sublimable substance in the liquid film is higher than the reference concentration range in the concentration determination process In the case of the upper limit value, the evaporation of the solvent from the liquid film is suppressed during the execution of the precipitation process.

According to this method, when the concentration of the sublimable substance in the liquid film is determined to be higher than the upper limit of the reference concentration range in the concentration determination process, the evaporation of the solvent from the liquid film of the treatment solution before drying is suppressed. If the evaporation of the solvent from the liquid film of the treatment solution before drying is suppressed, the ratio of the sublimable substance in the substance evaporated from the liquid film will increase. Thereby, the concentration of the sublimable substance in the liquid film of the treatment liquid before drying is reduced. Therefore, the concentration of the sublimable substance in the liquid film of the treatment solution before drying can be adjusted to be within the reference concentration range.

Therefore, even if the concentration of the sublimable substance in the liquid film of the pre-drying treatment solution is determined to be higher than the upper limit of the reference concentration range in the concentration determination process, a substrate with a reduced pattern collapse rate can be obtained.

In one embodiment of the present invention, the solvent evaporation suppression process includes a process of suppressing evaporation of the solvent from the liquid film by supplying vapor or mist of the solvent to the gas atmosphere in contact with the liquid film.

According to this method, by supplying the vapor or mist of the solvent to the gas atmosphere in contact with the liquid film of the pre-drying treatment liquid on the upper surface of the substrate, there is a gas atmosphere in contact with the liquid film of the pre-drying treatment liquid The amount of solvent increases. Therefore, the evaporation of the solvent from the liquid film of the treatment liquid before drying is suppressed.

In one embodiment of the present invention, the substrate processing method further includes a first abnormality notification process, and the first abnormality notification process is in the concentration determination process to determine that the concentration of the sublimable substance in the liquid film is not the reference concentration If the situation is within the scope, an abnormality will be reported. Therefore, it is possible to determine whether to continue the substrate processing at an appropriate time based on the notification of the abnormality.

In one embodiment of the present invention, the above-mentioned substrate processing method further includes: a film thickness measurement process in which the solid of the sublimable substance is deposited immediately before the solid of the sublimable substance is deposited by the evaporation of the solvent in the precipitation process, and the measurement of the liquid film Thickness; and the thickness determination process, which determines whether the thickness of the liquid film measured in the film thickness measurement process is within the reference thickness range of the solid of the sublimable substance.

According to this method, it is determined whether the thickness of the liquid film just before the precipitation of the solid of the sublimable substance, that is, the thickness of the liquid film when the concentration of the sublimable substance reaches the saturated concentration of the sublimable substance, is within the reference thickness range of the solid of the sublimable substance . By this, it can be determined whether the solid thickness of the sublimable substance formed on the upper surface of the substrate is appropriate.

When the thickness of the solid of the sublimable substance formed on the upper surface of the substrate is appropriate, after the precipitation process is completed, the solid of the sublimable substance of appropriate thickness is formed. Therefore, a substrate with a reduced pattern collapse rate can be obtained.

On the other hand, when the solid thickness of the sublimable substance formed on the upper surface of the substrate is inappropriate, the increase in the collapse rate of the pattern can be suppressed by interrupting the substrate processing.

In one embodiment of the present invention, the substrate processing method further includes a second abnormality notification process, and the second abnormality notification process is in the thickness determination process to determine that the thickness of the liquid film measured in the film thickness measurement process is not In the case of the above-mentioned reference thickness range, an abnormality will be reported. Therefore, it is possible to determine whether to continue the substrate processing at an appropriate time based on the notification of the abnormality.

In one embodiment of the present invention, the substrate processing method further includes: a first precipitation process, which evaporates the solvent from the pre-drying treatment liquid on the upper surface of the substrate to make the sublimable substance The solid is precipitated in the pre-drying treatment liquid on the upper surface of the substrate; the first dissolution process is to dissolve at least a part of the solid of the sublimable substance in the first precipitation process on the upper surface of the substrate The above-mentioned pre-drying treatment liquid; and the final precipitation process, which evaporates the above-mentioned pre-drying treatment liquid formed by dissolving the solvent from the solid of the sublimable substance in the first dissolution process, so that the sublimable substance is evaporated The solid is deposited on the upper surface of the substrate. Furthermore, the precipitation process is the first precipitation process, and the sublimation process is performed after the final precipitation process is completed. In addition, the first dissolution process is performed when it is determined that the thickness of the liquid film is within the reference thickness range in the thickness determination process.

When the solid of the sublimable substance starts to precipitate in the first precipitation process, the pre-drying treatment liquid remains on the upper surface of the substrate. In the first dissolution process, at least a part of the solid of the sublimation substance is dissolved in the pre-drying treatment liquid. Thereafter, in the final precipitation process, the solvent is again evaporated from the pre-drying treatment liquid. Thereby, the content of the solvent is reduced, and the solid of the sublimation substance is deposited on the upper surface of the substrate.

Before the solid of the sublimable substance is precipitated for the first time, the pre-drying treatment liquid not only exists between the patterns, but also exists above the patterns. In substrates such as semiconductor wafers or FPD substrates, the pattern spacing is narrow. When the pattern interval is narrow, the nature of the pre-drying treatment liquid existing between the patterns and the main body of the pre-drying treatment liquid, in other words, it is located from the surface of the pre-drying treatment liquid on the upper surface of the substrate to the pattern The pre-drying treatment liquid is different for the surface area. The difference in the nature of the two becomes significant as the pattern interval narrows.

If the pattern interval is narrow, the following situation exists: when the solid of the sublimable substance is precipitated for the first time, the solid of the sublimable substance is only precipitated in the main body of the treatment liquid before drying, and the solid of the sublimable substance does not exist or almost does not exist The incomplete precipitation area between the patterns is formed in the upper surface of the substrate. In this case, the surface tension of the pre-drying treatment liquid between the patterns is applied to the sides of the pattern. Therefore, when the solid of the sublimable substance is sublimated, the pattern in the incomplete precipitation area may collapse. This becomes the cause of the increase (deterioration) of the collapse rate of the pattern.

On the other hand, if the solid of the sublimable substance is dissolved in the pre-drying treatment liquid, and the solid of the sublimable substance is precipitated again, the solid of the sublimable substance will also be formed in a narrow space such as the space between the patterns. Crystalline nucleus. Therefore, as long as the solid of the sublimable substance precipitated in the first dissolution process is dissolved in the pre-drying treatment liquid, and the solid of the sublimable substance is precipitated again in the final precipitation process, even when the pattern interval is narrow , Can also prevent the generation of incomplete precipitation area, or reduce its area.

Furthermore, according to this method, the first dissolution process is started when the thickness of the liquid film of the treatment solution before drying is determined to be within the reference thickness range in the thickness determination process. In other words, the first dissolution process starts with the formation of a solid sublimation substance with an appropriate thickness as an opportunity. Therefore, the first dissolution process, the final precipitation process, and the sublimation process are performed only when the solid of the sublimable substance with an appropriate thickness is formed. After the sublimation process is over, a substrate with reduced pattern collapse rate can be obtained.

In the case where a solid with a proper thickness of the sublimable substance is not formed, the processes after the first precipitation process (the first dissolution process, the final precipitation process, and the sublimation process) may not be performed, and the substrate processing may be interrupted earlier.

In one embodiment of the present invention, the substrate processing method further includes: a first precipitation process, which evaporates the solvent from the pre-drying treatment liquid on the upper surface of the substrate to make the sublimable substance The solid is precipitated in the pre-drying treatment liquid on the upper surface of the substrate; the first dissolution process involves dissolving at least a part of the solid of the sublimable substance on the upper surface of the substrate. And the final precipitation process, which evaporates the pre-drying treatment liquid formed by dissolving the solvent from the solid of the sublimable substance, so that the solid of the sublimable substance is precipitated on the upper surface of the substrate. Furthermore, the precipitation process includes at least one of the first precipitation process and the final precipitation process, and the sublimation process is performed after the final precipitation process.

According to this method, after the precipitated solid of the sublimable substance is dissolved in the pre-drying treatment liquid, the solid of the sublimable substance is precipitated again. Therefore, even when the pattern interval is narrow, the generation of incomplete precipitation regions can be prevented, or the area can be reduced. In this way, the damage of the pattern can be reduced, and the collapse rate of the pattern can be reduced.

Furthermore, according to this method, in at least any one of the first precipitation process and the final precipitation process, the liquid film is determined before the solid of the sublimable substance is precipitated, that is, before the concentration of the sublimable substance reaches the saturation concentration of the sublimable substance Is the concentration of sublimable substances in the reference concentration range. When it is determined that the concentration of the sublimable substance in the liquid film is within the reference concentration range, a solid of the sublimable substance with an appropriate thickness is formed. In addition, since the solid of the sublimable substance is sublimated after the final precipitation process is completed, a substrate with reduced pattern collapse rate can be obtained.

On the other hand, when it is judged that the concentration of the sublimable substance in the liquid film is not within the reference concentration range, if the substrate processing is interrupted, the sublimation of the sublimable substance with an inappropriate thickness can be prevented beforehand. Thereby, the increase in the collapse rate of the pattern can be suppressed.

The collapse rate of the pattern depends on the solid thickness of the sublimable substance finally formed on the upper surface of the substrate. Therefore, the concentration determination process is preferably performed in the final precipitation process. However, the amount of solvent evaporated in the first dissolution process and the final precipitation process can be predicted. Therefore, even when the concentration determination process is performed in the first precipitation process, the solid of the sublimable material formed on the upper surface of the substrate can be determined based on the concentration of the sublimable substance in the liquid film in the first precipitation process Whether the thickness is appropriate.

Another embodiment of the present invention provides a substrate processing method, which includes: a pre-drying treatment liquid supply process, which is a solution obtained by dissolving a sublimable substance in a solvent, that is, the pre-drying treatment liquid is supplied to a patterned substrate On the upper surface, the liquid film of the pre-drying treatment liquid is formed on the upper surface of the substrate; the precipitation process involves evaporating the solvent from the liquid film to make the solid of the sublimable substance on the substrate The above-mentioned upper surface is deposited; a flatness measurement process, which is performed in the above-mentioned precipitation process, after the solid of the sublimable substance is deposited by the evaporation of the solvent, and then the above-mentioned sublimation is measured at multiple locations on the above-mentioned upper surface of the substrate The height position of the solid of the substance is measured to determine the flatness of the surface of the solid of the sublimable substance; the flatness determination process is to determine whether the flatness measured in the flatness determination process is within the reference flat range; and the sublimation process, It is to sublimate the solid of the sublimable substance when it is determined that the degree of flatness is within the reference flat range in the flatness determination process.

According to this method, a solution in which a sublimable substance is dissolved in a solvent is supplied to the upper surface of the substrate. Thereby, a liquid film of the treatment liquid before drying is formed on the upper surface of the substrate. Thereafter, the solvent is evaporated from the liquid film of the pre-drying treatment liquid. The concentration of sublimable substances in the liquid film of the treatment solution before drying rises with the evaporation of the solvent. If the concentration of the sublimation substance reaches the saturation concentration of the sublimation substance, the solid of the sublimation substance will precipitate in the liquid film of the treatment solution before drying.

When a part of the solid part of the sublimable substance has an excessively thin part or an excessively thick part, there is a possibility that the collapse rate of the pattern in the part may increase. Therefore, the flatness of the solid surface of the sublimable substance precipitated on the upper surface of the substrate is measured, and it is determined whether the measured flatness is within the reference flat range. Thereby, it can be checked whether a solid of sublimable substance with uniform thickness is formed on the entire area of the upper surface of the substrate.

When it is judged that the flatness of the solid of the sublimable substance is within the reference flat range, the solid of the sublimable substance is sublimated, so that a substrate with a reduced pattern collapse rate can be obtained. On the other hand, when it is determined that the flatness of the solid of the sublimable substance is not within the reference flat range, the substrate processing can be interrupted to suppress the occurrence of the substrate with an increase in the collapse rate of the pattern.

In another embodiment of the present invention, the above-mentioned substrate processing method further includes a solid removal process, and the above-mentioned solid removal process is performed by removing the removal liquid when it is determined in the flatness measurement process that the flatness is not within the reference flat range. It is supplied to the upper surface of the substrate, and the solid of the sublimable substance is removed from the upper surface of the substrate.

According to this method, when the flatness of the solid of the sublimable substance is not within the reference flat range, the solid of the sublimable substance is removed from the upper surface of the substrate by the removing liquid. Therefore, when there is an excessively thin part or an excessively thick part in a solid part of the sublimable material, the pattern can also be suppressed from being damaged. In addition, since the solids of sublimable substances on the upper surface of the substrate are removed, the substrate can be reused.

Another embodiment of the present invention provides a substrate processing apparatus including: a pre-drying treatment liquid supply unit, which dissolves a sublimable substance in a solvent, that is, a solution of the pre-drying treatment liquid as a liquid film formed on a patterned pattern The upper surface of the substrate is supplied to the upper surface of the substrate; a solvent evaporation unit that evaporates the solvent from the liquid film by the solid precipitation of the sublimable substance; a film thickness measurement unit that measures the thickness of the liquid film Thickness; a sublimation unit that sublimates the solid of the sublimable substance formed on the substrate; and a controller that determines whether the concentration of the sublimable substance in the liquid film is within a reference concentration range. According to this structure, the same effect as the above-mentioned substrate processing method is obtained.

With reference to the accompanying drawings, the above-mentioned objects, or other objects, features, and effects of the present invention will be clarified by the description of the embodiments described below.

In the following description, unless otherwise specified, the air pressure in the substrate processing apparatus 1 is maintained at the air pressure in the clean room where the substrate processing apparatus 1 is installed (for example, 1 air pressure or a value near it).

Fig. 1A is a schematic view of a substrate processing apparatus 1 according to an embodiment of the present invention viewed from above. FIG. 1B is a schematic diagram of the substrate processing apparatus 1 viewed from the side.

As shown in FIG. 1A, the substrate processing device 1 is a single-chip device that processes disk-shaped substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 includes: a load port LP that holds a carrier CA that houses a substrate W; a plurality of processing units 2 that use processing fluids such as processing liquid or processing gas to process the substrate W transported from the carrier CA on the load port LP; The manipulator, which transports the substrate W between the carrier CA on the load port LP and the processing unit 2; and the controller 3, which controls the substrate processing device 1.

The transport robot includes: an indexing robot IR, which carries in and out of the substrate W on the carrier CA on the load port LP; and a central robot CR, which carries in and out of the substrate W for a plurality of processing units 2. The indexing robot IR transfers the substrate W between the load port LP and the center robot CR, and the center robot CR transfers the substrate W between the indexing robot IR and the processing unit 2. The center robot CR includes a hand H1 that supports the substrate W, and the indexing robot IR includes a hand H2 that supports the substrate W.

A plurality of processing units 2 form a plurality of towers TW arranged around the central robot CR in a plan view. Fig. 1A shows an example in which four towers TW are formed. The central manipulator CR can enter any tower TW. As shown in FIG. 1B, each tower TW includes a plurality of (for example, 3) processing units 2 stacked one above the other.

FIG. 2 is a schematic view of the inside of the processing unit 2 included in the substrate processing apparatus 1 when viewed horizontally.

The processing unit 2 is a wet processing unit 2w that supplies the processing liquid to the substrate W. The processing unit 2 includes: a box-shaped chamber 4 with an internal space; a rotating chuck 10, which holds a substrate W horizontally in the chamber 4, and makes it pass through the center of the upper surface of the substrate W in the chamber 4 The vertical rotation axis A1 rotates; and the cylindrical processing cup 21, which surrounds the rotating chuck 10 around the rotation axis A1.

The chamber 4 includes: a box-shaped partition wall 5 provided with a loading/unloading port 5b through which the substrate W passes; and a shutter 7 which opens and closes the loading/unloading port 5b. The FFU (fan filter unit, fan filter unit) 6 is arranged on the air supply port 5 a provided on the upper part of the partition wall 5. The FFU 6 always supplies clean air (air filtered by a filter) into the chamber 4 from the air supply port 5a. The gas in the chamber 4 is discharged from the chamber 4 through an exhaust duct 8 connected to the bottom of the processing cup 21. Thereby, the downflow of clean air is always formed in the chamber 4. The flow rate of the exhaust gas discharged by the exhaust duct 8 is changed according to the opening degree of the exhaust valve 9 arranged in the exhaust duct 8.

The rotating chuck 10 includes: a disk-shaped rotating base 12 that is held in a horizontal position; a plurality of chuck pins 11 that hold the substrate W in a horizontal position above the rotating base 12; and a rotating shaft 13 that is self-rotating the base The central part of 12 extends downward; and the rotating motor 14 which rotates the rotating base 12 and the plural chuck pins 11 by rotating the rotating shaft 13. The rotating chuck 10 is not limited to a clamping chuck in which a plurality of chuck pins 11 are in contact with the outer peripheral surface of the substrate W, and may be a non-device forming surface, that is, the back surface (lower surface) of the substrate W by being attracted to the rotating chuck. The upper surface 12u of the base 12 is a vacuum chuck for holding the substrate W horizontally.

The processing cup 21 includes: a plurality of sheaths 24, which receive the processing liquid discharged from the substrate W to the outside; a plurality of cups 23, which receive the processing liquid guided downward by the plurality of sheaths 24; and a circle The cylindrical outer wall member 22 surrounds a plurality of sheaths 24 and a plurality of cups 23. FIG. 2 shows an example in which four sheaths 24 and three cups 23 are provided, and the outermost cup 23 and the third sheath 24 from the top are integrated.

The sheath 24 includes a cylindrical portion 25 that surrounds the rotating chuck 10 and an annular top portion 26 that extends obliquely upward from the upper end of the cylindrical portion 25 toward the rotation axis A1. A plurality of top portions 26 are overlapped up and down, and a plurality of cylindrical portions 25 are arranged concentrically. The annular upper end of the top portion 26 is equivalent to the upper end 24u of the sheath 24 surrounding the substrate W and the rotating base 12 in a plan view. The plurality of cups 23 are respectively arranged below the plurality of cylindrical parts 25. The cup 23 forms a ring-shaped liquid receiving groove for receiving the processing liquid guided downward by the sheath 24.

