KR20200000401A - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

A substrate processing method comprises: a treatment liquid film forming process for forming a treatment liquid film on a pattern forming surface by supplying treatment liquid including a sublimable material on the pattern forming surface of a substrate; a temperature maintaining process for maintaining a temperature of the treatment liquid film formed on the pattern forming surface in a temperature range higher than a melting point of the sublimable material and lower than a boiling point of the sublimable material; a thinning film process for thinning the treatment liquid film while the temperature of the treatment liquid film is in the temperature range; a solidification process of solidifying the treatment liquid film thinned by the thinning film process, after the temperature maintaining process, on the pattern formation surface to form a solidified body of a sublimable material; and a sublimation process of subliming the solidified body and removing the same from the pattern forming surface.

Description

Substrate processing method and substrate processing apparatus {SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS}

This invention relates to a substrate processing method and a substrate processing apparatus. Examples of substrates to be processed include semiconductor wafers, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, substrates for solar cells, and liquid crystal displays, plasma displays and organic ELs. And substrates for a flat panel display (FPD) such as an electroluminescence (Electroluminescence) display device.

In the manufacturing process of a semiconductor device, a wet substrate process is performed.

For example, the etching residue which is a reaction byproduct may exist in the surface (pattern formation surface) of the board | substrate which formed the fine pattern which has unevenness | corrugation through a dry etching process etc .. Moreover, metal impurities, organic pollutants, etc. may adhere to the pattern formation surface.

In order to remove these substances, chemical liquid treatment using chemical liquid is performed. As the chemical liquid, an etching liquid, a cleaning liquid and the like are used. After the chemical liquid treatment, a rinse treatment for removing the chemical liquid with the rinse liquid is performed. As the rinse liquid, deionized water or the like is used.

Then, the drying process which dries a board | substrate is performed by removing a rinse liquid.

In recent years, with the miniaturization of the uneven pattern formed on the pattern formation surface of a board | substrate, there exists a tendency for the aspect ratio (ratio of height and width of a convex part) of a convex part of a pattern to become large.

Therefore, at the time of a drying process, adjacent convex parts pull together by the surface tension which acts on the liquid surface (the interface of a rinse liquid and the gas on it) of the rinse liquid which entered into the recessed part between the convex parts of a pattern. You may collapse and collapse.

For example, a solution that can be changed into a solid by drying or chemical change is supplied to the pattern formation surface of the substrate, and then changed into a solid to form a support material for supporting the pattern. It is known to change to remove in the gas phase without passing through the liquid phase (see US Patent Application Publication No. 2013/008868).

According to this method, since the influence of the surface tension of a liquid can be eliminated, the pattern formation surface of a board | substrate can be dried, suppressing collapse of a pattern.

As a material for forming the support material, for example, a substance having so-called sublimation, which has a high vapor pressure at room temperature and changes into a gas phase without passing through a liquid phase in a solid phase (hereinafter may be described as a "sublimable substance"). This is used.

In the method using a sublimable substance, a process liquid containing a sublimable substance is supplied to the pattern formation surface of a board | substrate, a process liquid film is formed, and the formed process liquid film is solidified on a pattern formation surface, and a coagulation body is formed. Next, the pattern formation surface of a board | substrate can be dried by subliming and removing a solidified body, using the formed solidified body as a support material of the convex part of a pattern, suppressing collapse of a convex part.

When supplying the process liquid containing a sublimable substance to the pattern formation surface of a board | substrate, and forming a process liquid film, it is preferable to increase the rotational speed of a board | substrate, and to remove excess process liquid by centrifugal force. This is to make the film thickness of the processing liquid film as thin as possible to shorten the time required for formation of the coagulated body and its sublimation removal.

By the way, as the processing liquid film is rotated at high speed in accordance with the rotation of the substrate, the sublimable substance is more likely to vaporize from the liquid level of the processing liquid film.

Then, when the sublimable substance vaporizes, the heat of vaporization is taken away, whereby the temperature of the processing liquid film is lowered, thereby solidifying the processing liquid film. The advancing speed of the solidification phenomenon due to such unintended vaporization is slower than the solidification phenomenon in the intentional solidification step performed after the treatment liquid film is formed.

Therefore, the internal stress (strain) tends to remain in the solidified body formed on the pattern formation surface of the substrate due to the solidification of the processing liquid film, and the internal stress of the solidified body becomes large, which causes the pattern to collapse.

Moreover, since solidification of a process liquid film | membrane already starts from the process liquid supply process, there exists a tendency for the final film thickness of the coagulated body formed in the pattern formation surface of a board | substrate to go through a coagulation process. An excessively large film thickness of the coagulated body also increases one of the internal stresses remaining in the coagulated body, which causes one pattern to collapse.

Then, the objective of this invention is providing the substrate processing method and substrate processing apparatus which can dry the pattern formation surface of a board | substrate, suppressing collapse of a pattern.

In one embodiment of the present invention, a process liquid film forming step of supplying a process liquid containing a sublimable substance to a pattern forming surface of a substrate to form a process liquid film on the pattern forming surface, and the process formed on the pattern forming surface A process for maintaining the temperature of the liquid film at a temperature range equal to or higher than the melting point of the sublimable material and below the boiling point of the sublimable material, and the process liquid film is thinned while the temperature of the process liquid film is within the temperature range. And a solidification step of solidifying the processing liquid film thinned by the thinning step on the pattern formation surface to form a solidified body of the sublimable material after the temperature thinning step and the coagulation body. It provides the substrate processing method including the sublimation process of removing from the pattern formation surface.

According to this method, in the temperature holding step, by maintaining the temperature of the processing liquid film in the above-described temperature range, the processing liquid film can be prevented from solidifying and the processing liquid film before the solidification step can be maintained in the liquid phase. For example, even if partial solidification of a process liquid film | membrane occurs in a process liquid film formation process, it can re-melt in a temperature maintenance process and can be made into a liquid phase.

In the subsequent thinning process, the thickness of the processing liquid film is in the above temperature range, and while the solidification of the processing liquid film does not occur, the thickness of the solidified body formed in the solidification step can be reduced by making the processing liquid film thin. Can be.

Therefore, in the solidification process, a solidified body in which the internal stress is as small as possible and the film thickness is appropriately adjusted can be formed on the pattern formation surface of the substrate.

Therefore, according to this method, the pattern formation surface of a board | substrate can be dried, suppressing collapse of a pattern by subliming and removing a coagulation | solidification body in a subsequent sublimation process.

In one Embodiment of this invention, the said process liquid film formation process includes the process of forming the said process liquid film | membrane spread | diffused to the periphery of the said pattern formation surface. And the said thin film formation process includes the removal thin film formation process which makes the said process liquid film thin by removing a part of the said process liquid which comprises the said process liquid film from the said pattern formation surface, after stopping supply of the said process liquid.

According to this method, a process liquid film is thinned by removing a part of process liquid which comprises the process liquid film | membrane spread | diffused to the periphery of a pattern formation surface. Therefore, the processing liquid can be uniformly spread evenly over the entire pattern formation surface, and the film thickness of the solidified body formed in the solidification step can be appropriately reduced.

In one Embodiment of this invention, the said removal thin film formation process includes the board | substrate rotation process which keeps the said board | substrate horizontal and rotates. Therefore, the process liquid film can be thinned by the simple method of removing a part of the process liquid from the pattern formation surface by the centrifugal force by the rotation of the substrate.

In one embodiment of the present invention, the processing liquid film forming step includes a core forming step of forming, as the processing liquid film, a processing liquid core smaller than the diameter of the substrate in a predetermined region including the center of the pattern formation surface. do. The thinning step includes an enlarged thinning step of thinning the processing liquid film by diffusing the processing liquid core to the periphery of the pattern formation surface and making it thin.

According to this method, the thin process liquid film | membrane spread | diffused to the periphery of a pattern formation surface is formed by diffusing the process liquid core formed in the predetermined area | region containing the center of a pattern formation surface to the periphery of a pattern formation surface. Therefore, the film thickness of the coagulated body formed in a coagulation process can be reduced suitably. In addition, since the amount of processing liquid that is thin enough to spread to the periphery of the pattern formation surface may be supplied to the pattern formation surface, the amount of the processing liquid used for forming the coagulated body can be reduced.

In one embodiment of the present invention, the enlarged thin film forming step includes a substrate rotating step of holding and rotating the substrate horizontally. Therefore, the process liquid film can be thinned by the simple method of spreading the process liquid core thinly by the centrifugal force by the rotation of the substrate.

In one embodiment of this invention, the said core formation process includes the 1st board | substrate rotation process which keeps the said board | substrate horizontally, and rotates at a 1st rotation speed. The expanded thinning step includes a second substrate rotating step of holding the substrate horizontally and rotating at a second rotational speed higher than the first rotational speed.

According to this method, when the processing liquid core is formed, the substrate is rotated at a relatively low first rotational speed. Therefore, the centrifugal force acting on the processing liquid on the pattern formation surface is relatively small. Therefore, it is possible to form the processing liquid core uniformly diffused in the predetermined region while suppressing the processing liquid from diffusing toward the periphery of the substrate. On the other hand, when the processing liquid core is diffused to the periphery, the substrate is rotated at a relatively high second rotational speed. Therefore, the centrifugal force acting on the processing liquid on the pattern formation surface is relatively large. Therefore, the processing liquid can be quickly diffused to the periphery of the substrate.

In one Embodiment of this invention, the said substrate processing method further includes the process liquid supply stop process which stops supply of the said process liquid before starting the expansion thin film formation process. Thereby, the quantity of the process liquid discharged | emitted out of a board | substrate in a thin film formation process can be reduced. Therefore, the usage amount of the processing liquid can be further reduced.

In one embodiment of the present invention, the substrate processing method is a process liquid replenishing step of replenishing the processing liquid film by continuing supply of the processing liquid to the pattern formation surface during execution of the enlarged thin film formation process. It includes more. Therefore, the processing liquid can be spread evenly over the entire pattern formation surface.

In one Embodiment of this invention, the said process liquid film formed in the said pattern formation surface through the said board | substrate by supplying the temperature control medium to the back surface on the opposite side to the said pattern formation surface in the said board | substrate in the said board | substrate. And a temperature controlling medium supplying process to control the temperature of the. Therefore, the temperature of a process liquid film can be adjusted by the simple method of supplying a temperature control medium to the back surface of a board | substrate. Therefore, the structure of the substrate processing apparatus for implementing a substrate processing method can be simplified.

In one embodiment of this invention, the said solidification process supplies a refrigerant | coolant to the back surface on the opposite side to the said pattern formation surface in the said board | substrate, The said process is carried out to the temperature below the freezing point of the said sublimable substance through the said board | substrate. And a substrate cooling step of cooling the liquid film. The temperature control medium supplying step is further characterized by the fact that the first fruit of the first temperature below the melting point of the sublimable material and below the boiling point of the sublimable material is separated from the pattern forming surface on the substrate. Is performed after the first fruit supplying step and the first fruit supplying step to supply to the reverse side of the opposite side, and is equal to or more than the melting point of the sublimable material and less than the boiling point of the sublimable material and is lower than that of the first fruit. A 2nd fruit supply process of supplying 2 fruits to the back surface on the opposite side to the said pattern formation surface in the said board | substrate is included.

According to this method, a 2nd fruit supply process is performed after a 1st fruit supply process in a temperature maintenance process, and a board | substrate cooling process is performed in a subsequent solidification process. That is, the processing liquid film is not rapidly cooled from the first temperature to the temperature below the freezing point temperature of the sublimable substance in the solidification step, but in the temperature holding step, the second process temperature is lower than the first temperature. After cooling to temperature once, it cools from the 2nd temperature to the temperature below the freezing point temperature of a sublimable substance in a coagulation process. In this way, since the processing liquid film is cooled step by step, it is possible to suppress the occurrence of temperature nonuniformity in the processing liquid film during cooling. Therefore, generation | occurrence | production of the part which does not solidify in a process liquid film in a coagulation process can be suppressed, and generation | occurrence | production of the nonuniformity of the sublimation rate of the coagulation | solidification body in the sublimation process after a coagulation process can be suppressed.

In one embodiment of this invention, the said solidification process supplies a refrigerant | coolant to the back surface on the opposite side to the said pattern formation surface in the said board | substrate, The said process is carried out to the temperature below the freezing point of the said sublimable substance through the said board | substrate. And a substrate cooling step of cooling the liquid film.

According to this method, a solidification process can be performed by the simple method of supplying a refrigerant | coolant to the back surface of a board | substrate. Therefore, the process of a substrate processing method and the structure of the substrate processing apparatus for implementing it can be simplified.

In one embodiment of this invention, the said process of heat-processing is carried out by the heat transmitted to the said board | substrate from the heater unit which has the opposing surface which opposes the back surface on the opposite side to the said pattern formation surface in the said board | substrate. Heater temperature control process for adjusting the temperature. Therefore, the heat which generate | occur | produces in a heater unit can be evenly transmitted to the part which opposes the opposing surface in the back surface of a board | substrate.