The processing unit 2 includes a sheath elevating unit 27 for individually raising and lowering a plurality of sheaths 24. The sheath lifting unit 27 positions the sheath 24 at any position from the upper position to the lower position. The sheath lift unit 27 is also called a sheath lifter. FIG. 2 shows a state in which two sheaths 24 are arranged in the upper position and the remaining two sheaths 24 are arranged in the lower position. The upper position means that the upper end 24u of the sheath 24 is arranged above the holding position where the substrate W held by the rotating chuck 10 is arranged. The lower position means that the upper end 24u of the sheath 24 is arranged at a position lower than the holding position.

When the processing liquid is supplied to the rotating substrate W, at least one sheath 24 is arranged at the upper position. In this state, when the processing liquid is supplied to the substrate W, the processing liquid supplied to the substrate W is thrown away to the periphery of the substrate W. The thrown away processing liquid collides with the inner surface of the sheath 24 horizontally opposite to the substrate W, and is guided to the cup 23 corresponding to the sheath 24. Thereby, the processing liquid discharged from the substrate W is collected in the processing cup 21.

The processing unit 2 includes a plurality of nozzles for ejecting processing liquid to the substrate W held by the spin chuck 10. The plurality of nozzles include: a chemical liquid nozzle 31 which sprays chemical liquid onto the upper surface of the substrate W; a rinse liquid nozzle 35 which sprays a rinse liquid onto the upper surface of the substrate W; and a pre-drying treatment liquid nozzle 39 which sprays the liquid onto the substrate W The surface sprays the pre-drying treatment liquid; and the replacement liquid nozzle 43, which sprays the replacement liquid onto the upper surface of the substrate W.

The liquid medicine nozzle 31 may be a scanning nozzle that can move horizontally in the chamber 4, or a fixed nozzle that is fixed with respect to the partition wall 5 of the chamber 4. The same applies to the rinse liquid nozzle 35, the pre-drying treatment liquid nozzle 39, and the replacement liquid nozzle 43. 2 shows an example in which the chemical liquid nozzle 31, the rinse liquid nozzle 35, the pre-drying treatment liquid nozzle 39, and the replacement liquid nozzle 43 are scanning nozzles and are provided with four nozzle moving units corresponding to the four nozzles.

The chemical liquid nozzle 31 is connected to a chemical liquid pipe 32 that guides the chemical liquid to the chemical liquid nozzle 31. When the chemical liquid valve 33 installed in the chemical liquid pipe 32 is opened, the chemical liquid is continuously ejected downward from the ejection port of the chemical liquid nozzle 31. The chemical liquid sprayed from the chemical liquid nozzle 31 may include sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia water, hydrogen peroxide water, organic acid (for example, citric acid, oxalic acid, etc.), and organic alkali (for example, TMAH: tetramethylammonium hydroxide, etc.), a surfactant, and a preservative of at least one of the liquids, and it can also be other liquids.

Although not shown, the liquid medicine valve 33 includes: a valve body, which is provided with an annular valve seat through which liquid medicine can pass; a valve body, which can move relative to the valve seat; and an actuator, which causes the valve body to move Move between the closed position where the valve body is in contact with the valve seat and the open position where the valve body is away from the valve seat. The same applies to other valves. The actuator can be a pneumatic actuator or an electric actuator, or an actuator other than them. The controller 3 opens and closes the liquid medicine valve 33 by controlling the actuator.

The chemical liquid nozzle 31 is connected to a nozzle moving unit 34 that moves the chemical liquid nozzle 31 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 34 makes the chemical liquid nozzle 31 horizontal between the processing position where the chemical liquid sprayed from the chemical liquid nozzle 31 is supplied to the upper surface of the substrate W and the standby position where the chemical liquid nozzle 31 is located around the processing cup 21 in a plan view. move.

The washing liquid nozzle 35 is connected to a washing liquid pipe 36 that guides the washing liquid to the washing liquid nozzle 35. When the flushing fluid valve 37 installed in the flushing fluid pipe 36 is opened, the flushing fluid is continuously ejected downward from the ejection port of the flushing fluid nozzle 35. The rinse liquid sprayed from the rinse liquid nozzle 35 is, for example, pure water (DIW (Deionized Water)). The rinsing fluid can also be any one of carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and hydrochloric acid water with a dilution concentration (for example, about 10 ppm to 100 ppm).

The rinsing liquid nozzle 35 is connected to a nozzle moving unit 38 that moves the rinsing liquid nozzle 35 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 38 makes the rinse liquid nozzle 35 horizontal between the processing position where the rinse liquid ejected from the rinse liquid nozzle 35 is supplied to the upper surface of the substrate W and the standby position where the rinse liquid nozzle 35 is located around the processing cup 21 in a plan view. move.

The pre-drying treatment liquid nozzle 39 is connected to a pre-drying treatment liquid pipe 40 that guides the treatment liquid to the pre-drying treatment liquid nozzle 39. When the pre-drying treatment liquid valve 41 installed in the pre-drying treatment liquid piping 40 is opened, the pre-drying treatment liquid is continuously ejected downward from the nozzle 39 of the pre-drying treatment liquid. Similarly, the replacement liquid nozzle 43 is connected to a replacement liquid piping 44 that guides the replacement liquid to the replacement liquid nozzle 43. When the replacement liquid valve 45 installed in the replacement liquid piping 44 is opened, the replacement liquid is continuously ejected downward from the ejection port of the replacement liquid nozzle 43.

The pre-drying treatment liquid is a solution containing a sublimable substance as a solute and a solvent for dissolving the sublimable substance. The sublimable substance may also be a substance that changes from a solid to a gas without passing through a liquid under normal temperature (synonymous with room temperature) or normal pressure (pressure in the substrate processing apparatus 1, for example, 1 atmosphere or its vicinity).

The freezing point of the treatment solution before drying (the freezing point at 1 atmosphere, the same below) is lower than room temperature (for example, 23°C or its vicinity). The substrate processing apparatus 1 is arranged in a clean room maintained at room temperature. Therefore, even if the pre-drying treatment liquid is not heated, the pre-drying treatment liquid can be maintained as a liquid. The freezing point of the sublimation material is higher than the freezing point of the treatment solution before drying. The freezing point of sublimable substances is higher than room temperature. At room temperature, the sublimable substance is solid. The freezing point of the sublimation substance can also be higher than the boiling point of the solvent. The vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance.

The sublimation substance can be, for example, 2-methyl-2-propanol (alias: tert-Butyl alcohol, t-Butyl alcohol) or alcohols such as cyclohexanol, hydrogen fluorine Any one of carbon compound, 1,3,5-trioxane (alias: trioxane), camphor (alias: camphre, camper), naphthalene, and iodine, or other than them. Other substances.

The solvent can be selected from pure water, IPA, methanol, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), for example. , And at least one of the group consisting of ethylene glycol.

Hereinafter, an example in which the sublimable substance is camphor and the solvent is IPA or methanol will be described.

The freezing point of camphor is 175℃～177℃. No matter which solvent is IPA or methanol, the freezing point of camphor is higher than the boiling point of the solvent. The vapor pressure of IPA is higher than that of camphor. Similarly, the vapor pressure of methanol is higher than that of camphor. Therefore, IPA and methanol are easier to evaporate than camphor. The vapor pressure of IPA is higher than water, and the surface tension is lower than water. Similarly, the vapor pressure of methanol is higher than that of water, and the surface tension is lower than that of water. The molecular weights of IPA and methanol are both greater than that of water. The molecular weight of methanol is less than IPA.

As described below, the replacement liquid is supplied to the upper surface of the substrate W covered by the liquid film of the rinse liquid, and the pre-drying treatment liquid is supplied to the upper surface of the substrate W covered by the liquid film of the replacement liquid. As long as it is compatible with both the rinse liquid and the pre-drying treatment liquid, the replacement liquid may be any liquid. The replacement liquid is, for example, IPA (liquid). The replacement liquid may also be a mixed liquid of IPA and HFE, or a liquid other than these. The replacement liquid may be a liquid with the same name as the component of the pre-drying treatment liquid such as a solvent, or a liquid with a different name from any component of the pre-drying treatment liquid.

When the replacement liquid is supplied to the upper surface of the substrate W covered by the liquid film of the rinse liquid, most of the rinse liquid on the substrate W is washed away by the replacement liquid and discharged from the substrate W. The remaining trace amount of rinsing fluid is dissolved in the replacement fluid and diffused in the replacement fluid. The diffused rinsing liquid and the replacement liquid are discharged from the substrate W together. Therefore, the rinse liquid on the substrate W can be efficiently replaced with the replacement liquid. For the same reason, the replacement liquid on the substrate W can be efficiently replaced with the pre-drying treatment liquid. Thereby, the rinse liquid contained in the pre-drying treatment liquid on the substrate W can be reduced.

The pre-drying treatment liquid nozzle 39 is connected to a nozzle moving unit 42 that moves the pre-drying treatment liquid nozzle 39 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 42 causes the pre-drying treatment liquid nozzle 39 to supply the pre-drying treatment liquid ejected from the pre-drying treatment liquid nozzle 39 to the processing position on the upper surface of the substrate W, and the pre-drying treatment liquid nozzle 39 is located in the treatment cup 21 in a plan view. Move horizontally between the surrounding standby positions.

Similarly, the replacement liquid nozzle 43 is connected to a nozzle moving unit 46 that moves the replacement liquid nozzle 43 in at least one of the vertical direction and the horizontal direction. The nozzle moving unit 46 makes the replacement liquid nozzle 43 horizontal between the processing position where the replacement liquid ejected from the replacement liquid nozzle 43 is supplied to the upper surface of the substrate W and the standby position where the replacement liquid nozzle 43 is located around the processing cup 21 in a plan view. move.

The processing unit 2 includes a blocking member 51 disposed above the rotating chuck 10. FIG. 2 shows an example in which the blocking member 51 is a disk-shaped blocking plate. The blocking member 51 includes a circular plate portion 52 horizontally arranged above the rotating chuck 10. The blocking member 51 is horizontally supported by a cylindrical support shaft 53 extending upward from the central portion of the circular plate portion 52. The center line of the circular plate portion 52 is arranged on the rotation axis A1 of the substrate W. The lower surface of the disc portion 52 corresponds to the lower surface 51L of the blocking member 51. The lower surface 51L of the blocking member 51 is an opposite surface facing the upper surface of the substrate W. The lower surface 51L of the blocking member 51 is parallel to the upper surface of the substrate W and has an outer diameter greater than the diameter of the substrate W.

The blocking member 51 is connected to a blocking member elevating unit 54 that vertically raises and lowers the blocking member 51. The blocking member lifting unit 54 is also referred to as a blocking member lifter. The blocking member lifting unit 54 positions the blocking member 51 at any position from the upper position (the position shown in FIG. 2) to the lower position. The lower position is an approaching position where the lower surface 51L of the blocking member 51 approaches the upper surface of the substrate W until the scanning nozzles such as the chemical liquid nozzle 31 cannot enter the height between the substrate W and the blocking member 51. The upper position is a spaced position where the blocking member 51 is retracted until the scanning nozzle can enter the height between the blocking member 51 and the substrate W.

The plurality of nozzles include a center nozzle 55 that ejects a processing fluid such as a processing liquid or a processing gas downward through an upper central opening 61 formed at the center of the lower surface 51L of the blocking member 51. The center nozzle 55 extends up and down along the rotation axis A1. The center nozzle 55 is arranged in a through hole that penetrates the center portion of the blocking member 51 up and down. The inner peripheral surface of the blocking member 51 surrounds the outer peripheral surface of the center nozzle 55 at intervals in the radial direction (direction orthogonal to the rotation axis A1). The center nozzle 55 moves up and down together with the blocking member 51. The ejection port of the central nozzle 55 for ejecting the processing fluid is arranged above the central opening 61 of the blocking member 51.

The center nozzle 55 is connected to a gas piping 56 that guides the inert gas onto the center nozzle 55. The substrate processing apparatus 1 may include an upper temperature regulator 59 that heats or cools the inert gas sprayed from the center nozzle 55. When the gas valve 57 installed on the upper gas piping 56 is opened, the inert gas is continuously ejected downward from the outlet of the center nozzle 55 at a flow rate corresponding to the opening of the flow rate adjustment valve 58 that changes the flow rate of the inert gas. . The inert gas sprayed from the central nozzle 55 is nitrogen. The inert gas sprayed from the central nozzle 55 may also be a gas other than nitrogen such as helium or argon.

The inner peripheral surface of the blocking member 51 and the outer peripheral surface of the center nozzle 55 form a cylindrical upper gas flow path 62 extending up and down. The upper gas flow path 62 is connected to a gas piping 63 that guides the inert gas to the upper central opening 61 of the blocking member 51. The substrate processing apparatus 1 may include an upper temperature regulator 66 for heating or cooling the inert gas sprayed from the central opening 61 on the blocking member 51. When the gas valve 64 installed on the upper gas piping 63 is opened, the inert gas is drawn downward from the upper central opening 61 of the blocking member 51 at a flow rate corresponding to the opening of the flow rate adjusting valve 65 for changing the flow rate of the inert gas Spout continuously. The inert gas sprayed from the central opening 61 on the blocking member 51 is nitrogen. The inert gas sprayed from the central opening 61 on the blocking member 51 may also be a gas other than nitrogen such as helium or argon.

The plurality of nozzles includes a lower surface nozzle 71 that ejects the processing liquid to the center of the lower surface of the substrate W. The lower surface nozzle 71 includes a nozzle disc portion disposed between the upper surface 12u of the rotating base 12 and the lower surface of the substrate W; and a nozzle cylindrical portion extending downward from the nozzle disc portion. The ejection port of the lower surface nozzle 71 forms an opening at the center of the upper surface of the nozzle disc. When the substrate W is held by the spin chuck 10, the ejection port of the lower surface nozzle 71 faces the center of the lower surface of the substrate W up and down.

The lower surface nozzle 71 is connected to a heating fluid pipe 72 that guides warm water (pure water having a higher temperature than room temperature) as an example of the heating fluid to the lower surface nozzle 71. The pure water supplied to the lower surface nozzle 71 is heated by the heater 75 installed in the heating fluid pipe 72. When the heating fluid valve 73 installed in the heating fluid piping 72 is opened, the hot water is continuously directed upward from the spray port of the nozzle 71 on the lower surface at a flow rate corresponding to the opening of the flow adjustment valve 74 that changes the flow rate of the warm water. Squirting. Thereby, warm water is supplied to the lower surface of the substrate W.

The lower surface nozzle 71 is further connected to a cooling fluid pipe 76 that guides cold water (pure water lower than room temperature) as an example of the cooling fluid to the lower surface nozzle 71. The pure water supplied to the lower surface nozzle 71 is cooled by the cooler 79 installed in the cooling fluid pipe 76. When the cooling fluid valve 77 installed in the cooling fluid piping 76 is opened, the cooling water is continuously sprayed upward from the spray port of the lower surface nozzle 71 at a flow rate corresponding to the opening of the flow adjustment valve 78 that changes the flow rate of the cooling water. Thereby, cold water is supplied to the lower surface of the substrate W.

The outer peripheral surface of the lower surface nozzle 71 and the inner peripheral surface of the rotating base 12 form a cylindrical lower gas flow path 82 extending up and down. The lower gas flow path 82 includes a lower central opening 81 formed at the center of the upper surface 12 u of the rotating base 12. The lower gas flow path 82 is connected to a gas pipe 83 that guides the inert gas to the lower central opening 81 under the rotating base 12. The substrate processing apparatus 1 may also include a lower temperature regulator 86 for heating or cooling the inert gas sprayed from the central opening 81 under the rotating base 12. When the gas valve 84 installed under the lower gas piping 83 is opened, the inert gas is continuously flowed upward from the lower central opening 81 of the rotating base 12 at a flow rate corresponding to the opening of the flow rate adjustment valve 85 that changes the flow rate of the inert gas. Spit out.

The inert gas sprayed from the central opening 81 under the rotating base 12 is nitrogen. The inert gas ejected from the central opening 81 under the rotating base 12 may also be a gas other than nitrogen such as helium or argon. When the substrate W is held by the rotating chuck 10, if nitrogen gas is ejected from the central opening 81 under the rotating base 12, the nitrogen gas flows radially in all directions between the lower surface of the substrate W and the upper surface 12u of the rotating base 12. Thereby, the space between the substrate W and the rotating base 12 is filled with nitrogen gas.

Next, the film thickness measurement unit 91 will be described.

FIG. 3 is a schematic diagram of the horizontal observation film thickness measuring unit 91, the rotating chuck 10, and the blocking member 51. As shown in FIG. FIG. 4 is a schematic diagram of the film thickness measuring unit 91 and the rotating chuck 10 viewed from above. FIG. 5 is a cross-sectional view showing the inside of the housing 93 that houses the light-emitting element 92. As shown in FIG. Fig. 6 is a cross-sectional view taken along the line VI-VI shown in Fig. 5.

As shown in FIGS. 3 and 4, the substrate processing apparatus 1 includes a film thickness measuring unit 91 that measures the thickness (film thickness) of the liquid film present on the upper surface of the substrate W. As shown in FIG. The film thickness measurement unit 91 measures the film thickness by, for example, spectroscopic interferometry. The film thickness measuring unit 91 includes a light emitting element 92 that emits light to the upper surface of the substrate W held by the spin chuck 10; and a light receiving element 97 that receives light of the light emitting element 92 reflected by the upper surface of the substrate W. The light-emitting element 92 and the light-receiving element 97 are arranged at positions that do not overlap the rotating chuck 10 and the blocking member 51 in a plan view.

The light emitting element 92 is arranged in the housing 93. The light receiving element 97 is arranged in the housing 98. The light of the light emitting element 92 is emitted from the opening of the housing 93 covered by the transparent plate 94 to the outside of the housing 93. The light of the light emitting element 92 reflected by the upper surface of the substrate W passes through the opening of the housing 98 covered by the transparent plate 99 and enters the light receiving element 97 in the housing 98. The black dot Pi in FIG. 3 and FIG. The thickness of the liquid film on the substrate W is calculated based on the light incident on the light receiving element 97.

As shown in FIGS. 5 and 6, the film thickness measurement unit 91 includes a holder 95 that holds the light-emitting element 92 in the housing 93, and an electric motor 96 that moves the holder 95 relative to the housing 93. The holder 95 and the electric motor 96 are housed in the housing 93. The rotor and stator of the electric motor 96 are housed in the motor housing 96a, and the rotating shaft 96b of the electric motor 96 protrudes from the end of the motor housing 96a toward the axial direction of the electric motor 96. The rotating shaft 96b is connected to the holder 95, and the motor housing 96a is connected to the housing 93.

The rotation angle of the electric motor 96 is controlled by the controller 3. When the electric motor 96 rotates the rotating shaft 96b, the holder 95 and the light-emitting element 92 rotate together around the rotating axis A2 that is horizontal with respect to the housing 93. The white arrow in FIG. 5 indicates that the light-emitting element 92 rotates around the rotation axis A2. Thereby, the incident position where the light of the light emitting element 92 enters the upper surface of the substrate W moves within the upper surface of the substrate W, and the incident angle of the light of the light emitting element 92 with respect to the upper surface of the substrate W changes. Therefore, if the electric motor 96 is rotated, the light of the light emitting element 92 can be incident on a plurality of positions in the upper surface of the substrate W, and the film thickness can be measured at a plurality of positions in the upper surface of the substrate W.

If the incident position and incident angle change, it means that the path through which the reflected light of the light-emitting element 92 reflected by the upper surface of the substrate W passes has also changed. The light receiving element 97 may also be capable of moving in a manner that can receive the reflected light even if the path of the reflected light changes. For example, like the light-emitting element 92, an electric motor that moves the light-receiving element 97 relative to the housing 98 may be provided. Alternatively, a plurality of light-receiving elements 97 corresponding to one light-emitting element 92 may be provided. In these situations, even if the incident position and incident angle change, the reflected light is received by the light receiving element 97, and the thickness of the liquid film on the substrate W is measured.

When measuring the thickness of the liquid film on the substrate W, the controller 3 can rotate the substrate W on the rotating chuck 10 while setting the incident position at a fixed horizontal distance from the rotation axis A1, or the incident position It moves in the radial direction of the substrate W (the horizontal direction orthogonal to the rotation axis A1). In the latter case, the average value of a plurality of measured values can also be treated as the film thickness.

Next, the pre-drying treatment liquid supply device 101 will be described. FIG. 7 is a schematic diagram showing the pre-drying treatment liquid supply device 101 included in the substrate processing apparatus 1.

The substrate processing apparatus 1 includes a pre-drying processing liquid supply device 101 that supplies a pre-drying processing liquid to a pre-drying processing liquid nozzle 39 through a pre-drying processing liquid pipe 40. The pre-drying treatment liquid supply device 101 includes: a first tank 102A, which is equivalent to a stock solution tank for storing the stock solution of the pre-drying treatment liquid; and a second tank 102B, which corresponds to a solvent tank for storing the solvent of the pre-drying treatment solution.

The stock solution of the treatment solution before drying contains sublimable substances and solvents. The concentration of the sublimable substance in the stock solution of the pre-drying treatment solution is higher than that of the pre-drying treatment solution supplied to the substrate W. The stock solution of the pre-drying treatment liquid is diluted with the solvent supplied from the second tank 102B, and then supplied to the substrate W. When the sublimable substance is liquid at room temperature, the stock solution of the treatment solution before drying may not contain a solvent.

The pre-drying treatment liquid supply device 101 includes: a first circulation pipe 103A that circulates the stock solution in the first tank 102A; a first pump 104A that sends the stock solution in the first tank 102A to the first circulation pipe 103A; and 1 individual pipe 105A, which guides the stock solution in the first circulation pipe 103A to the pre-drying treatment liquid pipe 40. The pre-drying treatment liquid supply device 101 further includes: a first on-off valve 106A that opens and closes the inside of the first individual pipe 105A; and a first flow rate adjustment valve 107A that changes from the first individual pipe 105A to supply to the pre-drying treatment The flow rate of the treatment liquid before drying in the liquid piping 40.

Similarly, the pre-drying treatment liquid supply device 101 includes: a second circulation pipe 103B that circulates the solvent in the second tank 102B; and a second pump 104B that sends the solvent in the second tank 102B to the second circulation pipe 103B ; And the second individual piping 105B, which guides the solvent in the second circulation piping 103B to the pre-drying treatment liquid piping 40. The pre-drying treatment liquid supply device 101 further includes: a second opening and closing valve 106B that opens and closes the inside of the second individual pipe 105B; and a second flow rate adjustment valve 107B that changes from the second individual pipe 105B to the pre-drying process The flow rate of the treatment liquid before drying in the liquid piping 40.

The first individual piping 105A and the second individual piping 105B are connected to the pre-drying treatment liquid piping 40 via a mixing valve 108 that mixes the stock solution of the pre-drying treatment liquid and the solvent to produce the pre-drying treatment liquid. The pre-drying treatment liquid piping 40 is provided with not only a pre-drying treatment liquid valve 41 but also an in-pipe mixer 109. The in-pipe mixer 109 further mixes the pre-drying treatment liquid generated by the mixing valve 108. Thereby, the pre-drying treatment liquid obtained by uniformly mixing the sublimable substance and the solvent is supplied to the pre-drying treatment liquid nozzle 39.

The stock solution of the pre-drying treatment liquid supplied from the first tank 102A is supplied to the mixing valve 108 at a flow rate corresponding to the opening degree of the first flow rate adjusting valve 107A. The solvent supplied from the second tank 102B is supplied to the mixing valve 108 at a flow rate corresponding to the opening degree of the second flow adjustment valve 107B. Therefore, by changing the opening degrees of the first flow regulating valve 107A and the second flow regulating valve 107B, the concentration of the sublimable substance in the pre-drying treatment liquid supplied to the pre-drying treatment liquid nozzle 39 can be changed.

The pre-drying treatment liquid supply device 101 includes a densitometer 110 that measures the concentration of the pre-drying treatment liquid supplied to the pre-drying treatment liquid nozzle 39. The pre-drying treatment liquid supply device 101 includes a measurement pipe 111 branched from the pre-drying treatment liquid pipe 40. The concentration meter 110 is interposed in the measurement pipe 111. FIG. 7 shows an example in which the measuring pipe 111 is connected to the pre-drying treatment liquid pipe 40 at a position downstream of the in-pipe mixer 109. Therefore, in this example, the concentration of the pre-drying treatment liquid passing through both the mixing valve 108 and the in-pipe mixer 109 is measured by the densitometer 110. The concentration meter 110 may be installed in the pre-drying treatment liquid piping 40 between the pre-drying treatment liquid valve 41 and the in-pipe mixer 109 instead of being installed in the measurement piping 111.

FIG. 8 is a block diagram showing the hardware of the controller 3.

The controller 3 is a computer including a computer body 3a and a peripheral device 3d connected to the computer body 3a. The computer body 3a includes a CPU 3b (central processing unit) that executes various commands, and a main memory device 3c that stores information. The peripheral device 3d includes an auxiliary memory device 3e for storing information such as the program P, a reading device 3f for reading information from the removable medium RM, and a communication device 3g for communicating with other devices such as a host computer.

The controller 3 is connected to the input device 100A, the display device 100B, and the alarm device 100C. The input device 100A is operated by an operator such as a user or a maintenance person when inputting information into the substrate processing apparatus 1. The information is displayed on the screen of the display device 100B. The input device 100A may be any one of a keyboard, a pointing device, and a touch panel, or may be other devices. The touch panel display having both the input device 100A and the display device 100B can also be provided in the substrate processing apparatus 1. The alarm device 100C uses at least one of light, sound, text, and graphics to issue an alarm. When the input device 100A is a touch panel display, the input device 100A can also serve as the alarm device 100C.

The CPU 3b executes the program P stored in the auxiliary memory device 3e. The program P in the auxiliary memory device 3e can be pre-installed in the controller 3, or can be sent from the removable medium RM to the auxiliary memory device 3e via the reading device 3f, or can be communicated from an external device such as a host computer The device 3g is sent to the auxiliary memory device 3e.

The auxiliary memory device 3e and the removable medium RM are non-volatile memory that retains memory even if power is not supplied. The auxiliary memory device 3e is, for example, a magnetic memory device such as a hard disk drive. The removable medium RM is, for example, an optical disk such as a compact disk or a semiconductor memory such as a memory card. The removable medium RM is an example of a computer-readable recording medium on which the program P is recorded. The removable medium RM is a non-temporary tangible recording medium.

The auxiliary memory device 3e memorizes a plurality of process recipes. The process recipe specifies the processing content, processing conditions, and processing sequence of the substrate W. The plurality of process recipes are different from each other in at least one of the processing content, processing conditions, and processing sequence of the substrate W. The controller 3 controls the substrate processing apparatus 1 in a manner of processing the substrate W according to the process recipe specified by the host computer. The following processes are executed by the controller 3 controlling the substrate processing apparatus 1. In other words, the controller 3 is programmed to execute the following processes.

Next, an example of substrate processing will be described.

The substrate W to be processed is, for example, a semiconductor wafer such as a silicon wafer. The surface of the substrate W corresponds to the device forming surface on which devices such as transistors or capacitors are formed. The substrate W may be a substrate W on which a pattern PA (see FIG. 10A) is formed on the surface of the substrate W, which is the device forming surface, or may be a substrate W on which the pattern PA is not formed on the surface of the substrate W. In the latter case, the pattern PA can also be formed by the following chemical liquid supply process.

First, an example of substrate processing when the pre-drying treatment liquid is a solution of camphor and IPA (first substrate processing example) will be described.

FIG. 9 is a process diagram for explaining the substrate processing performed by the substrate processing apparatus 1. 10A to 10F are schematic diagrams showing the state of the substrate W when a solution of camphor and IPA is used. Figure 11 is a diagram of the equilibrium state of camphor and IPA. RT in Figure 11 means room temperature. Hereinafter, refer to FIG. 2 and FIG. 9. Refer to FIGS. 10A to 10F and FIG. 11 as appropriate.

When the substrate W is processed by the substrate processing apparatus 1, the carrying process (step S1 in FIG. 9) is performed, that is, the substrate W is carried into the chamber 4.

Specifically, when the blocking member 51 is at the upper position, all the sheaths 24 are at the lower position, and all the scanning nozzles are at the standby position, the central robot CR (refer to FIG. 1) supports the substrate W with the hand H1 while supporting the substrate W. Make the hand H1 enter the chamber 4. Then, the central robot CR places the substrate W on the hand H1 on the plurality of chuck pins 11 with the surface of the substrate W facing up. After that, a plurality of chuck pins 11 are pressed against the outer peripheral surface of the substrate W, and the substrate W is held. Thereby, the substrate W is held by rotating the chuck 10 (substrate holding process). The substrate holding process continues until the following sublimation process (step S10 in FIG. 9) ends. After the center robot CR places the substrate W on the rotating chuck 10, the hand H1 is retracted from the inside of the chamber 4.

Next, the upper gas valve 64 and the lower gas valve 84 are opened, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 start to spray nitrogen gas. Thereby, the space between the substrate W and the blocking member 51 is filled with nitrogen gas. Similarly, the space between the substrate W and the rotating base 12 is filled with nitrogen. On the other hand, the sheath lifting unit 27 raises at least one sheath 24 from the lower position to the upper position. After that, the rotation motor 14 is driven to start the rotation of the substrate W at a specific liquid supply speed (substrate rotation process). The substrate rotation process continues until the following sublimation process (step S10 in FIG. 9) ends.

Next, a chemical liquid supply process (step S2 in FIG. 9) is performed, that is, the chemical liquid is supplied to the upper surface of the substrate W to form a liquid film covering the entire upper surface of the substrate W.

Specifically, in a state where the blocking member 51 is located at the upper position and at least one sheath 24 is located at the upper position, the nozzle moving unit 34 moves the liquid chemical nozzle 31 from the standby position to the processing position. After that, the chemical liquid valve 33 is opened, and the chemical liquid nozzle 31 starts to spray the chemical liquid (the chemical liquid supply process, the chemical liquid ejection process). When a certain time elapses after opening the liquid medicine valve 33, the liquid medicine valve 33 is closed, and the spraying of the liquid medicine is stopped. After that, the nozzle moving unit 34 moves the chemical liquid nozzle 31 to the standby position.

The chemical liquid ejected from the chemical liquid nozzle 31 collides with the upper surface of the substrate W rotating at a specific chemical liquid supply speed, and flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the chemical liquid is supplied to the entire upper surface of the substrate W, and a liquid film of the chemical liquid covering the entire upper surface of the substrate W is formed. When the chemical liquid nozzle 31 sprays the chemical liquid, the nozzle moving unit 34 can move the liquid contact position by the liquid contact position of the chemical liquid on the upper surface of the substrate W through the center and the outer periphery, or make the liquid contact position stationary at the center. .

Next, a rinsing process (step S3 in FIG. 9) is performed, that is, pure water as an example of a rinsing liquid is supplied to the upper surface of the substrate W, and the chemical solution on the substrate W is rinsed.

Specifically, in a state where the blocking member 51 is located at the upper position and at least one sheath 24 is located at the upper position, the nozzle moving unit 38 moves the washing liquid nozzle 35 from the standby position to the processing position. After that, the flushing fluid valve 37 is opened, and the flushing fluid nozzle 35 starts to spray the flushing fluid (rinsing fluid supply process, flushing fluid spraying process). Before starting the spraying of pure water, the sheath lifting unit 27 can also move at least one sheath 24 vertically to replace the sheath 24 that catches the liquid discharged from the substrate W. When a certain time elapses after opening the flushing liquid valve 37, the flushing liquid valve 37 is closed, and the spraying of the flushing liquid is stopped. After that, the nozzle moving unit 38 moves the rinse liquid nozzle 35 to the standby position.

The pure water sprayed from the rinse liquid nozzle 35 collides with the upper surface of the substrate W rotating at a specific rinse liquid supply speed, and flows outward along the upper surface of the substrate W by centrifugal force. The chemical liquid on the substrate W is replaced with pure water sprayed from the rinse liquid nozzle 35. Thereby, a liquid film of pure water covering the entire upper surface of the substrate W is formed. When the rinsing liquid nozzle 35 sprays pure water, the nozzle moving unit 38 can move the liquid contact position with the pure water relative to the liquid contact position on the upper surface of the substrate W through the center and the outer periphery, or make the liquid contact position stationary at the center. .

Next, a replacement treatment process (step S4 in FIG. 9) is performed, that is, a replacement liquid that is compatible with both the rinse liquid and the pre-drying treatment liquid is supplied to the upper surface of the substrate W, and the pure water on the substrate W is replaced For replacement fluid.

Specifically, in a state where the blocking member 51 is located at the upper position and at least one sheath 24 is located at the upper position, the nozzle moving unit 46 moves the replacement liquid nozzle 43 from the standby position to the processing position. After that, the replacement liquid valve 45 is opened, and the replacement liquid nozzle 43 starts to discharge the replacement liquid (a replacement liquid supply process, a replacement liquid discharge process). Before starting the ejection of the replacement liquid, the sheath lifting unit 27 can also move at least one sheath 24 vertically to replace the sheath 24 that catches the liquid discharged from the substrate W. When a certain time elapses after opening the replacement liquid valve 45, the replacement liquid valve 45 is closed, and the ejection of the replacement liquid is stopped. After that, the nozzle moving unit 46 moves the replacement liquid nozzle 43 to the standby position.

The replacement liquid ejected from the replacement liquid nozzle 43 collides with the upper surface of the substrate W rotating at a specific replacement liquid supply speed, and flows outward along the upper surface of the substrate W by centrifugal force. The pure water on the substrate W is replaced with the replacement liquid sprayed from the replacement liquid nozzle 43. Thereby, a liquid film of the replacement liquid covering the entire upper surface of the substrate W is formed. When the replacement liquid nozzle 43 ejects the replacement liquid, the nozzle moving unit 46 can move the liquid contact position of the replacement liquid to the upper surface of the substrate W through the center and the outer periphery, or make the liquid contact position stationary at the center. . In addition, after the liquid film of the replacement liquid covering the entire upper surface of the substrate W is formed, the replacement liquid nozzle 43 can also stop the ejection of the replacement liquid while making the substrate W at a speed of the coating liquid (for example, more than 0 to 20 rpm or less). Speed) rotation.

Next, a pre-drying treatment liquid supply process (step S5 in FIG. 9) is performed, that is, the pre-drying treatment liquid is supplied to the upper surface of the substrate W, and a liquid film of the pre-drying treatment liquid is formed on the substrate W.

Specifically, in a state where the blocking member 51 is at the upper position and at least one sheath 24 is at the upper position, the nozzle moving unit 42 moves the pre-drying treatment liquid nozzle 39 from the standby position to the treatment position. After that, the pre-drying treatment liquid valve 41 is opened, and the pre-drying treatment liquid nozzle 39 starts to spray the pre-drying treatment liquid (pre-drying treatment liquid supply process, pre-drying treatment liquid discharge process). Before starting the spraying of the treatment liquid before drying, the sheath lifting unit 27 can also move at least one sheath 24 vertically to replace the sheath 24 that catches the liquid discharged from the substrate W. When a certain time elapses after opening the pre-drying treatment liquid valve 41, the pre-drying treatment liquid valve 41 is closed to stop the spraying of the pre-drying treatment liquid. After that, the nozzle moving unit 42 moves the pre-drying treatment liquid nozzle 39 to the standby position.