In one embodiment of this invention, the said temperature maintenance process includes the fruit supply process which supplies a fruit to the back surface on the opposite side to the said pattern formation surface in the said board | substrate by a fruit supply unit, The said solidification process is a And a refrigerant supplying step of supplying the refrigerant to the rear surface of the substrate by the refrigerant supply unit. And the said substrate processing method controls at least one of the supply stop timing of the fruit by the said fruit supply unit, and the supply start timing of the refrigerant by the said refrigerant supply unit, and adjusts the thin film formation period for the said thinning process, and The method further includes controlling the film thickness of the treatment liquid film after the thinning process.

According to this method, the film thickness of the processing liquid film after the thinning step can be adjusted by adjusting the thinning period for the thinning step by a simple method of controlling at least one of the fruit supply stop timing and the coolant supply start timing. . As a result, the film thickness of the solidified body can be adjusted.

More specifically, the thinning period can be adjusted by setting these timings and the timing of supply stop of the processing liquid by the processing liquid supplying step. For example, the timing of stopping supply of the fruit to the fruit path or starting timing of supply of the refrigerant to the refrigerant path may be set after the supply of the processing liquid by the processing liquid supplying step is stopped (including simultaneous). .

In one embodiment of this invention, the said heat path and the said refrigerant path share a piping at least partially. Thereby, the structure of the substrate processing apparatus for implementing a substrate processing method can be further simplified.

In one embodiment of this invention, the said coagulation process transfers heat from the said board | substrate to the cooler unit which has an opposing surface which opposes the back surface on the opposite side to the said pattern formation surface in the said board | substrate, and said said And a substrate cooling step of cooling the treatment liquid film to a temperature below the freezing point of the sublimable material. Therefore, the heat of the part which opposes the opposing surface of a cooler unit on the back surface of a board | substrate is equally deprived by a cooler unit, and a process liquid film is cooled equally.

In one embodiment of the present invention, the temperature holding step is started earlier than the processing liquid film forming step. Therefore, the processing liquid is supplied in the processing liquid film forming step in a state where the substrate is preheated to a temperature range equal to or higher than the melting point of the sublimable material and below the boiling point of the sublimable material. Therefore, solidification of the process liquid film in a process liquid film formation process can be suppressed further. Moreover, since the solidification of the process liquid film in a process liquid film formation process is suppressed, it is not necessary to remelt the solidified process liquid film in a temperature maintenance process, and the period of a temperature maintenance process can also be shortened.

In one embodiment of this invention, the said process liquid contains the said sublimable substance as a solute, and a solvent, The said temperature maintenance process makes the temperature of the said process liquid film formed in the said pattern formation surface less than the boiling point of the said solvent. It includes the step of maintaining. Thereby, boiling of the solvent in a temperature holding process can be suppressed. Therefore, it can suppress or prevent scattering of the process liquid on a pattern formation surface to the place where it is not intended by boiling.

In one embodiment of the present invention, the substrate processing method further includes a pretreatment liquid supplying step of supplying a pretreatment liquid mixed with the processing liquid to the pattern formation surface. After the pretreatment liquid supplying step, the processing liquid film forming step is performed.

According to this method, by first mixing with the pretreatment liquid supplied to the pattern formation surface of a board | substrate, it can be made to spread | distribute the process liquid smoothly and evenly on the pattern formation surface of a board | substrate.

In one Embodiment of this invention, the said substrate processing method is performed in parallel with the said sublimation process, and further includes the dew condensation prevention process which prevents the dew condensation on the said pattern formation surface.

According to this method, even when the solidification body absorbs heat of vaporization when the solidification body sublimes and the temperature of the solidification body or the substrate decreases, condensation of moisture in the atmosphere can be prevented from condensation on the solidification body or the pattern formation surface of the substrate. Therefore, it is possible to suppress the collapse of the pattern by the water condensation on the surface of the coagulation body, the sublimation of the coagulation body, or the surface tension generated by the water condensation on the pattern formation surface of the substrate. .

In order to prevent dew condensation, for example, a step of supplying an inert gas to the pattern formation surface of the substrate, an atmosphere blocking process of blocking the atmosphere of the space near the pattern formation surface, and a dehumidification process of dehumidifying the atmosphere around the substrate Etc. can be implemented. In the process of supplying an inert gas, in order to improve the effect of preventing condensation, it is preferable to use a high temperature inert gas that is higher than room temperature.

In one embodiment of the present invention, the substrate processing method further includes a sublimation promotion step that is executed in parallel with the sublimation step to promote sublimation of the coagulated body.

According to this method, the coagulation body can be sublimated in the shortest possible time, so that the duration of the sublimation step can be shortened.

In order to promote sublimation, for example, a pressure reduction step of depressurizing a space in the vicinity of the pattern formation surface of the substrate, a rotation sublimation promotion step of rotating the substrate, and an atmosphere heating step of heating the atmosphere near the pattern formation surface are performed. can do.

One embodiment of the present invention is a substrate processing apparatus used in the substrate processing method, comprising: a processing liquid supply unit supplying the processing liquid containing the sublimable substance to the pattern formation surface of the substrate; A temperature holding unit for maintaining the temperature of the processing liquid film formed on the pattern formation surface at a temperature equal to or higher than the melting point of the sublimable material and below the boiling point of the sublimable material, a thinning unit for thinning the processing liquid film, and A coagulation unit for solidifying a processing liquid film on the pattern formation surface to form the coagulation body, a sublimation unit for subliming the coagulation body and removing it from the pattern formation surface, the processing liquid supply unit, the temperature holding unit, and the A cone programmed to control the thinning unit, the coagulation unit and the sublimation unit to execute each step of the substrate processing method. Provided is a substrate processing apparatus including a controller.

According to this configuration, in the temperature holding step, by maintaining the temperature of the processing liquid film in the above-described temperature range, the processing liquid film can be prevented from solidifying and the processing liquid film before the solidification step can be maintained in the liquid phase. For example, even if partial solidification of a process liquid film | membrane occurs in a process liquid supply process, it can re-melt in a temperature maintenance process and can be made into a liquid phase.

In the subsequent thinning step, the thickness of the coagulation body formed in the coagulation step can be adjusted by thinning the process liquid film while the temperature of the process liquid film is in the above temperature range and no solidification of the process liquid film occurs. have.

Therefore, in the solidification process, a solidified body in which the internal stress is as small as possible and the film thickness is appropriately adjusted can be formed on the pattern formation surface of the substrate.

Therefore, according to this structure, in the next sublimation process, the pattern formation surface of a board | substrate can be dried, suppressing collapse of a pattern by subliming and removing a coagulation body.

An embodiment of the present invention provides a processing liquid supplying step of supplying a processing liquid containing a sublimable substance to a pattern forming surface of a substrate to form a processing liquid film on the pattern forming surface of the substrate, and a pattern forming surface of the substrate. The temperature holding step of maintaining the temperature of the processing liquid film formed in the temperature range above the melting point of the sublimable material and below the boiling point of the sublimable material, and stopping the supply of the processing liquid by the processing liquid supplying step. Thereafter, while the temperature of the processing liquid film is within the temperature range, a portion of the processing liquid constituting the processing liquid film is removed from the pattern formation surface to thin the processing liquid film, and after the temperature holding process, A solidification step of coagulating the processing liquid film thinned by the thinning step on the pattern formation surface to form a coagulation body, and by subliming the coagulation body, It provides the substrate processing method including the sublimation process of removing from the pattern formation surface.

According to this method, in the temperature holding step, by maintaining the temperature of the processing liquid film in the above-described temperature range, the processing liquid film can be prevented from solidifying and the processing liquid film before the solidification step can be maintained in the liquid phase. For example, even if partial solidification of a process liquid film | membrane occurs in a process liquid supply process, it can re-melt in a temperature maintenance process and can be made into a liquid phase.

In the subsequent thinning step, the temperature of the processing liquid film is in the above temperature range, and while the solidification of the processing liquid film does not occur, the excess processing liquid is removed to adjust the film thickness of the solidified body formed in the solidification step. Can be.

Therefore, in the solidification process, a solidified body in which the internal stress is as small as possible and the film thickness is appropriately adjusted can be formed on the pattern formation surface of the substrate.

Therefore, according to this method, the pattern formation surface of a board | substrate can be dried, suppressing collapse of a pattern by subliming and removing a coagulation | solidification body in a subsequent sublimation process.

In one Embodiment of this invention, the said temperature maintenance process makes the temperature of the said process liquid film formed in the said pattern formation surface through the said board | substrate by making a fruit contact the back surface on the opposite side to the said pattern formation surface in the said board | substrate. Substrate temperature control process for controlling the.

According to this method, the temperature holding step can be performed by a simple method of supplying fruit to the back surface of the substrate. Therefore, the structure of the substrate processing apparatus for implementing a substrate processing method can be simplified.

In one embodiment of this invention, the said substrate temperature control process is started earlier than the start of the said process liquid supply process.

According to this method, solidification of the process liquid film in a process liquid supply process can be further suppressed by supplying a fruit to the back surface of a substrate and performing a process liquid supply process in the state which heated the board | substrate previously. Moreover, since the solidification of the process liquid film in a process liquid supply process is suppressed, it is not necessary to remelt the solidified process liquid film in a temperature maintenance process, and the period of a temperature maintenance process can also be shortened.

In one embodiment of this invention, the said solidification process makes the said process through the said board | substrate by making the back surface on the opposite side to the said pattern formation surface in the said board | substrate contact the refrigerant | coolant of the temperature below the freezing point of the said sublimable substance. And a substrate cooling step of cooling the liquid film.

According to this method, a solidification process can be performed by the simple method of supplying a refrigerant | coolant to the back surface of a board | substrate. Therefore, the process of a substrate processing method and the structure of the substrate processing apparatus for implementing it can be simplified.

In one embodiment of this invention, the said temperature maintenance process includes the fruit supply process which supplies a fruit to the back surface on the opposite side to the said pattern formation surface in the said board | substrate by a fruit supply unit, The said solidification process is a And a refrigerant supplying step of supplying the refrigerant to the rear surface of the substrate by the refrigerant supply unit. And the said substrate processing method controls at least one of the supply stop timing of the said fruit by the said fruit supply unit, and the start timing of the supply of the said refrigerant by the said refrigerant supply unit, and adjusts the thin film formation period for the said thinning process, Therefore, the method further includes a step of controlling the film thickness of the processing liquid film after the thinning process.

According to this method, by the simple method of controlling at least one of the fruit supply stop timing and the refrigerant supply start timing, the thin film period for the thin film process can be adjusted to adjust the film thickness of the processing liquid film after the thin film process. As a result, the film thickness of the solidified body can be adjusted.

More specifically, the thinning period can be adjusted by setting these timings and the timing of supply stop of the processing liquid by the processing liquid supplying step.

For example, the timing of stopping supply of the fruit to the fruit path or starting timing of supply of the refrigerant to the refrigerant path may be set after the supply of the processing liquid by the processing liquid supplying step is stopped (including simultaneous). .

In one embodiment of this invention, the said heat path and the said refrigerant path share a piping at least partially.

According to this method, the structure of the substrate processing apparatus for implementing a substrate processing method can be further simplified.

In one embodiment of the present invention, the thinning step includes a substrate rotating step of holding and rotating the substrate horizontally.

According to this method, a process liquid film can be thinned by the simple method of rotating a board | substrate and removing excess process liquid by centrifugal force.

In one embodiment of this invention, the said substrate processing method further includes the preprocessing liquid supply process of supplying the pretreatment liquid mixed with the said process liquid to the pattern formation surface of the said board | substrate. And after the said pretreatment liquid supply process, the said process liquid supply process is performed.

According to this method, by first mixing with the pretreatment liquid supplied to the pattern formation surface of a board | substrate, the process liquid can be spread evenly evenly on the pattern formation surface of a board | substrate, and each process of a drying process can be performed.

In one embodiment of this invention, the said substrate processing method is performed in parallel with the said sublimation process, and further includes the dew condensation prevention process of preventing the dew condensation on the pattern formation surface of the said board | substrate.

According to this method, even when the solidification body absorbs heat of vaporization when the solidification body sublimes and the temperature of the solidification body or the substrate decreases, condensation of moisture in the atmosphere can be prevented from condensation on the solidification body or the pattern formation surface of the substrate. Therefore, it is possible to suppress the collapse of the pattern by the water condensation on the surface of the coagulation body, the sublimation of the coagulation body, or the surface tension generated by the water condensation on the pattern formation surface of the substrate. .

In order to prevent dew condensation, for example, a step of supplying an inert gas to the pattern formation surface of the substrate, an atmosphere blocking process of blocking the atmosphere of the space near the pattern formation surface, and a dehumidification process of dehumidifying the atmosphere around the substrate Etc. can be implemented. In the process of supplying an inert gas, in order to improve the effect of preventing condensation, it is preferable to use a high temperature inert gas that is higher than room temperature.

In one embodiment of the present invention, the substrate processing method further includes a sublimation promotion step that is executed in parallel with the sublimation step to promote sublimation of the coagulated body.

According to this method, the coagulation body can be sublimated in the shortest possible time, so that the duration of the sublimation step can be shortened.

In order to promote sublimation, for example, a depressurization step of depressurizing the space in the vicinity of the pattern formation surface of the substrate, a substrate rotation step of rotating the substrate, and an atmosphere heating step of heating the atmosphere near the pattern formation surface may be performed. Can be.

One embodiment of the present invention is a substrate processing apparatus used in the substrate processing method, comprising: a processing liquid supply unit supplying the processing liquid containing a sublimable substance to the pattern formation surface of the substrate; A temperature holding unit for maintaining the temperature of the processing liquid film formed on the pattern formation surface at a temperature equal to or higher than the melting point of the sublimable material and below the boiling point of the sublimable material; and a part of the processing liquid constituting the processing liquid film. A thinning unit which removes from the pattern forming surface to thin the processing liquid film, a solidifying unit which solidifies the processing liquid film on the pattern forming surface to form the coagulated body, and sublimates the solidified body to form the pattern forming surface. A sublimation unit to be removed from the substrate, the processing liquid supply unit, the temperature holding unit, the thinning unit, the coagulation unit, and the sublimation oil. Controls, and provides a substrate processing apparatus, including a controller that is programmed to execute the respective steps of the substrate processing method.

According to this configuration, in the temperature holding step, by maintaining the temperature of the processing liquid film in the above-described temperature range, the processing liquid film can be prevented from solidifying and the processing liquid film before the solidification step can be maintained in the liquid phase. For example, even if partial solidification of a process liquid film | membrane occurs in a process liquid supply process, it can re-melt in a temperature maintenance process and can be made into a liquid phase.

In the subsequent thinning step, while the temperature of the processing liquid film is in the above temperature range and the solidification of the processing liquid film does not occur, the excess processing liquid is removed and the film thickness of the solidified body formed in the solidification step is removed. I can adjust it.

Therefore, in the solidification process, a solidified body in which the internal stress is as small as possible and the film thickness is appropriately adjusted can be formed on the pattern formation surface of the substrate.

Therefore, according to this structure, in the next sublimation process, the pattern formation surface of a board | substrate can be dried, suppressing collapse of a pattern by subliming and removing a coagulation body.

One embodiment of the present invention is a mixed treatment liquid in which a first sublimable substance and a first additive different from the first sublimable substance are mixed, and a mixed treatment liquid having a lower solidification point than the first sublimable substance is a substrate. A mixed liquid film forming step of supplying a liquid film of the mixed processing liquid to the surface of the substrate, a solidifying step of solidifying the liquid film of the mixed processing liquid to form a coagulated body, and the coagulated body. And a sublimation process of subliming the first sublimable material to be removed from the surface of the substrate.

According to this method, the solidification point of a mixed process liquid is lower than the solidification point of a 1st sublimable substance by the solidification point fall by mixing of a 1st sublimable substance and a 1st additive. That is, under the temperature condition below the freezing point of a 1st sublimable substance, a mixed process liquid does not solidify but maintains a liquid phase. Therefore, even when the mixed liquid film forming step is performed under such temperature conditions, the liquid film of the mixed processing liquid can be satisfactorily formed without separately providing a temperature control mechanism for preventing solidification of the mixed processing liquid. And a coagulated body can be formed in the coagulation process after a mixed liquid film formation process. In the subsequent sublimation step, the first sublimable substance contained in the coagulated body can be sublimed to remove the coagulated body from the surface of the substrate.

Therefore, unintentional solidification of the mixed treatment liquid (sublimation treatment liquid) can be avoided while suppressing the increase in cost, and the surface of the substrate can be treated well.

In one embodiment of this invention, the solidification point of the said 1st sublimable substance is higher than normal temperature, and the solidification point of the said mixed process liquid is lower than normal temperature.

According to this method, the solidification point of a mixed process liquid is lower than normal temperature by the solidification point fall by mixing of a 1st sublimable substance and a 1st additive. In other words, at room temperature, the mixed treatment liquid maintains a liquid state without solidifying. Therefore, even when the mixed liquid film forming step is performed in a normal temperature environment, the liquid film of the mixed processing liquid can be satisfactorily formed. And a coagulated body can be formed in the coagulation process after a mixed liquid film formation process. In the subsequent sublimation step, the first sublimable substance contained in the coagulated body can be sublimed to remove the coagulated body from the surface of the substrate.

Therefore, unintentional solidification of the mixed processing liquid (processing liquid having sublimability) can be avoided under normal temperature environment while suppressing the cost increase, and the surface of the substrate can be treated well.

In one embodiment of this invention, the said 1st additive contains the solvent which does not have a sublimation property. In this case, the solvent may contain alcohol or water.

According to this method, the solidification point of a mixed process liquid can be reduced using a comparatively cheap solvent. Therefore, cost can be reduced.

In one embodiment of this invention, the said 1st additive contains a 2nd sublimable substance.

According to this method, if it is a 2nd sublimable substance, it will sublimate without going through a liquid phase. Therefore, the liquid residual after a sublimation process can be prevented reliably.

As described in one embodiment of the present invention, the solidification point of the first additive may be lower than that of the first sublimable substance.

In one embodiment of this invention, the said substrate processing method further includes the liquid mixture preparation process which mixes the said 1st sublimable substance and the said 1st additive, and produces | generates the said mixed process liquid. In this case, the mixed liquid film forming step may include a step of supplying the mixed processing liquid created by the mixed liquid creating step to the surface of the substrate.

According to this method, the mixed processing liquid can be formed during substrate processing. The mixed treatment liquid can be prepared as required.

In one embodiment of this invention, the said solidification process is the mixed refrigerant which mixed the refrigerant | coolant and the 2nd additive on the back surface on the opposite side to the surface of the said board | substrate so that the said liquid film of the said mixed process liquid may be cooled, and a solidification point is more than that of the said refrigerant | coolant. Supplying a low mixed refrigerant.

According to this method, the solidification point of the mixed refrigerant is lower than the solidification point of the refrigerant due to the solidification point drop caused by the mixing of the refrigerant and the second additive. That is, the mixed refrigerant maintains the liquid phase even at a temperature lower than the freezing point of the refrigerant. Therefore, the liquid mixed refrigerant maintained at a temperature lower than the freezing point of the refrigerant can be supplied to the rear surface of the substrate. Thereby, in the coagulation process, the liquid film of the mixed process liquid can be cooled to a lower temperature.

In this case, the said 2nd additive may be common with the said 1st additive.

In one embodiment of this invention, the said substrate processing method is the said mixing process, while the temperature of the said liquid film of the said mixed process liquid is in the temperature range more than the freezing point of the said mixed process liquid, and below the boiling point of the said mixed process liquid. A thinning process for thinning the liquid film of the liquid is further included. In this case, the solidification step may include a step of solidifying the liquid film of the mixed processing liquid thinned by the thinning step.

According to this method, by thinning the liquid film of the mixed liquid in the thinning step, the film thickness of the coagulated body formed in the coagulation step can be reduced.

Therefore, in the solidification process, a solidified body in which the internal stress is as small as possible and the film thickness is appropriately adjusted can be formed on the surface of the substrate.

One embodiment of the present invention is a mixed treatment liquid in which a first sublimable substance and a first additive different from the first sublimable substance are mixed, and a mixed treatment liquid having a lower solidification point than the first sublimable substance is a substrate. A substrate processing apparatus is provided, comprising a mixed processing liquid supply unit for supplying to a surface of a substrate, a solidifying unit for solidifying a liquid film of the mixed processing liquid, and a controller for controlling the mixed processing liquid supply unit and the solidifying unit.

And the mixed liquid film forming step of supplying the mixed processing liquid to the surface of the substrate by the mixed processing liquid supply unit to form the liquid film of the mixed processing liquid on the surface of the substrate, and the mixing. Program to perform a coagulation step of solidifying the liquid film of the processing liquid by the coagulation unit to form a coagulation body, and a sublimation step of subliming the first sublimable material contained in the coagulation body and removing it from the surface of the substrate. It is.

According to this structure, the solidification point of a mixed process liquid is lower than the solidification point of a 1st sublimable substance by the solidification point fall by mixing of a 1st sublimable substance and a 1st additive. That is, under the temperature condition below the freezing point of a 1st sublimable substance, a mixed process liquid does not solidify but maintains a liquid phase. Therefore, even if the mixed liquid film forming step is performed under such temperature conditions, the liquid film of the mixed processing liquid can be satisfactorily formed. And a coagulated body can be formed in the coagulation process after a mixed liquid film formation process. In the subsequent sublimation step, the first sublimable substance contained in the coagulated body can be sublimed to remove the coagulated body from the surface of the substrate.

Therefore, unintentional solidification of the mixed treatment liquid (sublimation treatment liquid) can be avoided while suppressing the increase in cost, and the surface of the substrate can be treated well.

The above-mentioned or another object, a characteristic, and an effect in this invention become clear by description of embodiment described below with reference to an accompanying drawing.

1 is a schematic plan view showing a layout of a substrate processing apparatus according to a first embodiment of the present invention.
FIG. 2: is a schematic cross section which shows schematic structure of the processing unit with which the said substrate processing apparatus is equipped.
3 is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus.
4 is a flowchart for explaining an example of substrate processing by the processing unit.
5A to 5H are schematic cross-sectional views for explaining the state of the substrate processing.
6 is a time chart for explaining the thinning step of the substrate processing and the steps before and after.
7 is an illustrative sectional view showing an enlarged main part of a modification of the processing unit included in the substrate processing apparatus.
FIG. 8: is a schematic cross section which shows schematic structure of the processing unit with which the substrate processing apparatus which concerns on 2nd Embodiment is equipped.
9 is a schematic view of a processing fluid supply pipe provided in the substrate processing apparatus.
10 is a block diagram showing an electrical configuration of main parts of the substrate processing apparatus according to the second embodiment.
11A to 11H are schematic sectional views for explaining the state of substrate processing by the processing unit according to the second embodiment.
12 is a schematic cross-sectional view for explaining a modification of the substrate processing by the processing unit according to the second embodiment.
13A and 13B are schematic sectional views for explaining another modification of substrate processing by the processing unit according to the second embodiment.
FIG. 14: is a schematic cross section which shows schematic structure of the processing unit with which the substrate processing apparatus which concerns on 3rd Embodiment is equipped.
15A to 15D are schematic sectional views for explaining the state of substrate processing by the processing unit according to the third embodiment.
FIG. 16: is a schematic cross section which shows schematic structure of the processing unit with which the substrate processing apparatus which concerns on 4th Embodiment is equipped.
17 is a flowchart for explaining a substrate processing by the processing unit according to the fourth embodiment.
18A to 18E are schematic sectional views for explaining the substrate processing by the processing unit according to the fourth embodiment.
19A and 19B are schematic sectional views for explaining the state of the particle holding layer in the substrate processing by the processing unit according to the fourth embodiment.
20 is a schematic sectional view illustrating a schematic configuration of a processing unit included in the substrate processing apparatus according to the fifth embodiment.
21 is a block diagram showing the electrical configuration of main parts of the substrate processing apparatus according to the fifth embodiment.
22A to 22C are schematic sectional views for explaining the substrate processing by the processing unit according to the fifth embodiment.
FIG. 23: is a schematic diagram of the cooler unit with which the processing unit which concerns on the modification of 5th Embodiment, and its periphery is.
FIG. 24: is a schematic diagram of the cooler unit with which the processing unit which concerns on the other modified example of 5th embodiment, and its periphery is.
25 is a schematic sectional view illustrating a schematic configuration of a processing unit included in the substrate processing apparatus according to the sixth embodiment.
It is a figure which shows the relationship between the density | concentration of IPA contained in a mixed process liquid, and the freezing point of the said mixed process liquid.
27 is a block diagram showing the electrical configuration of main parts of the substrate processing apparatus according to the sixth embodiment.
28 is a flowchart for explaining an example of substrate processing by a processing unit according to the sixth embodiment.
29A to 29C are schematic sectional views for explaining a state of substrate processing by the processing unit according to the sixth embodiment.
It is a figure which shows the relationship between the density | concentration of IPA contained in the mixed process liquid, and the collapse rate of the pattern formed in the surface of a board | substrate.
31 is a diagram illustrating a modification example according to the sixth embodiment.
32 is a flowchart for explaining another example of the substrate processing by the processing unit according to the sixth embodiment.

<1st embodiment>

1 is a schematic plan view showing the layout of the substrate processing apparatus 1 according to the first embodiment of the present invention. The substrate processing apparatus 1 is a sheet type apparatus which processes each board | substrate W, such as a silicon wafer, one by one. The substrate processing apparatus 1 is arrange | positioned in a clean room. In this embodiment, the board | substrate W is a disk-shaped board | substrate.