The pre-drying treatment liquid ejected from the pre-drying treatment liquid nozzle 39 collides with the upper surface of the substrate W rotating at a specific pre-drying treatment liquid supply speed, and flows outward along the upper surface of the substrate W by centrifugal force. The supply speed of the treatment liquid before drying is, for example, 500 rpm. The replacement liquid on the substrate W is replaced with the pre-drying treatment liquid ejected from the pre-drying treatment liquid nozzle 39. Thereby, a liquid film of the pre-drying treatment liquid covering the entire upper surface of the substrate W (pre-drying treatment liquid film 120) is formed (pre-drying treatment liquid film forming process). In this way, the pre-drying treatment liquid nozzle 39 is an example of a pre-drying treatment liquid supply unit that supplies the pre-drying treatment liquid to the upper surface of the substrate W so that the pre-drying treatment liquid film 120 is formed on the upper surface of the substrate W.

When the pre-drying treatment liquid nozzle 39 sprays the pre-drying treatment liquid, the nozzle moving unit 42 can move the liquid contact position of the dry pre-treatment liquid to the upper surface of the substrate W through the center and the outer periphery, or in the center The part makes the liquid contact position stationary.

Next, the film thickness reduction process is performed (step S6 in FIG. 9), that is, while maintaining the entire upper surface of the substrate W covered by the liquid film of the pre-drying treatment liquid, while reducing the thickness of the pre-drying liquid film 120 on the substrate W Thickness (film thickness).

Specifically, the blocking member elevating unit 54 moves the blocking member 51 from the upper position to the lower position. Then, in a state where the blocking member 51 is located at the lower position and the at least one sheath 24 is located at the upper position, the rotation motor 14 maintains the rotation speed of the substrate W at a film thickness reduction rotation speed. The rotation speed of the film thickness reduction can be equal to or different from the supply speed of the treatment liquid before drying. The pre-drying treatment liquid on the substrate W is also discharged from the substrate W to the outside by centrifugal force after the spraying of the pre-drying treatment liquid is stopped. Therefore, the thickness of the pre-drying treatment liquid film 120 on the substrate W is reduced. When the pre-drying treatment liquid on the substrate W is discharged to a certain extent, the discharge amount of the pre-drying treatment liquid from the substrate W per unit time is reduced to zero or substantially zero. Thereby, the thickness of the pre-drying treatment liquid film 120 on the substrate W is stabilized at a value corresponding to the rotation speed of the substrate W.

After the film thickness reduction process (step S6 in FIG. 9) reduces the thickness of the pre-drying liquid film 120, the first precipitation process (precipitation process) (step S7 in FIG. 9) is performed, that is, the solid 121 ( Refer to FIG. 10B) the pre-drying treatment liquid deposited on the substrate W.

Specifically, in a state where the blocking member 51 is located at the lower position and at least one sheath 24 is located at the upper position, the rotation motor 14 maintains the rotation speed of the substrate W at a specific first deposition speed. The first precipitation rate may be equal to or different from the supply rate of the treatment liquid before drying. The first precipitation rate is, for example, 500 rpm. Since the vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance, while the substrate W is rotating at the first precipitation speed, the solvent evaporates from the surface of the treatment liquid before drying at an evaporation rate greater than the evaporation rate of the sublimable substance. Fig. 10A shows the state where the solvent evaporates from the surface of the treatment liquid before drying.

If the evaporation of the solvent continues, the thickness of the treatment liquid film 120 before drying will gradually decrease, and the concentration of the sublimable substance on the surface of the treatment liquid film 120 and its vicinity will gradually increase. The evaporation of the solvent from the pre-drying liquid film 120 is performed, for example, without forcibly heating the pre-drying liquid film 120 on the substrate W. Therefore, when the pre-drying treatment liquid film 120 on the substrate W is maintained at room temperature or a temperature slightly lower than the room temperature, the solvent evaporates from the pre-drying treatment liquid. When the concentration of the sublimable substance on the surface of the treatment liquid film 120 before drying and its vicinity reaches the saturated concentration of the sublimable substance in the treatment liquid before drying, as shown in FIG. The surface of the film 120 is precipitated (room temperature precipitation process, liquid surface precipitation process). In the first precipitation process, the rotary motor 14 functions as a solvent evaporation unit that evaporates the solvent from the pre-drying treatment liquid film 120 by precipitation of the solid 121 of the sublimable substance.

As shown in FIG. 10B, when the solid 121 of the sublimable substance precipitates, it is located in the main body of the treatment liquid before drying. All or part of the pretreatment liquid becomes a solid 121 of sublimation material. FIG. 10B shows an example in which only the pre-drying treatment liquid on the surface side of the drying pre-treatment liquid film 120 in the drying pre-treatment liquid film 120 becomes a solid 121 of a sublimable substance, and the remaining pre-drying treatment liquid film 120 is maintained as a liquid. . In this example, the solid 121 of the sublimation material does not reach the upper surface of the pattern PA, and the pre-drying treatment liquid not only remains between the patterns PA, but also remains between the solid 121 of the sublimation material and the upper surface of the pattern PA. All or part of the surface of the treatment liquid film 120 before drying is covered by the horizontally spreading film-like solid 121 of the sublimable substance, in other words, is covered by the solidified film (solid film).

Next, the first dissolution process (step S8 in FIG. 9) is performed, that is, the pre-drying treatment liquid for dissolving the solid 121 of the sublimable substance on the substrate W.

Specifically, in a state where the blocking member 51 is located at the lower position and the at least one sheath 24 is located at the upper position, the rotation motor 14 maintains the rotation speed of the substrate W at a specific first dissolution speed. The first dissolution rate may be equal to or different from the supply rate of the treatment liquid before drying. The first dissolution rate is, for example, 500 rpm. Furthermore, the heating fluid valve 73 is opened, and the lower surface nozzle 71 starts to spray out warm water (pure water higher than room temperature). Before starting the spraying of warm water, the sheath lifting unit 27 can also move at least one sheath 24 vertically to replace the sheath 24 that catches the liquid discharged from the substrate W.

The warm water sprayed from the lower surface nozzle 71 collides with the center portion of the lower surface of the substrate W rotating at the first dissolving speed, and then flows outward along the lower surface of the substrate W. Thereby, the entire area of the substrate W is heated at a heating temperature higher than room temperature. The heat of the warm water is transferred through the substrate W to the pre-drying treatment liquid on the substrate W. The pre-drying liquid film 120 on the substrate W is heated indirectly via the substrate W (indirect heating process). Thereby, the temperature of the solid 121 of the sublimable substance and the liquid film 120 before drying on the substrate W is maintained at a temperature higher than room temperature.

As shown in FIG. 10C, when the temperature of the pre-drying treatment liquid film 120 on the substrate W is increased, the saturated concentration of the sublimable substance in the pre-drying treatment solution rises, and the solid 121 of the sublimable substance is dissolved on the substrate W. Pre-treatment liquid. The dissolution of the solid 121 of the sublimable substance in the pre-drying treatment liquid is promoted by the increase in the temperature of the pre-drying treatment liquid. Thereby, all or most of the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid on the substrate W. FIG. 10D shows an example in which all the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid.

After the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid, the solid 121 of the sublimable substance may be precipitated again, and the precipitated solid 121 of the sublimable substance may be dissolved in the pre-drying treatment liquid again. In other words, one repeating cycle from the first precipitation process (step S7 in FIG. 9) to the first dissolution process (step S8 in FIG. 9) may be performed more than two times.

"N" in Figure 9 means an integer greater than 0. When N is 1 or more, repeat the cycle more than 2 times, and then perform the final precipitation process (step S9 in FIG. 9). When N is 0, the first precipitation process (step S7 in FIG. 9) and the first dissolution process (step S8 in FIG. 9) are performed once respectively, and then, the final step of re-precipitating the solid 121 of the sublimable substance is performed. The precipitation process (step S9 in FIG. 9).

Specifically, when the blocking member 51 is at the lower position and the at least one sheath 24 is at the upper position, the rotation motor 14 maintains the rotation speed of the substrate W to a specific final precipitation speed. The final precipitation rate may be equal to or different from the supply rate of the treatment liquid before drying. The final precipitation speed is, for example, 500 rpm. The spraying of warm water from the nozzle 71 on the lower surface continues from the first dissolution process (step S8 in FIG. 9). Therefore, the pre-drying treatment liquid on the substrate W is also maintained at a temperature higher than room temperature during the rotation of the substrate W at the final precipitation speed.

As shown in FIG. 10D, while the substrate W is rotating at the final deposition speed, the solvent evaporates from the surface of the treatment liquid film 120 before drying. Therefore, the surface of the treatment liquid before drying gradually approaches the base of the pattern PA, and the concentration of the sublimation substance in the treatment liquid film 120 before drying gradually increases. When the concentration of the sublimable substance in the treatment liquid film 120 before drying reaches the saturated concentration of the sublimable substance in the treatment solution before drying, the solid 121 of the sublimable substance precipitates on the upper surface of the substrate W, and all or almost all of the pre-drying treatment The liquid disappears from the substrate W. In the final precipitation process, the rotary motor 14 and the lower surface nozzle 71 function as a solvent evaporation unit that evaporates the solvent from the pre-drying treatment liquid film 120 by precipitation of the solid 121 of the sublimable substance.

FIG. 10E shows an example in which all the treatment liquid before drying disappears, and the solid 121 of the sublimable substance precipitates between the patterns PA. FIG. 10E shows an example in which the thickness of the solid 121 of the sublimation material is greater than the height of the pattern PA.

Figure 11 is a diagram of the equilibrium state of camphor and IPA. The solution of camphor and IPA is equivalent to the pre-treatment solution for drying. The curve (coagulation curve) in Fig. 11 represents the freezing point of the solution of camphor and IPA. The thick broken lines in Figure 11 indicate that the first precipitation process (step S7 in Figure 9), the first dissolution process (step S8 in Figure 9), and the final precipitation process (step S9 in Figure 9) are performed once, which is Figure 9. The transition between the concentration of camphor and the temperature of the solution when N=0.

In FIG. 11, the thick straight line from point P1 to point P2 indicates that the first precipitation process is performed (step S8 in FIG. 9). When the first precipitation process (step S8 in FIG. 9) is performed, IPA evaporates from the solution of camphor and IPA, which is the pre-drying solution, and the concentration of camphor gradually rises. At this time, the temperature of the treatment solution before drying is maintained at room temperature or a temperature near it. When the concentration of camphor rises to the concentration of point P2 in FIG. 11, a solid 121 containing sublimable substances of camphor and IPA is formed by precipitation or solidification.

In FIG. 11, the thick straight line from point P2 to point P3 indicates that the first dissolution process is performed (step S8 in FIG. 9). When the first dissolution process (step S8 in FIG. 9) is performed, the temperature of the solution of camphor and IPA rises, and the temperature of the solid 121 of the sublimable substance rises to a temperature higher than the freezing point of the solution of camphor and IPA. Thereby, at least a part of the solid 121 of the sublimation substance melts or dissolves, and returns to the solution of camphor and IPA.

In FIG. 11, the thick straight line from point P3 to point P4 indicates that the final precipitation process is performed (step S9 in FIG. 9). As mentioned above, in the final precipitation process (step S9 in Figure 9), in order to precipitate the solid 121 of the sublimable substance again, the temperature of the solution of camphor and IPA is not lowered, but the solution of camphor and IPA is maintained high. At room temperature, the IPA will evaporate further. Therefore, compared with the solid 121 of the sublimable substance precipitated in the first precipitation process (step S7 of FIG. 9), the solid 121 of the sublimable substance with less IPA content is precipitated.

After the solid 121 of the sublimable substance is deposited between the patterns PA, a sublimation process is performed (step S10 in FIG. 9), that is, the solid 121 of the sublimable substance is sublimated and removed from the upper surface of the substrate W.

Specifically, in the state where the blocking member 51 is located at the lower position, the rotation motor 14 maintains the rotation speed of the substrate W at a specific sublimation speed. The sublimation speed can be equal to or different from the supply speed of the treatment liquid before drying. The sublimation speed is, for example, 1500 rpm. Furthermore, the upper gas valve 57 is opened, and the center nozzle 55 starts to spray nitrogen gas. In addition to opening the upper gas valve 57, or instead of changing the opening degree of the flow regulating valve 65, the flow rate of nitrogen gas sprayed from the central opening 61 on the blocking member 51 can be increased.

When the rotation of the substrate W at the sublimation speed starts, the sublimation of the solid 121 of the sublimable substance on the substrate W starts, and the solid 121 of the sublimable substance on the substrate W generates a gas containing the sublimable substance. The gas (gas containing the sublimable substance) generated by the solid 121 of the sublimable substance flows radially in the space between the substrate W and the blocking member 51 and is discharged from above the substrate W. Then, when a certain amount of time has passed after the start of sublimation, as shown in FIG. 10F, all solids 121 of sublimable substances are removed from the substrate W. After that, the rotation motor 14 is stopped, and the rotation of the substrate W is stopped. Furthermore, the upper gas valve 57 is closed, and the center nozzle 55 stops the ejection of nitrogen gas.

In this way, the center nozzle 55, the center opening 61 on the blocking member 51, and the rotation motor 14 function as a sublimation unit for sublimating the solid 121 of the sublimable substance on the upper surface of the substrate W.

Furthermore, instead of the above-mentioned blowing of nitrogen gas, a heat source such as a heating element or a lamp may be arranged above or below the substrate W, and the sublimable substance may be sublimated by heating by the heat source.

In addition, although described below, when the solid 121 of the sublimable substance on the substrate W precipitates, the detection value of the film thickness measurement unit 91 changes greatly. Therefore, the controller 3 can monitor the detection of the film thickness measurement unit 91 Value to determine whether the solid 121 of the sublimable substance has precipitated. Therefore, the controller 3 can also be controlled in the following manner: a threshold value is preset for the film thickness at any position on the upper surface of the substrate W measured by the film thickness measurement unit 91, and if the measured film thickness becomes below the threshold value, From the final precipitation process to the sublimation process.

Next, the unloading process (step S11 in FIG. 9) is performed, that is, the substrate W is unloaded from the chamber 4.

Specifically, the shielding member raising and lowering unit 54 raises the shielding member 51 to the upper position, and the sheath raising and lowering unit 27 lowers all the sheaths 24 to the lower position. Furthermore, the upper gas valve 64 and the lower gas valve 84 are closed, and the upper central opening 61 of the blocking member 51 and the lower central opening 81 of the rotating base 12 stop the ejection of nitrogen. After that, the central robot CR makes the hand H1 enter the chamber 4. After the plurality of chuck pins 11 release the holding of the substrate W, the central robot CR supports the substrate W on the rotating chuck 10 with the hand H1. After that, the center robot CR supports the substrate W with the hand H1 while retracting the hand H1 from the inside of the chamber 4. Thereby, the processed substrate W is carried out from the chamber 4.

Next, an example of substrate processing (second substrate processing example) when the pre-drying treatment liquid is a solution of camphor and methanol will be described.

The rough flow of the second substrate processing example is the same as that of the first substrate processing example, as shown in FIG. 9. Regarding the second substrate processing example, the process from the first dissolution process (step S8 in FIG. 9) to the final precipitation process (step S9 in FIG. 9) is different from the first substrate processing example. 1 The same applies to the substrate processing example. Therefore, the process from the first dissolution process to the final precipitation process in the second substrate processing example will be described below.

12A to 12D are schematic diagrams showing the state of the substrate W when a solution of camphor and methanol is used. Hereinafter, refer to FIG. 2 and FIG. 9. Refer to FIGS. 12A to 12D as appropriate.

After the first precipitation process (step S7 of FIG. 9) is used to precipitate the solid 121 of the sublimable substance, the first dissolution process (step S8 of FIG. 9) is performed, that is, the solid 121 of the sublimable substance is dissolved on the substrate W on the pre-treatment liquid for drying.

Specifically, in a state where the blocking member 51 is located at the lower position and the at least one sheath 24 is located at the upper position, the rotation motor 14 maintains the rotation speed of the substrate W at a specific first dissolution speed. The first dissolution rate may be equal to or different from the supply rate of the treatment liquid before drying. The first dissolution rate is, for example, 1500 rpm. When the substrate W is rotating at the first dissolving speed, the controller 3 may also close the upper gas valve 64 in order to stop the ejection of nitrogen from the central opening 61 on the blocking member 51. Alternatively, the controller 3 can also reduce the flow rate of nitrogen gas sprayed from the central opening 61 on the blocking member 51 by changing the opening degree of the flow regulating valve 65.

When the solvent is evaporated from the treatment liquid before drying by the first precipitation process (step S7 in Fig. 9), the heat of the treatment liquid before drying, which is equivalent to the heat of vaporization, is released together with the solvent in the gas atmosphere in the chamber 4 to dry The temperature of the surface of the pretreatment liquid decreases. When the solid 121 of the sublimable substance is formed, the solvent evaporated from the treatment liquid before drying is reduced, and therefore, the heat of the treatment liquid before drying released in the gas atmosphere is also reduced. At the same time, as shown in FIG. 12A, the heat in the gas atmosphere is transferred to the pre-drying treatment liquid through the solid 121 of the sublimable substance. Thereby, the temperature of the solid 121 of the sublimable substance on the substrate W and the pre-drying treatment liquid film 120 rises.

When the temperature of the solid 121 of the sublimable substance on the substrate W and the pre-drying treatment liquid film 120 rises, as shown in FIG. 12B, a part of the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid. The pre-treatment solution for drying is a solution of camphor and methanol. The solid 121 of the sublimation substance contains camphor. The solubility of camphor in methanol is greater than the solubility of camphor in IPA, and camphor is easily soluble in methanol. When a part of the camphor solid is dissolved in the methanol liquid, the remaining camphor solid is immediately dissolved in the methanol liquid. Thereby, all or most of the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid on the substrate W. FIG. 12C shows an example in which all the solids 121 of the sublimable substance are dissolved in the pre-drying treatment liquid.