The substrate processing apparatus 1 includes a plurality of processing units 2 that process the substrate W and a carrier C that accommodates a plurality of substrates W processed by the processing unit 2. I) A load port LP, a transfer robot IR and CR for transferring the substrate W between the load port LP and the processing unit 2, and a controller for controlling the substrate processing apparatus 1. It includes (3).

The transfer robot IR transfers the substrate W between the carrier C and the transfer robot CR. The transfer robot CR transfers the substrate W between the transfer robot IR and the processing unit 2. The plurality of processing units 2 have the same configuration, for example.

FIG. 2: is a schematic diagram which shows schematic structure of the processing unit 2 with which the substrate processing apparatus 1 was equipped.

The processing unit 2 maintains a box-shaped chamber 4 having an inner space and a single substrate W in a horizontal posture in the chamber 4 and passes vertically through the center of the substrate W. FIG. It includes a spin chuck 5 for rotating the substrate (W) around the rotation axis (A1) of.

The processing unit 2 includes a chemical liquid supply unit 6 for supplying a chemical liquid to a pattern formation surface that is an upper surface of the substrate W held by the spin chuck 5, and a substrate W held by the spin chuck 5. It further comprises a rinse liquid supply unit (7) for supplying a rinse liquid to the pattern formation surface of.

The processing unit 2 is supplied to the pretreatment liquid supply unit 8 for supplying a pretreatment liquid mixed with the processing liquid to the pattern formation surface of the substrate W held by the spin chuck 5, and to the spin chuck 5. The processing liquid supply unit 9 which supplies the processing liquid containing a sublimable substance is further included in the pattern formation surface of the board | substrate W hold | maintained.

The processing unit 2 includes a back supply unit 10 and a spin chuck 5 for supplying a temperature control medium to the back surface of the substrate W held by the spin chuck 5 on the opposite side to the pattern formation surface. It further includes a cylindrical processing cup 11 surrounding the. The temperature control medium is a fluid for adjusting the temperature of the processing liquid on the pattern formation surface of the substrate W via the substrate W. As shown in FIG. The temperature control medium contains fruit and a refrigerant. A fruit is a fluid for heating the process liquid on the pattern formation surface of the board | substrate W. FIG. The coolant is a fluid for cooling the processing liquid on the pattern formation surface of the substrate W. As shown in FIG.

The processing unit 2 performs the first condensation prevention unit 12, which executes a condensation preventing step of preventing condensation from occurring on the pattern formation surface of the substrate W when the solidifying body of the sublimable substance is sublimed. It further includes a second condensation preventing unit 13.

The chamber 4 is an FFU (fan filter unit) as a blowing unit that sends clean air from a box-shaped partition wall 14 and an upper portion of the partition wall 14 to the partition wall 14 (equivalent to the chamber 4). (15) and an exhaust device (16) for discharging gas in the chamber (4) from the lower portion of the partition wall (14).

As the spin chuck 5, a pinch type chuck that sandwiches the substrate W in the horizontal direction and holds the substrate W horizontally is adopted. Specifically, the spin chuck 5 includes a spin motor 17, a spin shaft 18 integrated with the drive shaft of the spin motor 17, and a disc attached substantially horizontally to the upper end of the spin shaft 18. It includes a spin base 19 of the shape. The spin shaft 18 is formed in a hollow shape in this embodiment.

The spin base 19 includes a horizontal circular upper surface 19a having an outer diameter larger than that of the substrate W. As shown in FIG. On the upper surface 19a, plural (three or more, for example, four) holding members 19b are disposed at the peripheral edge thereof. The plurality of clamping members 19b are arranged at equal intervals on the circumference corresponding to the outer circumferential shape of the substrate W at the peripheral edge of the upper surface 19a of the spin base 19, for example. have.

The spin chuck 5 is an example of the thinning unit which performs the thinning process which thins the process liquid film formed in the pattern formation surface of the board | substrate W by rotating and holding the board | substrate W horizontally. The spin chuck 5 is also an example of a sublimation promotion unit that performs a sublimation promotion step of promoting sublimation of the coagulated body by rotating the substrate when the coagulated body is sublimed.

The chemical liquid supply unit 6 includes a chemical liquid supply nozzle 20. The chemical liquid supply nozzle 20 is moved by the first nozzle moving mechanism 21. The chemical liquid supply nozzle 20 moves between the center position and the retracted position. The chemical | medical solution supply nozzle 20 opposes the rotation center position of the pattern formation surface of the board | substrate W when it is located in a center position. The chemical liquid supply nozzle 20 does not face the pattern formation surface of the board | substrate W when it is located in a retracted position. The rotation center position of the pattern formation surface of the board | substrate W is the intersection position with the rotation axis A1 in the pattern formation surface of the board | substrate W. As shown in FIG. The retracted position is the position outside of the spin base 19 in plan view.

The chemical liquid supply pipe 22 is connected to the chemical liquid supply nozzle 20. The chemical liquid supply pipe 22 is provided with a valve 23 for opening and closing the flow path.

Specific examples of the chemical liquid include an etching liquid and a cleaning liquid. More specifically, the chemical liquid may be hydrofluoric acid, SC1 liquid (ammonia hydrogen peroxide mixed solution), SC2 liquid (hydrogen peroxide mixed solution), ammonium fluoride, buffered hydrofluoric acid (mixed solution of hydrofluoric acid and ammonium fluoride), and the like.

The rinse liquid supply unit 7 includes a rinse liquid supply nozzle 24. The rinse liquid supply nozzle 24 is moved by the second nozzle moving mechanism 25. The rinse liquid supply nozzle 24 moves between the center position and the retracted position. The rinse liquid supply nozzle 24 faces the rotation center position of the pattern formation surface of the board | substrate W when it is located in a center position. The rinse liquid supply nozzle 24 does not face the pattern formation surface of the board | substrate W when it is located in a retracted position.

The rinse liquid supply pipe 26 is connected to the rinse liquid supply nozzle 24. The rinse liquid supply pipe 26 is provided with a valve 27 that opens and closes the flow path.

A specific example of the rinse liquid is deionized water (DIW), for example. The rinse liquid is not limited to DIW, and may be any of carbonated water, electrolytic ion water, hydrogen water, ammonia water, ozone water, and hydrochloric acid water having a dilution concentration (for example, about 10 to 100 ppm).

The pretreatment liquid supply unit 8 includes the pretreatment liquid supply nozzle 28. The pretreatment liquid supply pipe 30 is connected to the pretreatment liquid supply nozzle 28. The pretreatment liquid supply pipe 30 is provided with the valve 31 which opens and closes the flow path.

As a pretreatment liquid, the solvent etc. which mix with a process liquid are used. The processing liquid can be smoothly spread evenly on the pattern formation surface of the substrate W by supplying the pretreatment liquid to the pattern formation surface of the board | substrate W and spreading it evenly.

In particular, in the embodiment, it is preferable to use a solvent that is mixed with both the rinse liquid and the treatment liquid as the pretreatment liquid. When such a pretreatment liquid is used, the rinse liquid supplied in the pre-process and remaining on the pattern formation surface of the substrate W can be smoothly substituted with the treatment liquid through the pretreatment liquid. Therefore, the processing liquid can be evenly spread evenly on the pattern formation surface of the substrate W. FIG.

For example, the specific example of the pretreatment liquid mixed with both the aqueous rinse liquid and the treatment liquid containing a fluorohydrocarbon compound is an organic solvent represented by isopropyl alcohol (IPA), Various solvents to mix can be used.

The processing liquid supply unit 9 includes a processing liquid supply nozzle 32. The processing liquid supply pipe 34 is connected to the processing liquid supply nozzle 32. The processing liquid supply pipe 34 is provided with a valve 35 that opens and closes the flow path.

As the treatment liquid, a treatment liquid containing a sublimable substance is used. As a treatment liquid containing a sublimable substance, for example, a solution in which a sublimable substance, such as a melt of a sublimable substance, is contained in a molten state, or a solution in which a sublimable substance as a solute is dissolved in a solvent can be used. have. Here, the "melted state" refers to a state in which a sublimable substance is completely or partially dissolved to have fluidity and exhibit a liquid phase.

As the sublimable substance, various substances having a high vapor pressure at the first normal temperature and changing to a gas phase without passing through a liquid phase in a solid phase are used. 1st normal temperature is the temperature in the clean room of the state which is not in temperature control, and is the temperature in the processing unit 2 of the state which is not in temperature control. 1st normal temperature is 5 degreeC-35 degreeC, for example.

The back surface supply unit 10 includes the back surface supply nozzle 36. The back surface supply nozzle 36 passes through the hollow spin shaft 18 and has a discharge port 36a facing the center of the back surface of the substrate W at its upper end.

In this embodiment, the back surface supply nozzle 36 supplies a temperature control medium from the discharge port 36a toward the center position of the back surface of the board | substrate W, rotating the board | substrate W. As shown in FIG. The supplied temperature control medium is evenly spread over the entire back surface of the substrate W by the action of centrifugal force. When the supplied temperature control medium is a fruit, the processing liquid film formed on the substrate W and the pattern formation surface of the substrate W is heated. In addition, when the supplied temperature control medium is a refrigerant, the processing liquid film is cooled. The rotation center position of the back surface of the board | substrate W is the intersection position with the rotation axis A1 in the back surface of the board | substrate W. As shown in FIG.

The fruit supply pipe 37 is connected to the back surface supply nozzle 36. The fruit supply pipe 37 has a valve 38 for opening and closing the flow path and a valve 39 for adjusting the flow rate of the fruit flowing through the fruit supply pipe 37.

Moreover, the coolant supply pipe 40 is further connected to the back surface supply nozzle 36. The coolant supply pipe 40 is provided with a valve 41 for opening and closing the flow path and a valve 42 for adjusting the flow rate of the coolant flowing through the coolant supply pipe 40.

The heat supply pipe 37 and the refrigerant supply pipe 40 are connected to the back surface supply nozzle 36 via the shared pipe 43.

The back surface supply unit 10 maintains the temperature of the processing liquid film formed on the pattern formation surface of the substrate W at a temperature range (melting temperature range) that is equal to or higher than the melting point of the sublimable material and is less than the boiling point of the sublimable material. It is an example of a fruit supply unit which performs a temperature holding process. The fruit supply pipe 37, the shared pipe 43, and the back surface supply nozzle 36 constitute a fruit path of the fruit supply unit.

The back surface supply unit 10 is also an example of a refrigerant supply unit that performs a solidification step of solidifying a processing liquid film thinned by a thin film formation process on a pattern formation surface of a substrate W to form a solidified body of a sublimable material. The coolant supply pipe 40, the shared pipe 43, and the back supply nozzle 36 constitute a coolant path of the coolant supply unit.

The heat path and the coolant path share the shared pipe 43 and the back supply nozzle 36. That is, the heat path and the refrigerant path at least partially share a pipe. Therefore, the structure of the substrate processing apparatus 1 can be simplified.

One example of the fruit is DIW heated to a melting temperature range. One example of the refrigerant is DIW cooled to a temperature range (solidification temperature range) below the freezing point (melting point) of the sublimable material.

The processing cup 11 is disposed outside (the direction away from the rotation axis A1) from the substrate W held by the spin chuck 5. The processing cup 11 surrounds the spin base 19.

The processing cup 11 includes a plurality of guards 71 receiving liquids (chemical liquid, rinse liquid, pretreatment liquid, or processing liquid) that are scattered outward from the periphery of the substrate W held by the spin chuck 5, A plurality of cups 72 receiving the liquid guided downward by the plurality of guards 71 and a cylindrical outer wall member 73 surrounding the plurality of guards 71 and the plurality of cups 72 are included. In this embodiment, four guards 71 (first guard 71A, second guard 71B, third guard 71C and fourth guard 71D), and three cups 72 (first The example in which 1 cup 72A, the 2nd cup 72B, and the 3rd cup 72C) is provided is shown.

Each cup 72 has a shape of a groove open upward. Each guard 71 surrounds the spin base 19. The first guard 71A, the second guard 71B, the third guard 71C and the fourth guard 71D are arranged from the inside in this order. The first cup 72A receives the liquid guided downward by the first guard 71A. The second cup 72B receives the liquid guided downward by the second guard 71B. The 3rd cup 72C is integrally formed with the 2nd guard 71B, and receives the liquid guided by the 3rd guard 71C.

The processing unit 2 includes a guard elevating mechanism 74 for elevating four guards 71 separately. The guard elevating mechanism 74 raises and lowers each guard 71 between a lower value and an upper value. Each guard 71 is located in the side of the board | substrate W in the whole range of the movable range between an upper value and a lower value. The moving range includes upper and lower values.

The guard elevating mechanism 74 includes, for example, a ball screw mechanism (not shown) attached to each guard 71 and a motor (not shown) for imparting driving force to each ball screw.

When the chemical liquid mainly scatters from the substrate W, the guard elevating mechanism 74 raises and lowers the plurality of guards 71 so that the liquid scattered from the substrate W is received by the second guard 71B ( See FIG. 5A to be described later).

When the rinse liquid mainly scatters from the substrate W, the guard elevating mechanism 74 raises and lowers the plurality of guards 71 so that the liquid scattered from the substrate W is received by the first guard 71A. (See FIG. 5B, described below).

When the processing liquid mainly scatters from the substrate W, the guard elevating mechanism 74 raises and lowers the plurality of guards 71 so that the liquid scattered from the substrate W is received by the third guard 71C. (See FIG. 5E to FIG. 5G to be described later.)

When the guard elevating mechanism 74 dries the pattern formation surface of the board | substrate W, and the pretreatment liquid mainly scatters from the board | substrate W, the liquid which drips from the board | substrate W is 4th guard 71D. ), The plurality of guards 71 are lifted and received (see FIGS. 5C, 5D, and 5H described later). And the liquid received by the guard 71 is sent to the collection | recovery apparatus or waste liquid apparatus which is not shown in figure.

The 1st condensation prevention unit 12 opposes the pattern formation surface of the board | substrate W, and cuts off the atmosphere between the board | substrate W from the surrounding atmosphere, and the pattern of the board | substrate W. The first inert gas nozzle 45 which supplies an inert gas to the center area | region of a formation surface is included.

The blocking plate 44 is formed in a disk shape having a diameter substantially the same as or larger than that of the substrate W. As shown in FIG. The blocking plate 44 is arranged horizontally above the spin chuck 5. The hollow shaft 44a is fixed to the center of the upper surface of the blocking plate 44. The hollow shaft 44a extends in the vertical direction along the rotation axis A1.

A blocking plate elevating mechanism 46 for elevating the blocking plate 44 fixed to the hollow shaft 44a is connected to the hollow shaft 44a by elevating the hollow shaft 44a along the vertical direction. The blocking plate elevating mechanism 46 can raise and lower the blocking plate 44 between a proximal position (see FIG. 5H to be described later) and a spaced position (see FIG. 5A to be described later). When the blocking plate 44 is located in the proximal position, the bottom surface of the blocking plate 44 facing the pattern forming surface of the substrate W is close to the pattern forming surface of the substrate W. As shown in FIG. The separation position is a position above the proximity position.

In the state where the blocking plate 44 is lowered to the proximal position, the atmosphere between the lower surface of the blocking plate 44 and the pattern formation surface of the substrate W is cut off from the surrounding atmosphere. Thereby, the blocking plate 44 can suppress that the liquid which protruded from the guard 71 enters between the pattern formation surface of the board | substrate W and the lower surface of the blocking plate 44. In addition, when subliming the solidified body formed on the pattern formation surface of the substrate W, the amount of moisture contained in the atmosphere in contact with the solidified body can be limited. And moisture in an atmosphere can be prevented from condensing on the pattern formation surface of a solidified body or a board | substrate.

The first inert gas supply pipe 47 is connected to the first inert gas nozzle 45. The first inert gas supply pipe 47 is provided with a valve 48 that opens and closes the flow path.

A specific example of the inert gas is, for example, nitrogen gas (N ₂ ). Inert gas is a gas inert with respect to the surface and pattern of the board | substrate W. FIG. The inert gas is not limited to nitrogen gas, and may be, for example, a rare gas such as argon. In particular, in order to improve the effect of preventing dew condensation, it is preferable to use a high temperature inert gas that is hotter than room temperature. Room temperature is the temperature in a clean room, and is the temperature in the processing unit 2.

In this embodiment, the pretreatment liquid supply nozzle 28, the process liquid supply nozzle 32, and the first inert gas nozzle 45 extend in the vertical direction along the rotation axis A1, and extend to the hollow shaft 44a. It is accommodated in the nozzle accommodation member 80 which passed through in common. The lower end part of the nozzle accommodating member 80 opposes the center area | region of the upper surface of the board | substrate W. As shown in FIG. By discharging the pretreatment liquid from the discharge port of the pretreatment liquid supply nozzle 28, the pretreatment liquid is supplied to the center region of the pattern formation surface of the substrate W. As shown in FIG. Similarly, the processing liquid is supplied to the center region of the pattern formation surface of the substrate W by discharging the processing liquid from the discharge port of the processing liquid supply nozzle 32.

Each of the pretreatment liquid supply nozzle 28, the processing liquid supply nozzle 32, and the first inert gas nozzle 45 has a discharge port facing the pattern formation surface of the substrate W at the lower end. The pretreatment liquid supply nozzle 28, the process liquid supply nozzle 32, and the first inert gas nozzle 45 are elevated together with the blocking plate 44 fixed to the hollow shaft 44a.

The blocking plate 44 is lowered so that the lower surface of the blocking plate 44 is close to the pattern forming surface of the substrate W, and the discharge port of the first inert gas nozzle 45 is the pattern of the substrate W. It faces the rotation center position of a formation surface. In this state, the inert gas is supplied to the center region of the pattern formation surface of the substrate W by discharging the inert gas from the discharge port of the first inert gas nozzle 45. The supplied inert gas diffuses outward from the center region of the pattern formation surface of the substrate W to the outside in the atmosphere between the lower surface of the blocking plate 44 and the pattern formation surface of the substrate W. From the periphery of the pattern formation surface, it is discharged out of the atmosphere.

This dehumidifies the atmosphere between the lower surface of the blocking plate 44 and the pattern formation surface of the board | substrate W cut off from the surrounding atmosphere by the blocking plate 44. Therefore, when subliming the solidified body formed on the pattern formation surface of the board | substrate W, it can prevent that moisture in an atmosphere condenses on the solidification body and the pattern formation surface of a board | substrate. In particular, when supplying a high temperature inert gas, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W warms, and the effect which prevents dew condensation improves.

Moreover, sublimation of a coagulation body is accelerated | stimulated by the inert gas distribute | circulating on the surface of a coagulation body. In particular, in the case of supplying the high temperature inert gas, the atmosphere in the vicinity of the pattern formation surface of the substrate W is warmed, and the sublimation of the coagulated body is further promoted. Therefore, the 1st inert gas nozzle 45, the 1st inert gas supply pipe 47, and the valve 48 are also an example of a sublimation promotion unit which performs the sublimation acceleration | stimulation process which promotes sublimation of a coagulation body.

The second dew condensation prevention unit 13 is an annular cooling tube disposed in the processing cup 11 and surrounding the spin base 19 and disposed outside the substrate W (direction away from the rotation axis A1). 49).

The coolant supply pipe 50 is connected to the cooling tube 49. The coolant supply pipe 50 is downstream from the valve 42 of the coolant supply pipe 40, and is connected to an upstream side of the valve 41. The coolant supply pipe 50 is provided with a valve 51 that opens and closes the flow path. In addition, although not shown in figure, the refrigerant | coolant discharge piping which discharges the refrigerant | coolant which distribute | circulated in the cooling tube 49 out of the chamber 4 is connected to the cooling tube 49.

The valve 51 is opened, the refrigerant is circulated through the coolant supply pipe 50, the cooling pipe 49, and the coolant discharge pipe to cool the cooling pipe 49, thereby condensing moisture in the atmosphere to the surface of the cooling pipe 49. Can be removed from the atmosphere. Therefore, it is possible to prevent the moisture in the atmosphere from condensing on the solidification body or the pattern formation surface of the substrate W.

The FFU 15 is disposed above the partition 14 and is attached to the ceiling of the partition 14. The FFU 15 sends clean air into the chamber 4 from the ceiling of the partition 14. The exhaust device 16 is connected to the bottom of the outer wall member 73 of the processing cup 11 via an exhaust duct 52 connected to the outer wall member 73 of the processing cup 11, and processing cup 11. The inside of the processing cup 11 is sucked from the bottom of the outer wall member 73 of (). By the FFU 15 and the exhaust device 16, downflow (downflow) is formed in the chamber 4.

The FFU 15 and the exhaust device 16 form a downflow in the chamber 4 and dehumidify the inside of the chamber 4, so that condensation forms on the pattern formation surface of the substrate W when the coagulated body is sublimated. Implement a condensation prevention process to prevent occurrence. That is, the FFU 15 and the exhaust device 16 function as an example of the condensation prevention unit.

In addition, the FFU 15 and the exhaust device 16 perform a sublimation promotion step of promoting sublimation of the coagulated body by, for example, increasing the flow velocity of the downflow and promoting the ventilation in the chamber 4. That is, the FFU 15 and the exhaust device 16 also function as an example of a sublimation promotion unit.

Moreover, the exhaust apparatus 16 functions as an example of a sublimation promotion unit which performs the sublimation promotion process which promotes sublimation of a coagulated body by decompressing the inside of the process cup 11 from the bottom part of the process cup 11. .

A second inert gas nozzle 81 is provided between the inner circumferential surface of the hollow shaft 44a and the outer circumferential surface of the nozzle accommodation member 80. The second inert gas supply pipe 82 is connected to the second inert gas nozzle 81. The second inert gas supply pipe 82 is provided with a valve 83 that opens and closes the flow path.

The inert gas supplied from the second inert gas nozzle 81 is supplied to the space between the blocking plate 44 and the pattern formation surface of the substrate W. As shown in FIG. The inert gas supplied to the space between the blocking plate 44 and the pattern forming surface of the substrate W moves from the center region of the pattern forming surface of the substrate W toward the peripheral edge of the pattern forming surface of the substrate W. FIG. To form a stream of air. By this airflow, it is possible to push back the liquid that has popped out of the guard 71. Therefore, while the inert gas is being supplied from the second inert gas nozzle 81, the liquid splashed from the guard 71 can be prevented from adhering to the pattern formation surface of the substrate W. FIG. As a result, particles caused by jumping back from the guard 71 can be suppressed. In order to form airflow efficiently in the space between the blocking plate 44 and the pattern formation surface of the board | substrate W, it is preferable to place the blocking plate 44 in the proximal position.

In addition, the flow volume of the inert gas supplied from the 2nd inert gas nozzle 81 is a flow volume of the grade which does not accelerate the sublimation of a coagulated body.

When the temperature control medium is supplied from the back supply nozzle 36 to the back surface of the substrate W while the supply of the processing fluid to the pattern formation surface of the substrate W is stopped, the back surface of the substrate W When the temperature control medium supplied to the substrate 71 springs back from the guard 71 and adheres to the pattern formation surface of the substrate W, the temperature control medium adhered to the pattern formation surface of the substrate W is the pattern formation surface of the substrate W. FIG. It is not flushed away by the processing fluid supplied to it. Therefore, there exists a possibility that a particle may generate | occur | produce due to the temperature control medium adhering to the pattern formation surface of the board | substrate W. FIG.

Therefore, when the temperature control medium is being supplied from the back surface supply nozzle 36 to the back surface of the substrate W while the supply of the processing fluid to the pattern formation surface of the substrate W is stopped, the blocking plate 44 is removed. It is further preferable to locate at a proximal position.

On the other hand, while the processing fluid is being supplied to the pattern formation surface of the substrate W, if the blocking plate 44 is too close to the pattern formation surface of the substrate W, the processing is supplied to the pattern formation surface of the substrate W. The fluid may spring back from the pattern formation surface and adhere to the lower surface of the blocking plate 44. Therefore, while the process fluid is being supplied to the pattern formation surface of the board | substrate W, it is preferable that the blocking plate 44 is arrange | positioned at the process position which is a position between a spaced position and a proximity position.

3 is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus 1.

The substrate processing apparatus 1 includes a controller 3. The controller 3 is equipped with a microcomputer and controls the control object with which the board | substrate processing apparatus 1 was equipped according to the predetermined | prescribed control program. Specifically, the controller 3 includes a processor (CPU) 3A and a memory 3B in which a control program is stored, and the processor 3A executes the control program, whereby various kinds of control for substrate processing are performed. It is configured to run. In particular, the controller 3 includes the FFU 15, the exhaust device 16, the spin motor 17, the first nozzle moving mechanism 21, the second nozzle moving mechanism 25, and the blocking plate lifting mechanism 46. , The guard lifting mechanism 74, the valves 23, 27, 31, 35, 38, 39, 41, 42, 48, 51, 83 are programmed.

4 is a flowchart for explaining an example of substrate processing by a processing unit. 5A to 5H are schematic cross-sectional views for explaining the state of the substrate processing.

In the substrate processing by the processing unit 2, first, a chemical liquid processing step is executed (step S1). In the chemical liquid processing step, first, the substrate W is held horizontally on the spin chuck 5 (substrate holding step). The controller 3 drives the spin motor 17 to rotate the spin base 19 to start the rotation of the substrate W (substrate rotation step). In the chemical liquid processing step, the spin base 19 is rotated at a predetermined chemical liquid processing speed which is a substrate rotation speed. The chemical liquid processing speed is 800 rpm-1000 rpm, for example. The substrate holding step and the substrate rotating step are continued until the substrate processing is completed. In the chemical liquid processing step, the controller 3 controls the blocking plate elevating mechanism 46 to arrange the blocking plate 44 at a spaced position.