When the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid on the substrate W, the solvent evaporated from the pre-drying treatment liquid increases, and the temperature of the surface of the pre-drying treatment liquid decreases. Thereby, as shown in FIG. 12D, the concentration of the sublimable substance on the surface of the treatment liquid before drying rises, and the solid 121 of the sublimable substance is precipitated again on the surface of the treatment liquid before drying (step S7 in FIG. 9). When the solid 121 of the sublimable substance precipitates out again, as described above, the temperature of the solid 121 of the sublimable substance and the pre-drying treatment liquid rises, and the solid 121 of the sublimable substance is dissolved in the pre-drying liquid again (Step S8 in FIG. 9) .

In this way, when the pre-drying treatment solution is a solution of camphor and methanol, even if the temperature of the pre-drying treatment solution is not forcibly changed, the pre-drying treatment solution is simply placed on the upper surface of the substrate W and sublimated repeatedly Precipitation and dissolution of the solid 121 of sexual substances (natural precipitation process, natural dissolution process). The number of repetitions of a repetitive cycle from the first precipitation process (step S7 in FIG. 9) to the first dissolution process (step S8 in FIG. 9) increases with the increase of the standing time of the treatment solution before drying. Therefore, it is only necessary to set the number of repetitions of precipitation and dissolution of the solid 121 of the sublimable substance according to the allowable time.

When the solid 121 of the sublimable substance is precipitated, the vapor pressure of the solvent in the gas atmosphere in contact with the pre-drying process on the substrate W is maintained at the saturated vapor pressure of the solvent under the temperature of the gas atmosphere. When dissolving the solid 121 of the sublimable substance, maintain the temperature of the interface between the solid 121 of the sublimable substance and the liquid film 120 before drying to exceed the concentration of the sublimable substance when the solid 121 of the sublimable substance is dissolved before drying The value of the freezing point of the treatment liquid. In this way, the precipitation and dissolution of the solid 121 of the sublimable substance are repeated naturally.

When the solid 121 of the sublimable substance is precipitated and dissolved, the controller 3 can also cause at least one of the central nozzle 55 and the central opening 61 on the blocking member 51 to spray a gas such as nitrogen at a low flow rate. In this case, the vapor of the solvent can be quickly removed from the top of the substrate W, and the evaporation of the solvent can be promoted. Furthermore, as long as the gas is sprayed to the upper surface of the substrate W at a low flow rate, the temperature change at the interface between the solid 121 of the sublimable substance and the pre-drying liquid film 120 can be suppressed to the minimum. Therefore, the evaporation of the solvent can be promoted without hindering the dissolution of the solid 121 of the sublimable substance.

The FFU6 always supplies clean air into the chamber 4. The downflow of the clean air flowing to the upper surface of the substrate W is blocked by the blocking member 51. Thereby, the disturbance of the gas atmosphere on the substrate W can be suppressed. The controller 3 can also cause the FFU 6 to temporarily stop the supply of clean air when the solid 121 of the sublimable substance is precipitated and dissolved. In addition, in order to suppress the disturbance of the gas atmosphere on the substrate W, the controller 3 may also cause the rotation motor 14 to temporarily stop the rotation of the substrate W when the solid 121 of the sublimable substance is precipitated and dissolved.

After the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid, the final precipitation process (step S9 in FIG. 9) is performed, that is, the solid 121 of the sublimable substance is precipitated again.

Specifically, when the blocking member 51 is at the lower position and the at least one sheath 24 is at the upper position, the rotation motor 14 maintains the rotation speed of the substrate W to a specific final precipitation speed. The final precipitation rate may be equal to or different from the supply rate of the treatment liquid before drying. The final precipitation speed is, for example, 1500 rpm. While the substrate W is rotating at the final deposition speed, the solvent evaporates from the surface of the treatment liquid before drying. When the concentration of the sublimable substance in the treatment solution before drying reaches the saturated concentration of the sublimation substance in the treatment solution before drying, the solid 121 of the sublimation substance precipitates on the upper surface of the substrate W, and all or almost all of the treatment solution before drying The substrate W disappears (refer to FIG. 10E). Thereafter, a sublimation process for sublimating the solid 121 of the sublimable substance on the substrate W is performed (step S10 in FIG. 9).

As described above, when the pre-drying treatment liquid is a solution of camphor and methanol, only the pre-drying treatment liquid is placed on the upper surface of the substrate W, and the solid 121 of the sublimable substance is precipitated and dissolved repeatedly. When a small amount of the pre-drying treatment liquid remains on the substrate W, the solid 121 of the sublimable substance may be dissolved in the pre-drying treatment liquid before the solid 121 of the sublimable substance is sublimated. In order to prevent this, the solid 121 of the sublimable substance on the substrate W may be cooled. For example, the rotation speed of the substrate W can be increased, and the flow rate of the gas ejected to the upper surface of the substrate W can also be increased.

FIG. 13 is a graph showing the collapse rate of the pattern PA. The collapse rate A and the collapse rate B are values when the pre-drying treatment solution is a solution of camphor and IPA, and the collapse rate C is the value when the pre-drying treatment solution is a solution of camphor and methanol.

The "collapse rate A" is different from the substrate treatment shown in FIG. 9 and is the value when the solid 121 of the sublimable substance is precipitated once, and then the solid 121 of the sublimable substance is sublimated. The "collapse rate B" is the value when the solid 121 of the sublimable substance is precipitated twice, and then the solid 121 of the sublimable substance is sublimated. That is, the "collapse rate B" is the collapse rate when N=0 in FIG. 9. The "collapse rate C" is the value when the solid 121 of the sublimable substance is precipitated twice or more, and then the solid 121 of the sublimable substance is sublimated. Except for the composition of the treatment solution before drying and the number of times the solid 121 of the sublimable substance is precipitated, the processing conditions of the substrate W in the collapse rate A to the collapse rate C are the same.

The collapse rate A is lower than the value when the IPA drying of the substrate W is performed by removing the IPA on the substrate W by high-speed rotation of the substrate W and drying the substrate W. The collapse rate B is lower than the collapse rate A. Similarly, the collapse rate C is lower than the collapse rate A. The collapse rate C is lower than the collapse rate B. The collapse rate B is less than half of the collapse rate A. The collapse rate C is less than half of the collapse rate B. The collapse rate C is less than 1%, which is extremely low.

Since the collapse rate B is lower than the collapse rate A, so long as the solid 121 of the sublimable substance precipitated is dissolved in the pre-drying treatment liquid, and the solid 121 of the sublimable substance is precipitated again, the collapse rate of the pattern PA can be reduced. Since the collapse rate C is lower than the collapse rate B, when the sublimable substance is camphor, as long as methanol is used as a solvent instead of IPA as a solvent, the collapse rate of the pattern PA can be further reduced. Therefore, even when the intensity of the pattern PA is extremely low, the first precipitation process (step S7 in FIG. 9) and the first dissolution process (step S8 in FIG. 9) can be repeated once or more as in this embodiment. , It can reduce the collapse rate of the pattern PA. That is, even if N=0 in FIG. 9, the collapse rate of the pattern PA can be reduced.

According to research conducted by the inventors, when the gap G1 of the pattern PA (refer to FIG. 10A) is 30 nm or less, there are cases where a good collapse rate of the pattern PA cannot be obtained even if the sublimation drying is performed. It is believed that the reason is that the incomplete precipitation region where the solid 121 of the sublimable substance does not exist or hardly exists between the patterns PA is formed in the upper surface of the substrate W. Therefore, as long as the solid 121 of the sublimable substance precipitated is dissolved in the pre-drying treatment liquid, the solid 121 of the sublimable substance is precipitated again, even if the gap G1 of the pattern PA is a substrate W of 30 nm or less, it can be reduced. The collapse rate of pattern PA.

Next, the change in the thickness of the treatment liquid film 120 before drying will be described.

FIG. 14 is a graph showing the temporal change in the thickness of the pre-drying treatment liquid film 120 on the upper surface of the substrate W until the solid 121 of the sublimable substance is deposited from the pre-drying treatment liquid. The aspect ratio of the inset in FIG. 14 is different from the other parts in FIG. 14.

The multiple curves in FIG. 14 (the solid line curve, the single-dot chain line curve, and the dashed curve curve) represent the film thickness curves of the measured values when multiple pre-drying treatment solutions with different concentrations of sublimable substances are used. Except for the concentration of sublimable substances, the conditions for each measurement are the same. As shown in FIG. 14, regardless of the concentration of the sublimable substance, when the solid 121 of the sublimable substance is precipitated from the pre-drying treatment liquid, the thickness of the pre-drying treatment liquid film 120 decreases with the passage of time.

In FIG. 14, the thickness of the pre-drying treatment liquid film 120 is only measured until time T1. The reason is that at time T1, the solid 121 of the sublimable substance precipitates. In other words, the treatment liquid before drying is transparent. In contrast, the transparency of the solid 121 of the sublimation material is lower than the transparency of the treatment liquid before drying. Therefore, when the solid 121 of the sublimable substance precipitates, the detection value of the film thickness measuring unit 91 changes greatly, and the thickness of the treatment liquid film 120 before drying cannot be measured.

When the solid 121 of the sublimable substance precipitates, the detection value of the film thickness measuring unit 91 changes greatly. Therefore, the controller 3 can determine whether the solid 121 of the sublimable substance precipitates by monitoring the detection value of the film thickness measuring unit 91. Furthermore, the thickness of the pre-drying liquid film 120 immediately before precipitation of the solid 121 of the sublimable substance is substantially equal to the thickness of the solid 121 of the sublimable substance immediately after the solid 121 of the sublimable substance is precipitated. Therefore, the controller 3 can also measure the thickness of the solid 121 of the sublimable substance by measuring the thickness of the liquid film 120 before drying.

Moreover, as shown in FIG. 14, regardless of the concentration of the sublimable substance, the film thickness of the treatment solution before drying decreases sharply, and then gradually decreases. During the rapid decrease in the thickness of the pre-drying treatment liquid film 120, the thickness and the film thickness reduction rate of the pre-drying treatment liquid film 120 are almost the same in a plurality of pre-drying treatment liquids with different concentrations of sublimable substances. In other words, as long as the elapsed time is the same, regardless of the concentration of the sublimable substance, the thickness of the pre-drying treatment liquid film 120 decreases at approximately the same rate of decrease.

On the other hand, as shown in the inset in FIG. 14, during the period when the thickness of the treatment liquid film 120 is gradually reduced before drying, the difference in the film thickness reduction rate is observed in the plurality of pre-drying treatment solutions with different concentrations of sublimable substances. . It is believed that the reason is that if the concentration of the sublimable substance changes, the viscosity of the treatment solution before drying changes.

In detail, the higher the concentration of the sublimable substance in the treatment solution before drying, the higher the viscosity of the treatment solution before drying. The higher the viscosity of the pre-drying treatment liquid, the more difficult it is to use the centrifugal force generated by the rotation of the substrate W to be discharged to the outside of the substrate W. Therefore, the higher the concentration of sublimable substances in the treatment solution before drying, the smaller the slope of the graph. In other words, the higher the concentration of the sublimable substance in the pre-drying treatment liquid, the lower the film thickness reduction rate during the period during which the thickness of the pre-drying treatment liquid film 120 gradually decreases. Therefore, in the inset graph in Figure 14, the solid line shows the lowest concentration of sublimable substances in the pre-drying treatment solution, and the dotted line shows the second lowest concentration of sublimable substances in the pre-drying treatment solution, a single point The concentration of sublimable substances in the pre-drying treatment solution indicated by the chain line is the highest. That is, there is a correlation between the film thickness reduction rate and the concentration of the sublimable substance in the treatment solution before drying.

Therefore, as long as the film thickness reduction rate of a plurality of pre-drying liquid films 120 with different concentrations of sublimable substances is measured in advance and prepared as the reference data SD, the thickness of the pre-drying liquid film 120 on the substrate W can be monitored. , The concentration of the sublimable substance in the pre-drying treatment solution on the substrate W can be estimated based on the film thickness reduction rate. The reference data SD is, for example, stored in the main memory device 3c of the controller 3 (refer to FIG. 8). In order to compare with the film thickness reduction rate obtained by monitoring the thickness of the pre-drying treatment liquid film 120 on the substrate W during the substrate processing, the reference data SD stored in the main memory device 3c is referred to at any time.

If the thickness of the pre-drying liquid film 120 before the precipitation of the solid 121 of the sublimable substance is the same, the thickness of the solid 121 of the sublimable substance increases with the increase in the concentration of the sublimable substance, and with the decrease in the concentration of the sublimable substance And reduce. Therefore, by measuring the thickness of the liquid film 120 before drying and estimating the actual concentration of the sublimable substance, the thickness of the solid 121 of the sublimable substance can be estimated before the solid 121 of the sublimable substance is precipitated.

Fig. 15 is a flowchart showing the first example of the film thickness monitoring process. Hereinafter, refer to FIG. 2 and FIG. 15. The film thickness monitoring process is executed together with, for example, the first deposition process (step S7) at the beginning (see FIG. 9). That is, the film thickness monitoring process is only performed when the solid 121 of the sublimable substance is precipitated for the first time.

When starting the measurement of the thickness of the pre-drying treatment liquid film 120, the controller 3 determines whether the first precipitation process (precipitation process) has started (step S21 in FIG. 15). The initial judgment of whether the first precipitation process is started is performed based on, for example, whether the pre-drying treatment liquid valve 41 is opened, that is, whether the spraying of the pre-drying treatment liquid is stopped.

When the first precipitation process has not been started (No in step S21 in FIG. 15), that is, when the spraying of the treatment liquid before drying is stopped, the controller 3 judges the first precipitation process after a specific time has elapsed Whether to start (step S21 in Fig. 15). If the first precipitation process has started (Yes in step S21 in FIG. 15), that is, if the spraying of the pre-drying treatment liquid has been stopped, the controller 3 causes the film thickness measuring unit 91 to start drying the film thickness of the pre-treatment liquid The measurement (film thickness measurement process, step S22 in Figure 15).

During the film thickness measurement unit 91 measuring the thickness of the pre-drying liquid film 120, the controller 3 also measures the film thickness reduction rate of the pre-drying liquid film 120 based on the thickness of the pre-drying liquid film 120 (the film thickness reduction rate measurement process ).

The reference speed range representing the range of the appropriate film thickness reduction speed is based on the reference concentration range and reference data SD representing the concentration of the appropriate sublimable substance in the liquid film of the treatment liquid before drying, and is specified by the process recipe. The controller 3 judges whether the film thickness reduction speed is appropriate before the concentration of the sublimable substance in the liquid film 120 before drying reaches the saturation concentration. Step S23 of 15). In this way, it can be substantially determined whether the concentration of the solid of the sublimable substance in the liquid film 120 before drying is within the reference concentration range (concentration determination process).

When the film thickness reduction rate is appropriate, in other words, when the film thickness reduction rate is greater than or equal to the lower limit of the reference speed range and less than the upper limit of the reference speed range (in step S23 of FIG. 15, it is YES ), the controller 3 determines whether the solid 121 of the sublimable substance is precipitated in the first precipitation process (step S8 of FIG. 9) when the solid 121 of the sublimable substance is precipitated for the first time based on the detection value of the film thickness measuring unit 91 (FIG. 15的步骤S24). If the solid 121 of the sublimable substance is not precipitated (No in step S24 in FIG. 15), the controller 3 again determines whether the reduction rate of the film thickness is appropriate after a certain time has passed (step S23 in FIG. 15).

If the solid 121 of the sublimable substance has been precipitated (in step S24 of FIG. 15, yes), the controller 3 is based on the sublimation substance in the liquid film 120 before the precipitation of the solid 121 of the sublimable substance. The measured value of the film thickness measuring unit 91 when the concentration reaches the saturation concentration, to determine whether the thickness of the solid 121 of the sublimable substance is appropriate. In other words, the controller 3 determines whether the thickness of the solid 121 of the sublimable substance exceeds the lower limit of the reference thickness range and does not reach the upper limit of the reference thickness range (thickness determination process, step S25 in FIG. 15).

If the thickness of the solid 121 of the sublimable substance is appropriate (Yes in step S25 of FIG. 15), the controller 3 causes the film thickness measuring unit 91 to stop the measurement of the thickness of the liquid film 120 before drying (step S26 of FIG. 15) ). If the thickness of the solid 121 of the sublimable substance is not appropriate (No in step S25 of FIG. 15), the controller 3 causes the alarm device 100C (refer to FIG. 8) to generate an alarm (the second abnormality notification process, the step of FIG. 15) S27). After that, the measurement of the thickness of the pre-drying liquid film 120 by the film thickness measurement unit 91 is stopped (step S26 in FIG. 15).

Due to the failure of the first flow control valve 107A or the second flow control valve 107B (refer to Fig. 7) and other reasons, the concentration of the sublimable substance is outside the reference concentration range, and the film thickness reduction speed is greater than the reference speed range In the case of a limit value or when the film thickness reduction speed is less than the lower limit value of the reference speed range (No in step S23 in FIG. 15), the controller 3 causes the alarm device 100C (refer to FIG. 8) to generate an alarm (first The abnormal notification process, step S28 in Figure 15).

After that, the controller 3 starts the pre-drying treatment liquid removal process of removing the pre-drying treatment liquid from the upper surface of the substrate W before the solid 121 of the sublimable substance is deposited (step S29 in FIG. 15). The details of the pre-drying treatment liquid removal process are as follows. Then, the controller 3 causes the film thickness measurement unit 91 to stop the measurement of the film thickness of the treatment liquid before drying (step S26 in FIG. 15).

When the substrate processing is not interrupted, after the first precipitation process (step S7 in FIG. 9) and the film thickness monitoring process are performed, the first dissolution process (step S8 in FIG. 9) is started. When the pre-drying treatment liquid is a solution of a sublimable substance and IPA, in order to dissolve the precipitated solid 121 of the sublimable substance in the pre-drying treatment liquid, heating of the substrate W is started. Then, after repeating the first precipitation process and the first dissolution process for a specific number of times, the final precipitation process is performed, and the sublimation process is finally performed. In the case of N=0 in FIG. 9, the first precipitation process and the first dissolution process are not repeated, but the final precipitation process is performed, and the sublimation process is finally performed.

That is, when it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is within the reference concentration range, the sublimation process is performed after the final precipitation process is completed.

FIG. 16 is a schematic diagram for explaining an example of the process of removing the treatment liquid before drying in the first example of the film thickness monitoring process.

As described above, in order to determine whether the concentration of the sublimable substance contained in the pre-drying treatment liquid film 120 is appropriate, the controller 3 measures the rate of decrease in the thickness of the pre-drying treatment liquid film 120 (step S23 in FIG. 15). The reason is that if the concentration of the sublimable substance in the treatment liquid film 120 before drying is abnormal, that is, if the concentration of the sublimable substance in the treatment liquid film 120 before drying is outside the reference concentration range, the final precipitation process (Figure 9 The thickness of the solid 121 of the sublimable substance precipitated in step S9) will be larger or smaller than the intended value. If the thickness of the solid 121 of the sublimation substance immediately before sublimation is greater or less than the intended value, the collapse rate of the pattern PA may be deteriorated.

Therefore, the controller 3 implements the pre-drying treatment liquid removal process shown in FIG. 16 (step S29 in FIG. 15). FIG. 16 shows a state in which the replacement liquid nozzle 43 sprays a solvent corresponding to the replacement liquid onto the upper surface of the substrate W. As shown in FIG. Fig. 16 shows an example in which the pre-drying treatment liquid is a solution of camphor and IPA, and the solvent is IPA. When the pre-drying treatment liquid is a solution of camphor and methanol, methanol is sprayed from the replacement liquid nozzle 43 instead of IPA.

When the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is abnormal, as shown in FIG. 16, the controller 3 may also cause the replacement liquid nozzle 43 to spray the solvent. In this case, the pre-drying treatment liquid on the substrate W is replaced with a solvent, and a liquid film of the solvent covering the entire upper surface of the substrate W is formed. Therefore, before the solid 121 of the sublimable substance is deposited, the pre-drying treatment liquid with an inappropriate concentration of the sublimable substance can be removed from the substrate W. That is, when it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is not within the reference concentration range, the pre-drying treatment solution removal process is performed, that is, by the sublimation in the first precipitation process Before the solid 121 of the substance is deposited, a solvent as a removing liquid is supplied to the upper surface of the substrate W, and the pre-drying treatment liquid is removed from the upper surface of the substrate W.

In this way, when the pre-drying treatment liquid is a solution of camphor and IPA, in the pre-drying treatment liquid removal process, IPA functions as a removal liquid for removing the pre-drying treatment liquid from the upper surface of the substrate W. When the pre-drying treatment liquid is a solution of camphor and methanol, the methanol acts as a removal liquid during the removal process of the pre-drying treatment liquid. The removal liquid is preferably the same liquid as the solvent used for the drying pretreatment liquid, but it is not limited to this. The removal liquid only needs to have compatibility with the pre-drying treatment liquid, and may be a liquid of a different type from the solvent of the pre-drying treatment liquid.

After the controller 3 interrupts the first precipitation process and starts the pre-drying treatment liquid removal process (step S29 in FIG. 15), the controller 3 causes the film thickness measurement unit 91 to stop the measurement of the thickness of the treatment liquid film 120 before drying (step S29 in FIG. 15). S26).

In the substrate processing of this embodiment, when the solid 121 of the sublimable substance starts to precipitate in the first precipitation process, the pre-drying treatment liquid remains on the upper surface of the substrate W. In the first dissolution process, at least a part of the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid. Thereafter, in the final precipitation process, the solvent is again evaporated from the pre-drying treatment liquid. Thereby, the content of the solvent is reduced, and the solid 121 of the sublimable substance is deposited on the upper surface of the substrate W. After that, the solid 121 of the sublimable substance is sublimated and removed from the substrate W. In this way, the pre-drying treatment liquid is removed from the substrate W, and the substrate W is dried.

Before the solid 121 of the sublimable substance is precipitated for the first time, the pre-drying treatment liquid not only exists between the patterns PA, but also exists above the patterns PA. In a substrate W such as a semiconductor wafer or a substrate for FPD, the interval G1 between the patterns PA is relatively narrow. When the gap G1 between the patterns PA is narrow, the nature of the pre-drying treatment liquid existing between the patterns PA and the main body of the pre-drying treatment liquid, in other words, it is located on the surface (upper surface) of the self-drying pre-treatment liquid film 120 The pre-drying treatment liquid in the range up to the upper surface of the pattern PA is different. The difference in the properties of the two becomes significant as the interval G1 between the patterns PA becomes narrower.

If the gap G1 of the pattern PA is narrow, there is a situation that when the solid 121 of the sublimable substance is precipitated for the first time, the solid 121 of the sublimable substance is only precipitated in the main body of the treatment liquid before drying, and the solid 121 of the sublimable substance is not The incomplete precipitation region existing or hardly existing between the patterns PA is formed in the upper surface of the substrate W. In this case, the surface tension of the pre-drying treatment liquid between the patterns PA is applied to the sides of the pattern PA. Therefore, when the solid 121 of the sublimable substance is sublimed, the pattern PA in the incomplete precipitation area may collapse. This becomes the cause of the increase (deterioration) of the collapse rate of the pattern PA.

In contrast, if the precipitated solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid, and then the solid 121 of the sublimable substance is precipitated again, the sublimable substance will also be formed in a narrow space such as the space between the patterns PA. The crystalline nucleus of the solid 121. Therefore, as long as the solid 121 of the sublimable substance precipitated is dissolved in the pre-drying treatment liquid, and the solid 121 of the sublimable substance is precipitated again, even when the interval G1 of the pattern PA is narrow, incompleteness can be prevented. The generation of precipitation area, or reduce its area. In this way, the collapse rate of the pattern PA can be reduced.

The thickness of the solid 121 of the sublimable substance is substantially the same as the thickness of the pre-drying treatment liquid film 120 when the saturated concentration of the sublimable substance is reached. If the concentration of the sublimable substance in the pre-drying treatment liquid film 120 reaches the saturation concentration of the sublimable substance, the solid 121 of the sublimable substance is precipitated immediately thereafter. Therefore, as long as the concentration of the sublimable substance in the liquid film 120 before drying can be known before the concentration of the sublimable substance in the liquid film 120 reaches the saturation concentration of the sublimable substance, the solid of the sublimable substance can be predicted. The thickness of 121 is to avoid the formation of solid 121 of sublimation material of improper thickness.

Generally, in order to measure the concentration of a substance in a liquid, a device (not shown) for measuring the concentration needs to be brought into contact with the liquid. Since the pre-drying treatment liquid film 120 formed on the substrate W is relatively thin, it is difficult to make the equipment for concentration measurement contact the pre-drying treatment liquid film 120 without contacting the upper surface of the substrate W. Therefore, the pattern PA formed on the upper surface of the substrate may be damaged.

As described above, the inventors of the present application have discovered that there is a correlation between the film thickness reduction rate and the concentration of the sublimable substance in the liquid film 120 before drying. In this embodiment, before the solid 121 of the sublimable substance precipitates in the first precipitation process, the sublimable substance in the pre-drying treatment liquid film 120 is determined based on the film thickness reduction rate of the pre-drying treatment liquid film 120 Whether the concentration is within the reference concentration range (concentration determination process).

In detail, the thickness reduction rate of the pre-drying treatment liquid film 120 in the first precipitation process can be measured by continuously measuring the thickness of the pre-drying treatment liquid film 120 for a specific time by the film thickness measuring unit 91. Therefore, the controller 3 can substantially determine whether the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is the reference concentration by determining whether the film thickness reduction speed measured by the film thickness measuring unit 91 is within the reference speed range. Within range. Thereby, while avoiding difficult measurement, it is possible to determine whether the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is within the reference concentration range.

The amount of solvent evaporated in the first dissolution process and the final precipitation process can be predicted. Therefore, even when the concentration determination process is performed in the first precipitation process, it can be based on the drying pre-treatment liquid film 120 in the first precipitation process. It is determined whether the thickness of the sublimable substance solid 121 formed on the upper surface of the substrate W is appropriate.

Therefore, when it is determined that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is within the reference concentration range, after the final precipitation process is completed, a solid 121 of the sublimable substance with an appropriate thickness is formed. Therefore, as long as the substrate processing is continued to sublime the solid 121 of the sublimable substance, the collapse rate of the pattern PA on the upper surface of the substrate W can be reduced.

On the other hand, when it is determined that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is not within the reference concentration range, the sublimable substance can be removed from the upper surface of the substrate W by removing the liquid before the solid 121 of the sublimable substance is deposited. Removal of sublimable substances (treatment liquid removal process before drying). Thereby, it is possible to prevent the formation of the solid 121 of the sublimable substance with an inappropriate thickness on the upper surface of the substrate W beforehand. Therefore, the increase in the collapse rate of the pattern PA can be suppressed. Moreover, even when it is determined that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is not within the reference concentration range, the pre-drying treatment liquid on the upper surface of the substrate W is removed. Therefore, the substrate W can be reused.

Furthermore, in this embodiment, the concentration of the sublimable substance in the liquid film 120 before drying is estimated by comparing the reference data SD with the film thickness reduction rate measured in the first precipitation process. Therefore, in the first precipitation process, the concentration of the sublimable substance in the treatment liquid film 120 before drying can be easily estimated.

Furthermore, in this embodiment, when it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is not within the reference concentration range, the operator is notified of an abnormality (first abnormality notification process). Therefore, the operator can determine whether to continue the substrate processing at an appropriate time based on the notification of the abnormality.

In addition, in this embodiment, the thickness of the liquid film 120 before drying is measured by the film thickness measuring unit 91 immediately before the solid 121 of the sublimable substance is precipitated by the evaporation of the solvent (film thickness measuring process). Then, the controller 3 determines whether the thickness of the pre-drying liquid film 120 measured in the film thickness measurement process is within the reference thickness range of the solid 121 of the sublimation substance (thickness determination process).

Therefore, it is possible to determine whether the thickness of the pre-drying treatment liquid film 120 when the concentration of the sublimable substance in the pre-drying treatment liquid film 120 reaches the saturated concentration of the sublimable substance is within the reference thickness range of the solid 121 of the sublimable substance. It is determined whether the thickness of the solid 121 of the sublimable substance formed on the upper surface of the substrate W is appropriate.

When the thickness of the solid 121 of the sublimable substance formed on the upper surface of the substrate W is appropriate, after the final precipitation process is completed, the solid 121 of the sublimable substance of appropriate thickness is formed. Therefore, as long as the substrate processing is continued to sublime the solid 121 of the sublimable substance, a substrate W with a reduced collapse rate of the pattern PA can be obtained.

On the other hand, when the thickness of the solid 121 of the sublimable substance formed on the upper surface of the substrate W is inappropriate, by interrupting the substrate processing, the generation of the substrate W whose collapse rate of the pattern PA increases can be suppressed.

In this embodiment, in the thickness determination process, when it is determined that the film thickness measured in the film thickness measurement process is not within the above-mentioned reference thickness range, an abnormality is reported to the operator (the second abnormality notification process). Therefore, the operator can determine whether to continue the substrate processing at an appropriate time based on the notification of the abnormality.

In this embodiment, in the first precipitation process, the solvent is not evaporated from the pre-drying solution by heating the pre-drying treatment solution, but the pre-drying treatment solution is maintained at a temperature below room temperature while maintaining The solvent evaporates from the treatment liquid before drying. In this case, on the surface of the treatment solution before drying, the concentration of the sublimation substance increases locally, and the solid 121 of the sublimation substance precipitates on or near the surface of the treatment solution before drying (room temperature precipitation process). At the same time, the treatment liquid before drying remains between the solid 121 of the sublimation material and the upper surface of the pattern PA. The solid 121 of the sublimation substance is dissolved in the pre-drying treatment liquid.

In contrast, if the solvent is evaporated from the pre-drying treatment solution by heating the pre-drying treatment solution in the first precipitation process, the temperature of the pre-drying treatment solution rises to a value higher than room temperature, and the pre-drying treatment solution The concentration of sublimation substances rises. After the concentration of the sublimable substance is increased, the solid 121 of the sublimable substance is precipitated by natural cooling or forced cooling of the treatment liquid before drying, then most or the whole of the main body of the treatment liquid before drying becomes sublimable The case of the substance of the solid 121.

If the pre-drying treatment liquid does not remain above the pattern PA, the solid 121 of the sublimable substance will not be efficiently dissolved in the pre-drying treatment liquid. Even if the pre-drying treatment liquid remains between the patterns PA, the efficiency of the sublimation substance's solid 121 dissolving in the pattern PA is inferior to the efficiency of the sublimation substance's solid 121 dissolving in the main body of the drying pretreatment solution . Therefore, by maintaining a part of the main body of the treatment liquid before drying as a liquid, the solid 121 of the sublimable substance can be efficiently dissolved in the treatment liquid before drying.

Furthermore, in this embodiment, in the first dissolution process, the pre-drying treatment liquid on the upper surface of the substrate W is heated, so that the temperature of the pre-drying treatment liquid rises to a value higher than room temperature. The dissolution of the solid 121 of the sublimable substance in the pre-drying treatment liquid is promoted by the increase in the temperature of the pre-drying treatment liquid. Thereby, the solid 121 of the sublimable substance can be efficiently dissolved in the pre-drying treatment liquid. Furthermore, since the forced dissolution of the solid 121 of the sublimable substance starts with the start of heating, by changing the time when the heating is started, the forced dissolution of the solid 121 of the sublimable substance can be started at any time.

Also, in this embodiment, in the first dissolution process, the solid 121 of the sublimable substance and the pre-drying treatment liquid are not directly heated from above the substrate W, but indirectly heated via the substrate W (indirect heating) Process). If the solid 121 of the sublimable substance and the pre-drying treatment liquid are heated from above the substrate W, a part of the solid 121 of the sublimable substance on the surface of the pre-drying treatment liquid may be sublimated. In this case, a part of the sublimation material is wasted, and the final thickness of the solid 121 of the sublimation material is less than the intended value. If the solid 121 of the sublimable substance and the pre-drying treatment liquid are heated through the substrate W, the disappearance of the sublimable substance can be reduced.

Moreover, in this embodiment, in the final precipitation process, in order to precipitate the solid 121 of the sublimable substance on the substrate W, the pre-drying treatment liquid is heated while the solvent is evaporated from the pre-drying treatment liquid. Thereby, the solid 121 of the sublimable substance is precipitated from the high-temperature drying pretreatment liquid. The saturated concentration of the sublimable substance in the pre-drying treatment liquid increases with the increase in the temperature of the pre-drying treatment liquid. The ratio of the solvent contained in the solid 121 of the sublimable substance decreases as the saturation concentration of the sublimable substance increases. When the solid 121 of the sublimable substance is sublimated, the solvent contained in the solid 121 of the sublimable substance may produce a destructive force that degrades the pattern PA. Therefore, the collapse rate of the pattern PA can be further reduced by reducing the content of the solvent.

Furthermore, in this embodiment, in the first precipitation process, the solid 121 of the sublimable substance is precipitated on the surface of the pre-drying treatment liquid film 120 (liquid surface precipitation process). When the solvent evaporates from the treatment liquid before drying, the heat of the treatment liquid before drying, which is equivalent to the heat of vaporization, is released together with the solvent in the gas atmosphere, and the temperature of the surface of the treatment liquid before drying decreases. When the solid 121 of the sublimable substance is formed, the solvent evaporated from the treatment liquid before drying is reduced, and therefore, the heat of the treatment liquid before drying released in the gas atmosphere is also reduced. At the same time, the heat in the gas atmosphere is transferred to the pre-drying treatment liquid through the solid 121 of the sublimable substance. Thereby, the temperature of the interface between the solid 121 of the sublimation substance and the treatment liquid before drying rises. Therefore, even if the pre-drying treatment liquid on the substrate W is not forcibly heated, the solid 121 of the sublimable substance can be dissolved in the pre-drying treatment liquid (natural dissolution process).

The film thickness monitoring process is not limited to the flowchart shown in FIG. 15. For example, FIG. 17 shows a flowchart showing the flow of the second example of the film thickness monitoring process. The following FIG. 20 shows a flowchart showing the flow of the third example of the film thickness monitoring process. The following FIG. 22 shows a flowchart showing the flow of the fourth example of the film thickness monitoring process.

In the film thickness monitoring process of the second example shown in FIG. 17, the difference from the film thickness monitoring process of the first example (refer to FIG. 15) is the following: When the concentration is higher than the upper limit of the reference concentration range, and when the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is lower than the lower limit of the reference concentration range, different processes are started.

In the film thickness monitoring process of the second example, when the film thickness reduction speed is greater than the upper limit of the reference speed range or the film thickness reduction speed is less than the lower limit of the reference speed range (in step S23 of FIG. 17) , No), the controller 3 causes the alarm device 100C (refer to FIG. 8) to generate an alarm (the first abnormality notification process, step S28 in FIG. 17). Thereafter, the controller 3 determines whether the film thickness reduction speed is less than the lower limit of the reference speed range (step S31 in FIG. 17).

When the film thickness reduction rate is less than the lower limit of the reference speed range (Yes in step S31 of FIG. 17), that is, the concentration of the sublimable substance in the treatment liquid film 120 before drying is higher than the reference concentration range In the case of the upper limit value, the controller 3 starts the solvent evaporation suppression process for suppressing the solvent evaporation from the liquid film on the substrate W (step S32 in FIG. 17). Thereby, the concentration of the sublimable substance in the liquid film 120 before drying is reduced and adjusted to be within the reference concentration range.