Next, the controller 3 controls the 1st nozzle movement mechanism 21, and arrange | positions the chemical | medical solution supply nozzle 20 in the center position above the board | substrate W. Next, as shown in FIG. And the controller 3 opens the valve 23. Thereby, as shown to FIG. 5A, the chemical | medical solution 53 is supplied from the chemical | medical solution supply nozzle 20 toward the pattern formation surface which is the upper surface of the board | substrate W of a rotating state. The supplied chemical liquid 53 is evenly spread over the entire surface of the pattern formation surface of the substrate W by the action of the centrifugal force.

After the chemical liquid treatment for a certain period of time, by replacing the chemical liquid on the pattern formation surface of the substrate W with a rinse liquid, a rinse processing step of removing the chemical liquid from the pattern formation surface of the substrate W is performed (step S2). In the rinse processing step, the controller 3 closes the valve 23 and stops the supply of the chemical liquid 53 from the chemical liquid supply nozzle 20. Then, the controller 3 moves the chemical liquid supply nozzle 20 to the retracted position.

Next, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined rinse processing speed which is a substrate rotation speed. The rinse processing speed is 800 rpm-1000 rpm, for example. In the rinse processing step, the controller 3 controls the blocking plate elevating mechanism 46 to hold the blocking plate 44 at a spaced position following the chemical liquid processing step.

Next, the controller 3 controls the 2nd nozzle movement mechanism 25, and arrange | positions the rinse liquid supply nozzle 24 in the center position above the board | substrate W. Next, as shown in FIG. And the controller 3 opens the valve 27. Thereby, as shown in FIG. 5B, the rinse liquid 54 is supplied from the rinse liquid supply nozzle 24 toward the pattern formation surface of the board | substrate W of a rotating state. The supplied rinse liquid 54 is spread evenly over substantially the entire surface of the pattern formation surface of the substrate W by the action of centrifugal force, thereby replacing the chemical liquid.

After the rinse treatment for a certain period, with reference to Fig. 5C, a pretreatment liquid supplying step of replacing the rinse liquid on the pattern formation surface of the substrate W with the pretreatment liquid (step S3). In the pretreatment liquid supply step, the controller 3 closes the valve 27 and stops the supply of the rinse liquid 54 from the rinse liquid supply nozzle 24. Then, the controller 3 moves the rinse liquid supply nozzle 24 to the retracted position.

The controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined pretreatment liquid supply speed which is a substrate rotation speed. The pretreatment liquid supply speed is 100 rpm-500 rpm, for example.

And the controller 3 controls the blocking plate elevating mechanism 46, and arrange | positions the blocking plate 44 in a process position. After the blocking plate 44 reaches the processing position, the controller 3 opens the valve 83. As a result, an inert gas such as nitrogen gas is supplied from the second inert gas nozzle 81. And the inert gas supplied from the 2nd inert gas nozzle 81 forms the airflow which moves toward the periphery of the pattern formation surface of the board | substrate W from the center area | region of the pattern formation surface of the board | substrate W. As shown in FIG.

Then, the controller 3 opens the valve 31. Thereby, the pretreatment liquid 55 is supplied from the pretreatment liquid supply nozzle 28 toward the pattern formation surface of the board | substrate W of a rotating state. The supplied pretreatment liquid 55 is spread evenly over substantially the entire surface of the pattern formation surface of the substrate W by the action of centrifugal force, and replaces the rinse liquid.

After supplying the pretreatment liquid for a certain period, the controller 3 closes the valve 31 and stops the supply of the pretreatment liquid from the pretreatment liquid supply nozzle 28.

Next, referring to FIG. 5D and FIG. 5E, the process liquid supply process (step S4) which supplies a process liquid on the pattern formation surface of the board | substrate W, and the temperature of the process liquid supplied are kept in a melting temperature range. The temperature holding step (substrate temperature adjusting step, step S5) is executed. In this substrate processing, the temperature holding step is started earlier than the start of the processing liquid supplying step.

That is, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined processing liquid supply speed which is a substrate rotation speed. The processing liquid supply speed is 100 rpm-500 rpm, for example.

And the controller 3 controls the blocking plate elevating mechanism 46, and arrange | positions the blocking plate 44 in the proximal position. In the state where the blocking plate 44 is arrange | positioned in the proximity position, the controller 3 opens the valve 38. As shown in FIG. Thereby, through the fruit supply pipe 37 and the back surface supply nozzle 36 which comprise a fruit path | route, as shown in FIG. 5D, the back surface supply nozzle 36 toward the back surface of the board | substrate W of a rotation state. The fruit 56 is supplied from the discharge port 36a at the upper end of the. In the state where the blocking plate 44 is disposed in the proximal position, by supplying the fruit 56, it is confirmed that the fruit 56, which has popped out of the fourth guard 71D, adheres to the pattern forming surface of the substrate W. FIG. It can be suppressed.

The supplied fruit 56 is spread evenly over substantially the entire rear surface of the substrate W by the action of the centrifugal force, and the pretreatment liquid 55 on the pattern forming surface of the substrate W and the substrate W is heated. The temperature of heating considers the thickness of the board | substrate W, etc., and sets the process liquid supplied at a next process to a melting temperature range.

Next, the controller 3 continuously rotates the spin base 19 at the processing liquid supply speed, and continues to supply the fruit 56 to the back surface of the substrate W, and to the pattern formation surface of the substrate W. Supply the processing liquid.

Specifically, the controller 3 controls the blocking plate elevating mechanism 46 to arrange the blocking plate 44 at the processing position. The controller 3 opens the valve 35 in a state where the blocking plate 44 is disposed at the processing position. Thereby, as shown to FIG. 5E, a process liquid is supplied from the process liquid supply nozzle 32 toward the pattern formation surface of the board | substrate W of a rotation state. The supplied processing liquid is spread evenly over substantially the entire surface of the pattern formation surface of the substrate W while being mixed with the pretreatment liquid by the action of centrifugal force, thereby replacing the pretreatment liquid. And the process liquid film 57 is formed in the pattern formation surface of the board | substrate W (process liquid film formation process).

Next, referring to FIG. 5F, a thinning step (step S6) of thinning the processing liquid film 57 formed on the pattern formation surface of the substrate W is performed while continuing the temperature holding step (step S5).

Specifically, first, the controller 3 controls the blocking plate elevating mechanism 46 to arrange the blocking plate 44 in a proximal position. In the state where the blocking plate 44 is disposed in the proximal position, the controller 3 closes the valve 35 and stops the supply of the processing liquid to the pattern formation surface of the substrate W. As shown in FIG. By stopping the supply of the processing liquid in the state where the blocking plate 44 is disposed in the proximal position, the fruit 56 that has been returned from the third guard 71C can be suppressed from adhering to the pattern forming surface of the substrate W. FIG. have. After that, the blocking plate 44 is held in the proximal position until the sublimation step (step S8) described later is completed.

In addition, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined thinning speed which is a substrate rotation speed. The thin film formation speed is 800 rpm-1000 rpm, for example.

Then, as described above, the centrifugal force due to the rotation of the substrate W acts on the processing liquid on the substrate W, and a part of the processing liquid on the substrate W is discharged from the peripheral edge of the substrate W, thereby processing The liquid film 57 is thinned (removal thinning step). Therefore, the processing liquid can be uniformly spread evenly over the entire pattern formation surface, and the film thickness of the processing liquid film 57 can be appropriately reduced. Furthermore, the film thickness of the solidification body 59 formed in the solidification process mentioned later can be reduced suitably. In addition, the treatment liquid film 57 can be thinned by a simple method of removing a part of the treatment liquid from the pattern formation surface by centrifugal force due to the rotation of the substrate W. FIG.

Next, the temperature holding step (step S5) is completed, and as shown in FIG. 5G, by supplying a coolant to the back surface of the substrate W, the thinned processing liquid film 57 is solidified to form a solidified body 59. The solidification process (step S7) to be performed is performed.

Specifically, first, the controller 3 closes the valve 38, stops the supply of the fruit 56 to the fruit path, and ends the temperature holding step (step S5).

Next, the controller 3 opens the valve 41 and forms a refrigerant path downstream from the connection position of the refrigerant supply pipe 40 among the refrigerant supply pipe 40 and the heat supply pipe 37, and the rear surface supply nozzle. Supply of the coolant to 36 is started. The timing at which the valve 41 is opened to start the supply of the coolant to the coolant path may be simultaneous with or after the timing at which the valve 38 is closed and the supply of the coolant to the heat path is stopped.

Then, a refrigerant | coolant is supplied toward the back surface of the board | substrate W of a rotation state from the discharge port 36a of the upper end of the back surface supply nozzle 36 via a refrigerant | coolant path | route.

The coolant supplied to the rear surface of the substrate W is spread evenly over substantially the entire rear surface of the substrate W by the action of centrifugal force to replace the fruit. Thereby, cooling of the process liquid film 57 formed in the pattern formation surface of the board | substrate W is started.

The controller 3 controls the spin motor 17 while continuing to supply the coolant 58 to the rear surface of the substrate W to rotate the spin base 19 at a predetermined solidification speed, which is the substrate rotation speed. Let's do it. The speed at the time of solidification is 100 rpm-500 rpm, for example. As a result, the processing liquid film 57 formed on the pattern formation surface of the substrate W solidifies to form the solidified body 59.

However, the coolant is gradually supplied to the rear surface of the substrate W while pushing the fruit remaining in the shared portion between the refrigerant path and the fruit path, that is, the shared pipe 43 and the back surface supply nozzle 36. In addition, the refrigerant gradually replaces the fruit on the back surface of the substrate W. As shown in FIG. Therefore, while the substrate W has a predetermined heat capacity, the temperature of the processing liquid film 57 formed on the pattern formation surface of the substrate W gradually decreases.

Therefore, after the temperature holding step (step S5) is finished, the processing liquid film 57 formed on the pattern formation surface of the substrate W is delayed from the time point at which the valve 41 is opened and the supply of the coolant to the coolant path is started. Solidification (solidification process, step S7) is started.

By setting the heat capacity of the substrate W based on the temperature of the fruit and the coolant, the flow rate and the thickness of the fruit and the coolant, and the like, the solidification of the process liquid film 57 can be started from the time when the cooling of the process liquid film 57 is started. The period until can be made constant.

In this case, the length of the period (thinning period) in which the processing liquid film 57 is thinned by discharging the processing liquid from the substrate W can be adjusted by controlling the timing of starting cooling of the processing liquid film 57. In this embodiment, the timing for starting cooling of the processing liquid film 57 is to close the valve 35 to stop the supply of the fruit to the fruit path, and instead to open the valve 41 to supply the refrigerant to the refrigerant path. It is the timing to start supply.

By adjusting the length of the thinning period, the film thickness of the processing liquid film 57 after the thinning step can be adjusted. For example, the longer the thinning period is, the smaller the film thickness of the processing liquid film 57 can be.

6 is a time chart for explaining the thinning during substrate processing and the steps before and after the process.

As shown in FIG. 6, when the timing at which the cooling of the processing liquid film 57 is started is later than the stop of the supply of the processing liquid to the pattern formation surface of the substrate, the cooling of the processing liquid film 57 is started. The thinning process begins before.

Although not shown, when the timing at which cooling of the processing liquid film 57 is started coincides with the time when the supply of the processing liquid to the pattern formation surface of the substrate W is stopped, the thinning process is started at this time. At the point where solidification of the treatment liquid film starts, the thinning process is completed.

Therefore, as shown in FIG. 6, when the timing which starts cooling of the process liquid film 57 is made later than the stop of supply of the process liquid to the pattern formation surface of the board | substrate W, the process liquid film 57 The period (thinning period T) of a thinning process becomes long compared with the case where the timing which starts cooling is made simultaneously with the time of stopping supply of a process liquid to the pattern formation surface of a board | substrate. As a result, the film thickness of the processing liquid film 57 becomes smaller.

Therefore, the length of the thinning period T is adjusted by selecting whether to start the cooling of the processing liquid film 57 at the same time as stopping the supply of the processing liquid or later than stopping the supply of the processing liquid. The film thickness of the processing liquid film 57 can be controlled.

However, it is necessary to keep the film thickness of the processing liquid film 57 after thinning within a range larger than the height of the convex portion of the pattern on the pattern formation surface of the substrate W. This is because when the thickness of the processing liquid film 57 is smaller than the height of the convex portion of the pattern, collapse of the pattern may occur due to surface tension.

Next, with reference to FIG. 5H, the sublimation process (step S8) which sublimes the formed solidified body 59 and removes from the pattern formation surface of the board | substrate W is performed. In parallel with the sublimation step, a condensation prevention step (step S9) for preventing condensation on the pattern formation surface of the substrate W and a sublimation acceleration step (step S10) for promoting sublimation of the coagulated body are performed.