On the other hand, when the film thickness reduction speed is greater than the upper limit of the reference speed range (No in step S31 of FIG. 17), that is, the concentration of the sublimable substance in the treatment liquid film 120 before drying is low When the reference concentration range is lower than the limit value, the controller 3 starts to promote the solvent evaporation promotion process for the solvent to evaporate from the pre-drying treatment liquid film 120 (step S33 in FIG. 17). Thereby, the concentration of the sublimable substance in the liquid film 120 before drying is increased and adjusted to be within the reference concentration range.

After starting the solvent evaporation suppression process or the solvent evaporation promotion process, as in the first example of the film thickness monitoring process shown in FIG. 15, the controller 3 causes the film thickness measurement unit 91 to stop the measurement of the thickness of the treatment liquid film 120 before drying ( Step S26 in Figure 17).

FIG. 18 is a schematic diagram for explaining an example of the solvent evaporation suppression process. In the solvent evaporation suppression process, for example, mist or vapor of the solvent is supplied to the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51. FIG. 18 shows an example in which the pre-drying treatment liquid is a solution of camphor and IPA, and the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51 is filled with nitrogen containing mist or vapor of IPA. When the pre-drying treatment liquid is a solution of camphor and methanol, nitrogen gas containing methanol mist or vapor is sprayed onto the upper surface of the substrate W. Nitrogen is equivalent to the carrier gas that transports the mist or vapor of the solvent to the direction of the substrate W.

When spraying to the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51, it is sufficient to supply nitrogen gas to the IPA (liquid) in the tank (so-called bubbling). In this way, a plurality of nitrogen bubbles are formed in the IPA, and the nitrogen containing the mist or vapor of the IPA is released from the surface of the IPA in the tank. It is sufficient to make at least one of the central nozzle 55 and the central opening 61 on the blocking member 51 spray the nitrogen gas.

If mist or vapor of the solvent is supplied to the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51, the vapor pressure of the solvent in the gas atmosphere in contact with the pre-drying treatment liquid film 120 increases. Therefore, evaporation of the solvent from the pre-drying treatment liquid film 120 is suppressed. On the other hand, since the vapor pressure of the sublimable substance in the gas atmosphere does not change, although it is a trace amount, the sublimable substance evaporates from the treatment liquid before drying. Therefore, assuming that the concentration of the sublimable substance is higher than the upper limit of the reference concentration range, as long as the mist or vapor of the solvent is supplied to the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51, the The concentration of the sublimable substance in the treatment liquid film 120 before drying is set to a concentration within the reference concentration range, so that the solid 121 of the sublimable substance of the intended thickness can be precipitated.

FIG. 19 is a schematic diagram for explaining an example of the solvent evaporation promotion process. In the solvent evaporation promotion process, for example, gas such as mist or vapor not containing IPA is supplied to the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51. The controller 3 can cause the central nozzle 55 to spray nitrogen gas, and can also cause the central opening 61 on the blocking member 51 to spray nitrogen gas. When the central nozzle 55 has sprayed nitrogen gas, the controller 3 can also increase the opening of the flow regulating valve 58 (refer to FIG. 2). When nitrogen has been sprayed from the central opening 61 on the blocking member 51, the controller 3 can also increase the opening of the flow regulating valve 65 (refer to FIG. 2).

If nitrogen gas is supplied to the space between the upper surface of the substrate W and the lower surface 51L of the blocking member 51, the vapor pressure of the solvent in the gas atmosphere in contact with the pre-drying treatment liquid film 120 decreases. Therefore, the evaporation of the solvent from the pre-drying treatment liquid is promoted. Strictly speaking, the vapor pressure of sublimable substances in a gas atmosphere is also very small, but it is lowered. However, since the vapor pressure of the sublimable substance is much lower than that of the solvent, the solvent mainly evaporates from the treatment liquid before drying. Therefore, the concentration of the sublimable substance in the pre-drying treatment liquid film 120 can be set to a concentration within the reference concentration range, and the solid 121 of the sublimable substance of the intended thickness can be precipitated.

The nitrogen gas sprayed from the central nozzle 55 and the central opening 61 on the blocking member 51 promotes the precipitation of the solid 121 of the sublimable substance. Therefore, the central nozzle 55 and the central opening 61 on the blocking member 51 serve as a solvent evaporation unit And function.

By comparing the film thickness reduction rate immediately before the solvent evaporation suppression process or the solvent evaporation promotion process and the film thickness reduction rate included in the reference data SD, it is possible to calculate the evaporation amount of the solvent from the liquid film 120 before drying. To what extent is appropriate, the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is set as the concentration within the reference concentration range. As long as the solvent evaporation suppression process or the solvent evaporation promotion process is performed in such a way that the evaporation volume of the solvent becomes the appropriate evaporation volume, the thickness of the pre-drying treatment liquid film 120 when the concentration of the sublimable substance reaches the saturated concentration can be easily adjusted to the appropriate The thickness. Furthermore, the solid 121 of sublimation material of proper thickness can be precipitated.

In the second example of the film thickness monitoring process, when the concentration of the sublimable substance in the liquid film 120 before drying is determined to be higher than the upper limit of the reference concentration range in the concentration determination process, the vapor of the solvent or The mist is supplied to the gas atmosphere in contact with the pre-drying treatment liquid film 120 to suppress the evaporation of the solvent from the pre-drying treatment liquid film 120 (solvent evaporation suppression process).

By supplying solvent vapor or mist to the gas atmosphere connected to the pre-drying treatment liquid film 120, the amount of solvent (solvent vapor pressure) present in the gas atmosphere connected to the pre-drying treatment liquid film 120 increases . This can prevent the solvent from evaporating from the pre-drying liquid film 120. If the solvent is prevented from evaporating from the pre-drying treatment liquid film 120, the ratio of the sublimable substances in the substances evaporated from the pre-drying treatment liquid film 120 increases. Therefore, the concentration of the sublimable substance in the liquid film 120 before drying decreases. Thereby, the concentration of the sublimable substance in the liquid film 120 before drying can be adjusted to be within the reference concentration range.

Therefore, even if it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is higher than the upper limit of the reference concentration range, the solvent evaporation suppression process is performed. Therefore, after the sublimation process, the reduction can be obtained. The substrate W for the collapse rate of the pattern PA.

In addition, in the second example of the film thickness monitoring process, when it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying liquid film 120 is lower than the lower limit of the reference concentration range, the first During the execution of the precipitation process, an inert gas is supplied to the gas atmosphere connected to the pre-drying treatment liquid film 120 to promote the evaporation of the solvent from the pre-drying treatment liquid film 120 (solvent evaporation promotion process).

By promoting the evaporation of the solvent from the pre-drying treatment liquid film 120, the concentration of the sublimable substance in the pre-drying treatment liquid film 120 increases. Thereby, the concentration of the sublimable substance in the liquid film 120 before drying can be adjusted to be within the reference concentration range. Therefore, even if it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is lower than the lower limit of the reference concentration range, the solvent evaporation promotion process is performed. Therefore, after the sublimation process, it is possible to reduce The substrate W for the collapse rate of the pattern PA.

In the third example of the film thickness monitoring process shown in Figure 20, the difference from the second example of the film thickness monitoring process (refer to Figure 17) is the following: the film thickness reduction rate is less than the lower limit of the reference speed range (Yes in step S31 of FIG. 20), that is, when the concentration of the sublimable substance in the treatment liquid film 120 before drying is higher than the upper limit of the reference concentration range, the controller 3 starts to The thin-filming process of thinning the liquid film 120 before drying on the substrate W (step S34 in FIG. 20).

When the film thickness reduction rate is greater than the upper limit of the reference speed range (No in step S31 of FIG. 20), that is, the concentration of the sublimable substance in the treatment liquid film 120 before drying is lower than the reference concentration range In the case of the lower limit value, the controller 3 starts the solvent evaporation promotion process in the same way as the second example of the film thickness monitoring process (step S33 in FIG. 20).

During the thin filming process, the controller 3 causes the rotation motor 14 to accelerate the rotation of the substrate W. Thereby, the centrifugal force of the pre-drying treatment liquid film 120 acting on the substrate W is increased, and the amount of the pre-drying treatment liquid discharged to the outside of the substrate W is increased.

21A and 21B are schematic diagrams for explaining the thin film process. FIG. 21A shows the state before the rotation of the substrate W is accelerated, and FIG. 21B shows the state after the rotation of the substrate W is accelerated. Specifically, the rotation speed of the substrate W is changed from the first deposition speed (for example, 500 rpm) to a filming speed higher than the first deposition speed (for example, 1500 rpm).

When the concentration of the sublimable substance in the pre-drying treatment liquid film 120 is higher than the upper limit of the reference concentration range, the thickness of the solid 121 of the sublimable substance immediately before sublimation is greater than the intended value. If the thickness of the pre-drying liquid film 120 on the substrate W is reduced, the amount of sublimable substances contained in the pre-drying liquid film 120 is reduced, and therefore, the thickness of the solid 121 of the sublimable substance is also reduced.

Therefore, in the third example of the film thickness monitoring process, when the concentration of the sublimable substance in the treatment liquid film 120 before drying is higher than the upper limit of the reference concentration range, by increasing the rotation speed of the substrate W, The centrifugal force acts on the pre-drying treatment liquid film 120, and the thickness of the pre-drying treatment liquid film 120 is reduced before the solid 121 of the sublimation material is deposited. Thereby, the thickness of the solid 121 of the sublimable substance formed on the upper surface of the substrate W can be reduced, and the solid 121 of the sublimable substance of the intended thickness can be precipitated. Therefore, even if it is determined in the concentration determination process that the concentration of the sublimable substance in the pre-drying liquid film 120 is higher than the upper limit of the reference concentration range, the thinning process is performed. Therefore, after the sublimation process, a reduced pattern can be obtained. Substrate W for the collapse rate of PA.

When the pre-drying treatment solution is a solution of camphor and IPA, the fourth example of the film thickness monitoring process shown in FIG. 22 can also be performed. The difference between the fourth example of the film thickness monitoring process and the first example of the film thickness monitoring process (refer to Figure 15) is the following: When the thickness of the solid 121 of the sublimable substance is determined to be within the reference thickness range (in the figure) In step S25 of 22, yes), the controller 3 starts the first dissolution process (step S45 of FIG. 22). That is, the controller 3 starts the supply of a heating liquid such as warm water to the lower surface of the substrate W, and starts the heating of the liquid film of the pre-drying treatment liquid on the upper surface of the substrate W via the substrate W. Thereafter, the film thickness measurement unit 91 is caused to stop the measurement of the film thickness of the pre-drying treatment liquid (step S26 in FIG. 22).

In the fourth example of the film thickness monitoring process, the first dissolution process is started with the formation of a solid 121 of a sublimable substance with an appropriate thickness as an opportunity. Therefore, the first dissolution process, the final precipitation process, and the sublimation process are performed only when the solid 121 of the sublimable substance with an appropriate thickness is formed. After the sublimation process is completed, a substrate W with a reduced collapse rate of the pattern PA can be obtained. When the solid 121 of the sublimable substance with an appropriate thickness is not formed, the processes after the first precipitation process (the first dissolution process, the final precipitation process, and the sublimation process) may not be performed, and the substrate processing may be interrupted earlier.

When the time from the precipitation of the solid 121 of the sublimable substance to the sublimation is short, before the solid 121 of the sublimable substance is dissolved in the pre-drying treatment liquid, in other words, before the heating of the pre-drying treatment liquid is started, the sublimable substance Part or all of the solid 121 may be sublimated. In this case, as long as the solid 121 of the sublimable substance is monitored for precipitation, the heating of the treatment liquid before drying can be started at the optimal time, and the solid 121 of the sublimable substance that is sublimated unintentionally can be reduced.

The present invention is not limited to the content of the above-mentioned embodiment, and various modifications can be made.

As described above, in the above-mentioned substrate processing, the film thickness monitoring process is performed together with the first deposition process (step S7). However, when the pre-drying treatment liquid is a solution of camphor and IPA, the thickness of the pre-drying treatment liquid film can also be monitored every time the solid 121 of the sublimable substance is precipitated.

In addition, when the pre-drying treatment liquid is a solution of camphor and IPA, the thickness of the pre-drying treatment liquid film 120 can also be monitored as shown by the two-dot chain line in FIG. 9, and the final precipitation process (step S9 in FIG. 9) ) Together. In other words, when the pre-drying treatment solution is a solution of camphor and IPA, it should be monitored together with at least one of the first precipitation process (step S7 in Figure 9) and the final precipitation process (step S9 in Figure 9). The thickness of the treatment liquid film 120 is sufficient.

Unlike the substrate processing of the above embodiment (refer to FIG. 9), as shown in FIG. 23, it is also possible to perform sublimation without dissolving the solid 121 of the sublimable substance precipitated in the pre-drying treatment liquid film 120 in the pre-drying treatment liquid. Substrate processing.

In the substrate processing of FIG. 23, after the film thickness reduction process (step S6), a precipitation process (step S50) is performed to precipitate solids of sublimable substances on the upper surface of the substrate W, and then, a sublimation process is performed (step S10). ). Then, any one of the first to third examples of the film thickness monitoring process is performed together with the deposition process (step S50).

In the first precipitation process (step S7 in FIG. 9) for the first precipitation of the solid 121 of the sublimable substance, the pre-drying treatment liquid film 120 may not be maintained at a temperature below room temperature, but higher than Heating is performed at the heating temperature of room temperature, while evaporating the solvent from the pre-drying treatment liquid on the substrate W.

In the final precipitation process (step S9 in FIG. 9) of the first substrate processing example, it is also possible to stop the forced heating of the pre-drying treatment liquid on the substrate W, while allowing the solvent to evaporate from the pre-drying treatment liquid instead of one side. The pre-drying treatment liquid on the substrate W is heated to evaporate the solvent from the pre-drying treatment liquid.

When dissolving the solid 121 of the sublimable substance in the pre-drying treatment liquid, heating gas higher than room temperature can also be sprayed onto the upper or lower surface of the substrate W instead of being used as a heating liquid higher than room temperature. One example of warm water is supplied to the lower surface of the substrate W. For example, at least one of the central nozzle 55 and the central opening 81 under the rotating base 12 can also be used to spray nitrogen gas at a higher temperature than room temperature. A heating element that generates Joule heat by energization, or a lamp that emits light to the substrate W may be arranged on at least one of the upper and lower sides of the substrate W. For example, at least one of the rotating base 12 and the blocking member 51 may be placed in the heating body.

The solid 121 of the sublimation substance can also be removed by the treatment unit 2 which is different from the wet treatment unit 2w. The processing unit 2 for removing the solid 121 of sublimable substances may be a part of the substrate processing apparatus 1 or a part of the substrate processing apparatus 1 different from the substrate processing apparatus 1. In other words, the substrate processing apparatus 1 equipped with the wet processing unit 2w and the substrate processing apparatus 1 equipped with the processing unit 2 of the solid 121 for removing sublimable substances can also be installed in the same substrate processing system before removing the solid 121 for sublimable substances. , The substrate W is transferred from the substrate processing apparatus 1 to another substrate processing apparatus 1.

When the pre-drying treatment liquid can be used to replace the rinse liquid on the substrate W such as pure water, the pre-drying treatment liquid supply process may be performed instead of the replacement liquid supply process of replacing the rinse liquid on the substrate W with the replacement liquid.

In addition to the circular plate portion 52, the blocking member 51 may also include a cylindrical portion extending downward from the outer periphery of the circular plate portion 52. In this case, if the blocking member 51 is arranged at the lower position, the substrate W held by the spin chuck 10 is surrounded by the cylindrical portion 25.

The blocking member 51 may also rotate around the rotation axis A1 together with the rotating chuck 10. For example, the blocking member 51 may also be placed on the rotating base 12 in a manner that does not contact the substrate W. In this case, the blocking member 51 is connected to the rotating base 12, and therefore, the blocking member 51 rotates in the same direction as the rotating base 12 at the same speed.

The blocking member 51 may be omitted. However, when a liquid such as pure water is supplied to the lower surface of the substrate W, it is preferable to provide a blocking member 51. The reason is that the blocking member 51 can be used to block the droplets flowing from the lower surface of the substrate W back to the upper surface of the substrate W along the outer peripheral surface of the substrate W, or the droplets splashing inward from the processing cup 21. It can reduce the liquid mixed into the pre-drying treatment liquid on the substrate W.

If it is not necessary to change the incident position of the light of the light-emitting element 92 with respect to the upper surface of the substrate W, the electric motor 96 of the film thickness measuring unit 91 may be omitted.

When the light of the light-emitting element 92 is incident on the upper surface of the substrate W substantially perpendicularly, the housing 93 of the film thickness measuring unit 91 may also house the light-receiving element 97 in addition to the light-emitting element 92. In this case, the light (reflected light) of the light emitting element 92 reflected by the upper surface of the substrate W passes through the opening of the housing 93 covered by the transparent plate 94 and is received by the light receiving element 97 in the housing 93 .

When both the light-emitting element 92 and the light-receiving element 97 are contained in the housing 93, the controller 3 can also move the housing 93 horizontally so that the light of the light-emitting element 92 is incident on the upper surface of the substrate W The incident position moves in the radial direction of the substrate W. Specifically, a scanning arm holding the housing 93 above the substrate W held by the rotating chuck 10 and an electric actuator for horizontally moving the scanning arm in the chamber 4 may also be provided in the processing unit 2.