Specifically, the controller 3 closes the valve 41 and stops the supply of the coolant 58 to the rear surface of the substrate W. As shown in FIG. In addition, the controller 3 drives the FFU 15 and the exhaust device 16 to form a downflow in the chamber 4, and further, through the exhaust duct 52, from the bottom of the processing cup 11. The inside of the processing cup 11 is reduced in pressure. Thereby, sublimation of the coagulation body 59 is accelerated | stimulated, and dew condensation is prevented (sublimation promotion process and dew condensation prevention process).

As described above, the controller 3 controls the blocking plate elevating mechanism 46 to hold the blocking plate 44 in a proximal position. Thereby, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W, specifically, the atmosphere between the blocking plate 44 and the board | substrate W is cut off from the surrounding atmosphere, and dew condensation is prevented (prevents dew condensation). fair).

Moreover, the controller 3 opens the valve 48 and supplies an inert gas to the center area | region of the pattern formation surface of the board | substrate W from the discharge port of the lower end of the 1st inert gas nozzle 45. FIG. By the supplied inert gas, the atmosphere between the lower surface of the blocking plate 44 and the pattern formation surface of the substrate W is dehumidified to prevent condensation (condensation prevention step). In particular, when supplying a high temperature inert gas, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W warms, and the effect which prevents dew condensation improves.

Moreover, sublimation of the coagulation body 59 is accelerated | stimulated by the inert gas distribute | circulating on the surface of the coagulation body 59 (sublimation promotion process). In particular, in the case of supplying the high temperature inert gas, the atmosphere in the vicinity of the pattern formation surface of the substrate W is warmed, and the sublimation of the coagulated body 59 is further promoted.

In addition, the controller 3 opens the valve 51 to circulate the refrigerant to cool the cooling tube 49. Thereby, the cooling tube 49 can function as a dew condensation trap, moisture can be condensed on the surface of the cooling tube 49, and can be removed from the atmosphere. That is, condensation is prevented (condensation prevention step).

In this state, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined first sublimation speed which is the substrate rotation speed. The first sublimation speed is, for example, 100 rpm to 500 rpm. Next, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined second sublimation speed which is the substrate rotation speed. The second sublimation speed is, for example, 500 rpm to 1500 rpm. Thereby, the solidified body 59 formed in the pattern formation surface of the board | substrate W is sublimed and removed, and the pattern formation surface of the board | substrate W is dried (sublimation process and sublimation promotion process).

According to this embodiment, in the temperature holding step, solidification of the processing liquid film 57 is suppressed by maintaining the temperature of the processing liquid film 57 in the melting temperature range. Thereby, the process liquid film 57 before a coagulation process can be maintained in a liquid phase. For example, even if partial solidification of the processing liquid film 57 occurs in the processing liquid supplying step (processing liquid film forming step), it can be remelted in the temperature holding step to form a liquid phase.

In the subsequent thinning process, the solidification body formed in the solidification step is made by thinning the processing liquid film 57 while the temperature of the processing liquid film 57 is in the melting temperature range and solidification of the processing liquid film does not occur. The film thickness of 59 can be reduced.

Therefore, in the solidification process, the solidification body 59 in which the internal stress is as small as possible and the film thickness was appropriately adjusted can be formed in the pattern formation surface of the board | substrate W. As shown in FIG.

As a result, since the influence of the surface tension of the liquid can be eliminated, the pattern formation surface of the substrate W can be dried while suppressing collapse of the pattern.

Moreover, according to this embodiment, the temperature holding process can be performed by the simple method of supplying a fruit to the back surface of the board | substrate W. Moreover, in FIG. Moreover, the solidification process can be performed by the simple method of supplying a refrigerant | coolant to the back surface of the board | substrate W. As shown in FIG. Therefore, the structure of the substrate processing apparatus for implementing a substrate processing method can be simplified.

In this embodiment, the substrate temperature adjusting step is started earlier than the start of the processing liquid supplying step. Therefore, by supplying the fruit to the back surface of the substrate W and executing the processing liquid supplying step with the substrate W heated in advance, solidification of the processing liquid film 57 in the processing liquid supplying step can be further suppressed. Can be. Moreover, since the solidification of the process liquid film 57 in a process liquid supply process is suppressed, it is not necessary to remelt the solidified process liquid film 57 in a temperature maintenance process. Therefore, the period of the temperature holding step can be shortened.

FIG. 7 is a schematic cross-sectional view showing an enlarged main part of a modification of the processing unit 2 included in the substrate processing apparatus 1 according to the first embodiment.

The processing unit 2 of the example of FIG. 7 has a first discharge port 60 and a second discharge port 61 for discharging an inert gas in place of the blocking plate 44 and the first inert gas nozzle 45. The use of one inert gas nozzle 62 is different from the embodiment described using the examples of the foregoing drawings. However, since the other structure and each process using a processing unit are the same as the example of each previous figure, a change point is demonstrated below, especially referring also to the processing unit 2 of FIG.

The first discharge port 60 is provided at the lower end of the inert gas nozzle 62 so as to face the pattern formation surface of the substrate W, similarly to the discharge port 45a of the first inert gas nozzle 45. have. As shown by the solid arrow in the drawing, the first discharge port 60 discharges the inert gas in the substantially vertical direction along the rotation axis A1 to the center region of the pattern formation surface of the substrate W. As shown in FIG. An inert gas supply pipe 63 is connected to the first discharge port 60. The inert gas supply pipe 63 is provided with a valve 64 that opens and closes the flow path.

The second discharge port 61 is annularly opened to the outer circumferential surface of the lower end of the inert gas nozzle 62. As shown by the broken-line arrow in the figure, the second discharge port 61 discharges the inert gas laterally and radially along the pattern formation surface of the substrate W. As shown in FIG. An inert gas supply pipe 65 is connected to the second discharge port 61. The inert gas supply pipe 65 is provided with a valve 66 that opens and closes the flow path.

A nozzle elevating mechanism 67 for elevating the inert gas nozzle 62 along the vertical direction is connected to the inert gas nozzle 62. By the nozzle elevating mechanism 67, the inert gas nozzle 62 has a proximity position (see FIG. 7) in which the first discharge port 60 is brought close to the pattern formation surface of the substrate W, and the first discharge port 60. Is lifted between the spaced apart positions spaced apart upward from the proximal position.

The inert gas nozzle 62 is lowered so that the first discharge port 60 is close to the pattern formation surface of the substrate W, and the first discharge port 60 of the inert gas nozzle 62 is the substrate W. FIG. ) To the rotation center position of the pattern formation surface.

In this state, when the inert gas is discharged laterally and radially from the second discharge port 61 of the inert gas nozzle 62 along the pattern forming surface of the substrate W, the pattern forming surface of the substrate W is formed. On the surface, a gas flow of inert gas is formed from the rotational center position of the substrate W to the circumference. Thereby, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W is interrupted | blocked from the surrounding atmosphere.

Moreover, an inert gas is supplied to the center area | region of the pattern formation surface of the board | substrate W by discharging an inert gas from the 1st discharge port 60 of the inert gas nozzle 62. FIG. The supplied inert gas diffuses outward from the center region of the pattern formation surface of the substrate W onto the pattern formation surface of the substrate W, and is discharged out of the atmosphere from the peripheral edge of the pattern formation surface of the substrate W. . Thereby, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W is dehumidified. Therefore, when subliming the solidified body 59 formed on the pattern formation surface of the board | substrate W, it can prevent that moisture in an atmosphere condenses on the solidification body 59 and the pattern formation surface of the board | substrate W ( Condensation prevention process). Moreover, sublimation of a coagulation body is accelerated | stimulated by the inert gas distribute | circulating on the surface of the coagulation body 59 (sublimation promotion process).

In particular, in the case of supplying a high temperature inert gas that is hotter than room temperature, the atmosphere in the vicinity of the pattern formation surface of the substrate W is warmed, the effect of preventing condensation is improved, and the sublimation of the solidified body 59 is further promoted. do.

<2nd embodiment>

FIG. 8: is a schematic cross section which shows schematic structure of the processing unit 2P with which the substrate processing apparatus 1P which concerns on 2nd Embodiment is equipped. In FIG. 8, the same code | symbol is attached | subjected to the member same as the member demonstrated so far, and the description is abbreviate | omitted (the same also in FIGS. 9-11H mentioned later).

The difference between the processing unit 2P according to the second embodiment and the processing unit 2 according to the first embodiment is mainly different from that of the chemical liquid supply nozzle 20 and the rinse liquid supply nozzle 24. 28), the process liquid supply nozzle 32 and the 1st inert gas nozzle 45 are accommodated in the nozzle accommodating member 80, and the back surface supply nozzle 36 processes a fruit supply pipe 37 instead. The fluid supply pipe 90 is connected.

In the second embodiment, since the chemical liquid supply nozzle 20 and the rinse liquid supply nozzle 24 are accommodated in the nozzle accommodation member 80, the processing unit 2P includes the nozzle moving mechanisms 21 and 22. It is not.

In addition, the processing unit 2P uses the processing liquid supply nozzle 32 and the processing liquid in order to maintain the temperature of the processing liquid in the processing liquid supply nozzle 32 and the processing liquid supply pipe 34 above the melting point of the sublimable substance. And a heater 99 for heating at least one of the supply pipes 34. The heater 99 is built in the hollow shaft 44a, for example.

The heater 99 can heat the processing liquid remaining in the processing liquid supply nozzle 32 and the processing liquid supply pipe 34. In addition, the heat of the heater 99 is transferred from the processing liquid supply nozzle 32 and the processing liquid supply pipe 34 to the discharge port 32a of the processing liquid supply nozzle 32, whereby the discharge port 32a is heated. Therefore, the amount of heat of the processing liquid remaining in the processing liquid supply pipe 34 and the discharge port 32a of the processing liquid supply nozzle 32 can be replenished. Therefore, solidification of the processing liquid remaining in the processing liquid supply pipe 34 and the discharge port 32a of the processing liquid supply nozzle 32 can be suppressed or prevented.

9 is a schematic view of the processing fluid supply pipe 90. The processing fluid supplied to the back surface supply nozzle 36 according to the second embodiment includes not only a temperature control fluid but also a chemical liquid and a rinse liquid. The processing fluid supply pipe 90 includes a processing fluid supply pipe 100, a processing fluid common pipe 101, a first fruit supply pipe 102, a second fruit supply pipe 103, and a refrigerant supply pipe ( 104, a rinse liquid delivery pipe 105, and a chemical liquid delivery pipe 106.

The processing fluid liquid supply pipe 100 sends the processing fluid from the processing fluid common pipe 101 to the discharge port 36a of the back surface supply nozzle 36. The first fruit feeding pipe 102 sends the first fruit to the processing fluid common pipe 101 from the first fruit supply source 112. The second fruit feeding pipe 103 sends the second fruit from the second fruit supply source 113 to the processing fluid common pipe 101. The coolant liquid supply pipe 104 sends a coolant from the coolant supply source 114 to the processing fluid common pipe 101. The rinse liquid supply pipe 105 sends the rinse liquid from the rinse liquid supply source 115 to the processing fluid common pipe 101. The chemical liquid delivery pipe 106 sends the chemical liquid from the chemical liquid supply source 116 to the processing fluid common pipe 101. The processing fluid common pipe 101 is connected to a drain pipe 107 for discharging the processing fluid in the processing fluid common pipe 101.

The processing fluid supply pipe 100 is provided with a valve 120 that opens and closes a flow path in the processing fluid delivery pipe 100. A valve 122 for opening and closing the flow path in the first fruit feeding pipe 102 is interposed in the first fruit feeding pipe 102. In the 2nd fruit feed pipe 103, the valve 123 which opens and closes the flow path in the 2nd fruit feed pipe 103 is interposed. The coolant liquid supply pipe 104 is provided with a valve 124 that opens and closes a flow path in the coolant liquid supply pipe 104. The rinse liquid feed pipe 105 is provided with a valve 125 that opens and closes a flow path in the rinse liquid feed pipe 105. The chemical liquid delivery pipe 106 is provided with a valve 126 for opening and closing the flow path in the chemical liquid delivery pipe 106. The drain pipe 107 is provided with a valve 127 for opening and closing the flow path in the drain pipe 107.

The 1st fruit discharged from the discharge port 36a of the back surface supply nozzle 36 is a fluid (for example, DIW) which heats the board | substrate W, and the 1st temperature (for example, 60 degreeC) in a melting temperature range 80 DEG C). The second fruit discharged from the discharge port 36a of the back surface supply nozzle 36 is a fluid (for example, DIW) that heats the substrate W, and the second fruit is a temperature lower than the first temperature within the melting temperature range. The temperature is maintained at, for example, 25 ° C. The coolant is a fluid (for example, DIW) that cools the substrate W, and is maintained at a temperature (for example, 4 ° C. to 19 ° C.) within a solidification temperature range.