In the above-mentioned embodiment, the film thickness measuring unit 91 cannot measure the liquid film of the treatment liquid before drying after the solid 121 of the sublimable substance is deposited. Unlike the above-mentioned embodiment, a film thickness measuring unit 191 that can measure the thickness of the solid 121 of a sublimable substance can also be used as the film thickness measuring unit (see FIG. 25A). The film thickness measurement unit 191 houses the light-emitting element 191A and the light-receiving element 191B in the same casing 191C. The film thickness measuring unit 191 can be moved along the rotation diameter direction of the substrate W by the moving unit 192, for example. Specifically, a scanning arm holding the housing 191C above the substrate W held by the rotating chuck 10 and an electric actuator for horizontally moving the scanning arm in the chamber 4 may also be provided in the processing unit 2.

Therefore, the film thickness measuring unit 191 can measure the thickness of the solid 121 (solid film) of the sublimable substance deposited on the upper surface of the substrate W at multiple locations on the upper surface of the substrate W while moving above the substrate W. A plurality of black dots Pi in FIG.

As long as the film thickness measurement unit 191 can measure multiple locations on the upper surface of the substrate W, the fifth example of the film thickness monitoring process shown in FIG. 24 can be performed. The fifth example of the film thickness monitoring process shown in FIG. 24 is different from the first example of the film thickness monitoring process shown in FIG. The flatness measurement process of the flatness of the surface and the flatness determination process for judging whether the surface of the solid 121 of the sublimation substance is flat.

Specifically, when the thickness of the solid 121 of the sublimable substance is appropriate (Yes in step S25 in FIG. 24), the movement of the film thickness measuring unit 191 in the direction of the rotation diameter of the substrate W is started (in FIG. 24, it is YES). Step S51). Thereby, as shown in FIG. 25A, the flatness of the surface of the solid 121 of the sublimable substance is measured (the flatness measurement process).

The degree of flatness refers to, for example, the degree of unevenness in the height position of the surface of the solid 121 of the sublimation material measured at a plurality of locations. The height position of the surface of the solid 121 of the sublimable substance can be directly measured by the film thickness measuring unit 191, or the height position of the solid 121 of the sublimable substance measured by the film thickness measuring unit 191 The thickness is calculated. The smaller the unevenness of the height position of the solid 121 of the sublimable substance measured at multiple locations, the flatter the surface of the solid 121 of the sublimable substance.

In addition, it is determined whether the surface of the solid 121 of the sublimable substance is sufficiently flat (flatness determination process, step S52 in FIG. 24). Thereby, it can be checked whether the solid 121 of sublimable substance with uniform thickness is formed on the whole area of the upper surface of the substrate W.

Specifically, when the flatness measured in the flatness measurement process is within the reference flat range (Yes in step S52 of FIG. 24), that is, the surface of the solid 121 of the sublimable substance is sufficiently flat In this case, the measurement of the thickness of the pre-drying liquid film 120 by the film thickness measurement unit 191 is stopped (step S26 in FIG. 24). Thereafter, as usual, the sublimation process is performed (step S10 in FIG. 9). Therefore, a substrate W with a reduced collapse rate of the pattern PA can be obtained.

When the flatness measured in the flatness measurement process is not within the reference flat range (No in step S52 of FIG. 24), that is, when the surface of the solid 121 of the sublimable substance is not flat enough, The solid 121 of the sublimable substance is removed from the upper surface of the substrate W (solid removal process, step S53 of FIG. 24). In the solid removal process, as shown in FIG. 25B, the solvent corresponding to the replacement liquid is supplied from the replacement liquid nozzle 43 to the upper surface of the substrate W on which the solid 121 of the sublimable substance is formed.

FIG. 25B shows an example in which the pre-drying treatment liquid is a solution of camphor and IPA, and the solvent is IPA. When the pre-drying treatment liquid is a solution of camphor and methanol, methanol is sprayed from the replacement liquid nozzle 43 instead of IPA. Thereby, as shown in FIG. 25C, the solid 121 of the sublimable substance is removed. After that, the measurement of the thickness of the pre-drying liquid film 120 by the film thickness measurement unit 191 is stopped (step S26 in FIG. 24).

In the film thickness monitoring process of the fifth example, the solid removal process is performed. Therefore, when a part of the solid 121 of the sublimation substance has an excessively thin part or an excessively thick part, the pattern PA can also be suppressed from inverting Bad. In addition, since the solid 121 of the sublimable substance on the upper surface of the substrate W is removed, the substrate W can be reused.

In this way, when the pre-drying treatment liquid is a solution of camphor and IPA, in the solid removal process, the IPA functions as a solid removal liquid that removes the solid 121 of sublimable substances from the upper surface of the substrate W. When the pre-drying treatment liquid is a solution of camphor and methanol, in the solid removal process, methanol serves as a solid removal liquid. The solid removal liquid is preferably the same liquid as the solvent used for the drying pretreatment liquid, but it is not limited to this. The solid removal liquid may be a liquid of a different type from the solvent of the treatment liquid before drying as long as it can remove the solid 121 of the sublimable substance.

The substrate processing device 1 is arranged in a clean room, and the temperature in the substrate processing device 1 is maintained at the same or approximately the same value as the temperature in the clean room, but the temperature in the substrate processing device 1 may also be different from the temperature in the clean room. For example, the substrate processing apparatus 1 may also include an air conditioner that adjusts the temperature in the substrate processing apparatus 1.

When the pre-drying treatment liquid is a solution of camphor and methanol, if the temperature in the substrate processing apparatus 1, more specifically, the temperature in the chamber 4 is higher than the temperature of the surface of the pre-drying treatment liquid when the sublimable substance is deposited (Hereinafter referred to as "surface temperature during precipitation"), only by placing the pre-drying treatment liquid on the upper surface of the substrate W, the temperature of the interface between the solid 121 of the sublimation substance and the pre-drying treatment liquid rises, and the sublimation substance The solid 121 is dissolved in the pre-drying treatment liquid. Thereby, the precipitation and dissolution of sublimable substances are repeated naturally.

When the temperature in the clean room is lower than the surface temperature during precipitation, the controller 3 can also maintain the internal space of the chamber 4 at a temperature higher than the surface temperature during precipitation to allow the air conditioner to adjust the substrate processing apparatus 1 temperature. Similarly, when the air pressure in the clean room is a value that is not suitable for the precipitation and dissolution of sublimable substances, the controller 3 can also change the output of the FFU 6 (refer to Fig. 2) and the setting of the exhaust valve 9 (refer to Fig. 2) At least one of the openings. In this case, at least one of the flow rate of the gas supplied into the chamber 4 and the flow rate of the gas discharged from the chamber 4 is changed, and the air pressure in the chamber 4 is maintained to be suitable for the precipitation of sublimable substances and Dissolved value.

The substrate processing apparatus 1 may also include at least one of a thermometer for measuring the temperature in the chamber 4 and a barometer for measuring the air pressure in the chamber 4. During the processing of the substrate W by the processing unit 2, when at least one of the temperature and the air pressure in the chamber 4 changes significantly, the controller 3 can also stop the loading of the substrate W under the chamber 4 until Both the temperature and the air pressure in the chamber 4 are maintained at values suitable for the precipitation and dissolution of sublimable substances.

The substrate processing apparatus 1 is not limited to an apparatus for processing a disc-shaped substrate W, and may be an apparatus for processing a polygonal substrate W.

The embodiments of the present invention have been described in detail, but they are only specific examples for clarifying the technical content of the present invention. The present invention should not be limited to these specific examples for interpretation. The scope of the present invention is only provided by the accompanying The scope of patent application is limited.

This application corresponds to Japanese Patent Application No. 2018-248018 filed to the Japan Patent Office on December 28, 2018, and the entire disclosure of this application is incorporated herein by reference.

1: Substrate processing equipment 2: processing unit 2w: wet processing unit 3: Controller 3a: Computer body 3b: CPU 3c: Main memory device 3d: peripheral devices 3e: auxiliary memory device 3f: Reading device 3g: communication device 4: chamber 5: The partition wall 5a: air outlet 5b: Moving in and out 6: FFU 7: Block gate 8: Exhaust duct 9: Exhaust valve 10: Rotating chuck 11: Chuck pin 12: Rotate the base 12u: upper surface 13: Rotation axis 14: Rotating motor 21: Handling the cup 22: Outer wall components 23: Cup 24: Sheath 24u: upper end 25: Cylinder 26: top 27: Sheath lifting unit 31: Liquid Nozzle 32: Liquid piping 33: Liquid valve 34: Nozzle moving unit 35: Flushing fluid nozzle 36: Flushing fluid piping 37: Flushing fluid valve 38: Nozzle moving unit 39: Nozzle of treatment liquid before drying 40: Pre-drying treatment liquid piping 41: Treatment liquid valve before drying 42: Nozzle moving unit 43: Replacement fluid nozzle 44: Replacement fluid piping 45: Replacement fluid valve 46: Nozzle moving unit 51: Interrupting member 51L: lower surface 52: Disc section 53: fulcrum 54: Interrupting member lifting unit 55: Center nozzle 56: Upper gas piping 57: Upper gas valve 58: Flow adjustment valve 59: Upper temperature regulator 61: Upper central opening 62: Upper gas flow path 63: Upper gas piping 64: Upper gas valve 65: Flow adjustment valve 66: Upper temperature regulator 71: Nozzle on the lower surface 72: Heating fluid piping 73: Heating fluid valve 74: Flow adjustment valve 75: heater 76: Cooling fluid piping 77: Cooling fluid valve 78: Flow adjustment valve 79: cooler 81: Lower central opening 82: Lower gas flow path 83: Lower gas piping 84: Lower gas valve 85: Flow adjustment valve 86: Lower temperature regulator 91: Film thickness measurement unit 92: Light-emitting element 93: Shell 94: Board 95: retainer 96: electric motor 96a: Motor housing 96b: Rotation axis 97: light receiving element 98: shell 99: Board 100A: Input device 100B: display device 100C: Alarm device 101: Treatment liquid supply device before drying 102A: Canister 1 102B: Canister 2 103A: 1st loop piping 103B: 2nd cycle piping 104A: 1st pump 104B: 2nd pump 105A: 1st individual piping 105B: 2nd individual piping 106A: The first on-off valve 106B: The second on-off valve 107A: The first flow adjustment valve 107B: 2nd flow control valve 108: Mixing valve 109: In-tube mixer 110: Concentration meter 111: Measurement piping 120: Treatment liquid film before drying 121: solid 191: Film thickness measurement unit 191A: Light-emitting element 191B: Light receiving element 191C: Shell 192: mobile unit A: collapse rate A1: Rotation axis A2: Rotating axis B: collapse rate C: collapse rate CA: Carrier CR: Central manipulator G1: interval H1: hand H2: hands IR: Indexing robot LP: Load port P: program PA: Pattern Pi: black dot RM: removable media SD: Benchmark data TW: Tower W: substrate

Fig. 1A is a schematic view of a substrate processing apparatus according to an embodiment of the present invention viewed from above. Fig. 1B is a schematic view of the substrate processing apparatus viewed from the side. Fig. 2 is a schematic view of the inside of the processing unit included in the above-mentioned substrate processing apparatus viewed horizontally. Fig. 3 is a schematic view of the film thickness measuring unit, the rotating chuck, and the blocking member included in the above-mentioned processing unit when viewed horizontally. Fig. 4 is a schematic view of the film thickness measuring unit and the rotating chuck viewed from above. Fig. 5 is a cross-sectional view showing the inside of a case housing the light-emitting element included in the film thickness measurement unit. Fig. 6 is a cross-sectional view taken along the line VI-VI shown in Fig. 5. Fig. 7 is a schematic diagram showing a pre-drying treatment liquid supply device included in the above-mentioned substrate treatment apparatus. FIG. 8 is a block diagram showing the hardware of the controller included in the substrate processing apparatus. FIG. 9 is a flowchart for explaining an example of substrate processing performed by the above-mentioned substrate processing apparatus. Fig. 10A is a schematic diagram showing the state of the substrate when a solution of camphor and IPA is used. Fig. 10B is a schematic diagram showing the state of the substrate when a solution of camphor and IPA is used. Fig. 10C is a schematic diagram showing the state of the substrate when a solution of camphor and IPA is used. Fig. 10D is a schematic diagram showing the state of the substrate when a solution of camphor and IPA is used. Fig. 10E is a schematic diagram showing the state of the substrate when a solution of camphor and IPA is used. Fig. 10F is a schematic diagram showing the state of the substrate when a solution of camphor and IPA is used. Figure 11 is a diagram of the equilibrium state of camphor and IPA. Fig. 12A is a schematic diagram showing the state of the substrate when a solution of camphor and methanol is used. Fig. 12B is a schematic diagram showing the state of the substrate when a solution of camphor and methanol is used. Fig. 12C is a schematic diagram showing the state of the substrate when a solution of camphor and methanol is used. Fig. 12D is a schematic diagram showing the state of the substrate when a solution of camphor and methanol is used. Figure 13 is a graph showing the collapse rate of the pattern. Fig. 14 is a graph showing the temporal change of the thickness of the liquid film of the pre-drying treatment liquid on the upper surface of the substrate until the solid of the sublimable substance is deposited from the pre-drying treatment liquid. Fig. 15 is a flowchart showing the flow of the first example of the film thickness monitoring process. FIG. 16 is a schematic diagram for explaining the abnormality processing process in the first example of the above-mentioned film thickness monitoring process. FIG. 17 is a flowchart showing the flow of the second example of the above-mentioned film thickness monitoring process. FIG. 18 is a schematic diagram for explaining the solvent evaporation suppression process in the second example of the above-mentioned film thickness monitoring process. 19 is a schematic diagram for explaining the solvent evaporation promotion process in the second example of the above-mentioned film thickness monitoring process. FIG. 20 is a flowchart showing the flow of the third example of the above-mentioned film thickness monitoring process. 21A is a schematic diagram for explaining the thin film forming process in the third example of the above-mentioned film thickness monitoring process. FIG. 21B is a schematic diagram for explaining the thin film forming process in the third example of the above-mentioned film thickness monitoring process. Fig. 22 is a flowchart showing the flow of the fourth example of the above-mentioned film thickness monitoring process. FIG. 23 is a flowchart for explaining another example of substrate processing performed by the above-mentioned substrate processing apparatus. FIG. 24 is a flowchart showing the flow of the fifth example of the above-mentioned film thickness monitoring process. FIG. 25A is a schematic diagram for explaining the flatness measurement process in the above-mentioned substrate processing. FIG. 25B is a schematic diagram for explaining the solid removal process in the above-mentioned substrate processing. FIG. 25C is a schematic diagram for explaining the solid removal process in the above-mentioned substrate processing.

Claims (6)

A substrate processing method, which includes: The process of supplying pre-drying treatment liquid is a process of supplying a solution obtained by dissolving a sublimable substance in a solvent, that is, a pre-drying treatment liquid onto the upper surface of a patterned substrate, and forming a liquid film of the pre-drying treatment liquid on the above The above-mentioned upper surface of the substrate; The precipitation process involves evaporating the solvent from the liquid film to precipitate the solid of the sublimable substance on the upper surface of the substrate; The film thickness reduction rate measurement process is to measure the rate at which the thickness of the liquid film is reduced by the evaporation of the solvent, that is, the rate of film thickness reduction, before the solids of the sublimable substance are precipitated in the precipitation process; The reduction speed determination process, which determines whether the above-mentioned film thickness reduction speed measured in the above-mentioned film thickness reduction speed measurement process is within the reference speed range; and The sublimation process involves sublimating the solid of the sublimable substance after the completion of the precipitation process when it is determined that the film thickness reduction speed is within the reference speed range in the reduction speed determination process. The substrate processing method of claim 1, wherein the reference speed range is based on a reference concentration range and reference data, and the reference concentration range represents the above-mentioned liquid film in the liquid film when the film thickness reduction speed falls within the above-mentioned reference speed range The concentration range of the sublimable substance is created by measuring the above-mentioned film thickness reduction rate of each liquid film of the pre-drying treatment liquid with different concentrations of the above-mentioned sublimable substance in advance. A substrate processing method, which includes: The process of supplying pre-drying treatment liquid is a process of supplying a solution obtained by dissolving a sublimable substance in a solvent, that is, a pre-drying treatment liquid onto the upper surface of a patterned substrate, and forming a liquid film of the pre-drying treatment liquid on the above The above-mentioned upper surface of the substrate; The precipitation process involves evaporating the solvent from the liquid film to precipitate the solid of the sublimable substance on the upper surface of the substrate; A film thickness measurement process, which is in the above precipitation process, measuring the thickness of the liquid film just before the solid of the sublimable substance is precipitated by the evaporation of the solvent; The thickness determination process is to determine whether the thickness of the liquid film measured in the film thickness measurement process is within the reference thickness range of the solid of the sublimable substance; and The sublimation process is in the thickness determination process. When it is determined that the thickness of the liquid film measured in the film thickness measurement process is within the reference thickness range, after the precipitation process is completed, the sublimable substance is Solid sublimation. For example, the substrate processing method of claim 3, which further includes an abnormality notification process, and the abnormality notification process is to notify an abnormality when it is determined that the thickness of the liquid film is not within the reference thickness range during the thickness determination process. Such as the substrate processing method of claim 3 or 4, which further includes: The flatness measurement process is performed in the above-mentioned precipitation process. When the thickness of the liquid film is determined to be within the above-mentioned reference thickness range in the above-mentioned thickness determination process, the above-mentioned measurement is carried out at multiple locations on the upper surface of the substrate. The height position of the solid surface of the sublimable substance, and the flatness of the solid surface of the sublimable substance is measured; and The flatness determination process is to determine whether the flatness measured in the above-mentioned flatness determination process is within the reference flat range; In the flatness determination process, when it is determined that the flatness measured in the flatness measurement process is within the reference flat range, the sublimation process is performed after the precipitation process is completed. For the substrate processing method of claim 5, which further includes a solid removal process, the solid removal process is performed by supplying a removing liquid to the substrate when it is determined in the flatness measurement process that the flatness is not the reference flatness range. The upper surface of the substrate, and the solid of the sublimable substance is removed from the upper surface of the substrate.

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