FIG. 10 is a block diagram showing the electrical configuration of main parts of the substrate processing apparatus 1P according to the second embodiment. The controller 3 of the substrate processing apparatus 1P includes an FFU 15, an exhaust device 16, a spin motor 17, a blocking plate lifting mechanism 46, a guard lifting mechanism 74, a heater 99, It is programmed to control the valves 23, 27, 31, 35, 48, 83, 120, 122, 123, 124, 125, 126, 127.

In the processing unit 2P according to the second embodiment, the same substrate processing as that in the flowchart shown in FIG. 4 is possible. 11A to 11H are schematic cross-sectional views for explaining the state of substrate processing performed by the processing unit 2P.

In the substrate processing by the processing unit 2P, first, the chemical liquid processing step is executed (step S1). In the chemical liquid processing step, first, the substrate W is held horizontally on the spin chuck 5 (substrate holding step). The controller 3 drives the spin motor 17 to rotate the spin base 19 to start the rotation of the substrate W (substrate rotation step). In the chemical liquid processing step, the spin base 19 is rotated at a predetermined chemical liquid processing speed. The chemical liquid processing speed is 800 rpm-1000 rpm, for example. The substrate holding step and the substrate rotating step are continued until the substrate processing is completed. In the chemical liquid processing step, the controller 3 controls the blocking plate elevating mechanism 46 to arrange the blocking plate 44 at a spaced position.

Next, the controller 3 opens the valve 23. Thereby, as shown to FIG. 11A, chemical liquid 53 is supplied from the chemical liquid supply nozzle 20 toward the pattern formation surface which is the upper surface of the board | substrate W of a rotation state. The supplied chemical liquid 53 is evenly spread over the entire surface of the pattern formation surface of the substrate W by the action of the centrifugal force.

Then, the controller 3 opens the valves 120 and 126. Thereby, the chemical | medical solution 153 is supplied from the back surface supply nozzle 36 toward the back surface which is a lower surface of the board | substrate W of a rotating state. The supplied chemical liquid 153 is evenly spread on the entire front surface of the back surface of the substrate W by the action of centrifugal force.

After the chemical liquid treatment for a certain period of time, by replacing the chemical liquid on the pattern formation surface of the substrate W with a rinse liquid, a rinse processing step of removing the chemical liquid from the pattern formation surface of the substrate W is performed (step S2).

In the rinse processing step, the controller 3 closes the valve 23 and stops the supply of the chemical liquid 53 from the chemical liquid supply nozzle 20. And the controller 3 opens the valve 27. Thereby, as shown in FIG. 11B, the rinse liquid 54 is supplied from the rinse liquid supply nozzle 24 toward the pattern formation surface of the board | substrate W of a rotation state. The supplied rinse liquid 54 is spread evenly over substantially the entire surface of the pattern formation surface of the substrate W by the action of centrifugal force, thereby replacing the chemical liquid 53.

Then, the controller 3 closes the valve 126 and opens the valve 125. Thereby, the rinse liquid 154 is supplied from the back surface supply nozzle 36 instead of the chemical liquid 153 toward the back surface which is the lower surface of the board | substrate W of a rotating state. The supplied rinse liquid 154 spreads evenly over the entire front surface of the rear surface of the substrate W by the action of centrifugal force to replace the chemical liquid 153.

In the rinse processing step, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined rinse processing speed which is a substrate rotation speed. The rinse processing speed is 800 rpm-1000 rpm, for example. In the rinse processing step, the controller 3 controls the blocking plate elevating mechanism 46 to hold the blocking plate 44 at a spaced position following the chemical liquid processing step.

After the rinse treatment for a certain period, a pretreatment liquid supplying step of replacing the rinse liquid on the pattern formation surface of the substrate W with the pretreatment liquid (step S3).

In the pretreatment liquid supply step, the controller 3 closes the valve 27 and stops the supply of the rinse liquid 54 from the rinse liquid supply nozzle 24. The controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined pretreatment liquid supply speed which is a substrate rotation speed. The pretreatment liquid supply speed is 300 rpm-500 rpm, for example. The controller 3 controls the blocking plate elevating mechanism 46 to move the blocking plate 44 from the spaced position to the processing position. Then, the controller 3 opens the valve 83. As a result, the inert gas is supplied from the second inert gas nozzle 81 to the space between the substrate W and the blocking plate 44.

Then, the controller 3 opens the valve 31. Thereby, as shown in FIG. 11C, the pretreatment liquid 55 is supplied from the pretreatment liquid supply nozzle 28 toward the pattern formation surface of the board | substrate W of a rotation state. The supplied pretreatment liquid 55 is spread evenly over substantially the entire surface of the pattern formation surface of the substrate W by the action of centrifugal force, and replaces the rinse liquid. Then, the controller 3 closes the valve 125 and opens the valve 122. Thereby, the 1st fruit 156 is supplied instead of the rinse liquid 154 from the back surface supply nozzle 36 toward the back surface which is a lower surface of the board | substrate W of a rotation state (1st fruit supply process). The supplied first fruit 156 is evenly spread on the entire front surface of the back surface of the substrate W by the action of the centrifugal force. By supplying the first fruit 156, the temperature of the substrate W is adjusted to a temperature within the melting temperature range. If the temperature of the pretreatment liquid 55 supplied from the pretreatment liquid supply nozzle 28 is set to a temperature within the melting temperature range, the temperature adjustment of the substrate W can be performed more quickly.

After supplying the pretreatment liquid for a certain period, the controller 3 closes the valve 31 and stops the supply of the pretreatment liquid from the pretreatment liquid supply nozzle 28.

Next, the process liquid supply process (step S4) which supplies a process liquid on the pattern formation surface of the board | substrate W, and the temperature of the process liquid supplied by supplying a temperature control medium to the back surface of the board | substrate W are predetermined | prescribed. A temperature holding step (temperature control medium supplying step, step S5) to maintain the temperature range is performed. In 2nd Embodiment, the temperature holding process is started earlier than the start of a process liquid supply process (process liquid film formation process).

In the processing liquid supply step, the processing liquid film 57 is formed on the pattern formation surface of the substrate W by supplying the processing liquid on the pattern formation surface of the substrate W (process liquid film formation step). In the processing liquid film forming step, first, as shown in FIG. 11D, the processing liquid film 57 includes a processing liquid core (process liquid reservoir) 150 smaller than the diameter of the substrate W, including the center of the pattern formation surface. It forms in the center area | region to make (core formation process). The processing liquid core 150 formed in the core forming step may be diffused to a predetermined region wider than the central region if the processing liquid core 150 does not reach the periphery of the substrate W, that is, smaller than the diameter of the substrate W. The discharge amount of the processing liquid from the processing liquid supply nozzle 32 in the core forming step is smaller than the discharge amount of the processing liquid when the processing liquid film 57 is supplied to the entire pattern formation surface of the substrate W. FIG.

Specifically, in the core formation step, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined core formation speed (first rotation speed) (first substrate rotation). fair). As for a core formation speed, 10 rpm-50 rpm are suitable, for example. In addition, the core formation speed may be less than 10 rpm, and rotation of the board | substrate W may be stopped (that is, 0 rpm). In the core forming step, since the substrate W is rotated at a relatively low speed, the processing liquid is uniformly dispersed in the predetermined region (remaining in the central region) while preventing the processing liquid from diffusing toward the periphery of the substrate W. The core 150 may be formed. Even during execution of the core forming step, the supply of the first fruit 156 to the back surface of the substrate W is continued. Since the substrate W is rotated at a relatively low speed, the first fruit 156 supplied to the rear surface of the substrate W falls downward from the rear surface before reaching the periphery of the rear surface of the substrate W by centrifugal force. do.

Next, the thinning process (step S6) which thins the process liquid film 57 formed in the pattern formation surface of the board | substrate W is performed, continuing a temperature holding process (step S5).

Specifically, with reference to FIG. 11E, first, the controller 3 controls the blocking plate elevating mechanism 46, and lowers the blocking plate 44 from the processing position to place it in a proximal position. In the state where the blocking plate 44 is arranged in the proximal position, the controller 3 closes the valve 35 and stops the supply of the processing liquid to the pattern formation surface of the substrate W (processing liquid supply stop step ). By stopping the supply of the processing liquid in the state where the blocking plate 44 is disposed in the proximal position, it is possible to suppress the attachment of the temperature regulating medium that springs back from the third guard 71C to the pattern formation surface of the substrate W. FIG. have.

In addition, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined enlargement thin film formation speed (second rotational speed) (second substrate rotation step). The enlarged thin film formation speed is 3000 rpm, for example. In the thin film formation process, since the substrate W is rotated relatively at a high speed, the processing liquid core 150 formed in the center region of the pattern formation surface is rapidly diffused and thinned to the periphery of the substrate W (expanded thin film formation process).

In the enlarged thin film thinning process, the controller 3 closes the valve 122 and opens the valve 123. As a result, the supply of the first fruit 156 from the back surface supply nozzle 36 to the back surface of the substrate W is stopped, and the second fruit (from the back surface supply nozzle 36 to the back surface of the substrate W ( 157) is started (second fruit feeding step). In the enlarged thin film thinning step, since the substrate W rotates relatively at a high speed, the second fruit 157 supplied to the rear surface of the substrate W diffuses to the peripheral edge of the rear surface of the substrate W. As shown in FIG.

The thin processing liquid film 57 diffused to the periphery of the pattern formation surface is formed by a simple method of diffusing the processing liquid core 150 to the periphery of the pattern formation surface by centrifugal force by the rotation of the substrate W. As shown in FIG. Therefore, the film thickness of the coagulation body 59 formed in the coagulation process performed after a thin film formation process can be reduced suitably. In addition, since the processing liquid in an amount enough to be diffused to the periphery of the pattern formation surface may be supplied to the pattern formation surface, the amount of the processing liquid used for forming the coagulation body 59 can be reduced.

Moreover, in this substrate process, since the process liquid supply stop process is performed before the expansion thin film formation process starts, the quantity of the process liquid discharged out of the board | substrate W in a thin film formation process can be reduced. Therefore, the usage amount of the processing liquid can be further reduced.

In the enlarged thin film formation step shown in FIG. 11E, the processing liquid supply stop step is performed. However, as shown in FIG. 12, the processing liquid supply stop step is not performed, and the substrate W is moved to the pattern formation surface during the expansion thin film formation step. Supply of the processing liquid may be continued. Thereby, a process liquid is replenished to the process liquid film 57 on the pattern formation surface of the board | substrate W (process liquid replenishment process). Therefore, the processing liquid can be spread evenly over the entire pattern formation surface. As shown in FIG. 12, when supplying the process liquid to the pattern formation surface of the board | substrate W during an enlargement thin film formation process, without performing a process liquid supply stop process, the blocking plate 44 is located in a process position. Is placed.

Next, the temperature holding step (step S5) is completed, and the solidification step (step S7) is performed to solidify the thinned processing liquid film 57 to form the coagulation body 59.

Specifically, first, in the case where the supply of the processing liquid is continued during the expansion thinning process, the controller 3 closes the valve 35 to stop the supply of the processing liquid to the pattern formation surface, and the blocking plate lifting mechanism The control plate 46 is controlled to place the blocking plate 44 in the proximal position. In the case where the supply of the processing liquid is stopped during the expansion thinning process, the blocking plate 44 is held in the proximal position.

And the controller 3 closes the valve 123, and stops supply of the 2nd fruit 157 to the back surface of the board | substrate W. As shown in FIG. This completes the temperature holding step (step S5). As shown in FIG. 11F, the controller 3 opens the valve 124 to start the supply of the coolant 58 to the rear surface of the substrate W. As shown in FIG.

Then, the controller 3 controls the spin motor 17 while continuing to supply the coolant 58 to the back surface of the substrate W to rotate the spin base 19 at a predetermined solidification speed. The speed at the time of solidification is 100 rpm-500 rpm, for example. Thereby, as shown to FIG. 11G, the process liquid film 57 formed in the pattern formation surface of the board | substrate W solidifies, and the solidified body 59 is formed.

Next, the sublimation process (step S8) which sublimes the formed solidified body 59 and removes from the pattern formation surface of the board | substrate W is performed. In parallel with the sublimation step, a condensation prevention step (step S9) for preventing condensation on the pattern formation surface of the substrate and a sublimation acceleration step (step S10) for promoting sublimation of the coagulated body are performed.

Specifically, the controller 3 closes the valve 124 to stop the supply of the coolant 58 to the rear surface of the substrate W. As shown in FIG. In addition, the controller 3 drives the FFU 15 and the exhaust device 16 to form a downflow in the chamber 4, and further, through the exhaust duct 52, from the bottom of the processing cup 11. The inside of the processing cup 11 is reduced in pressure. Thereby, sublimation of the coagulation body 59 is accelerated | stimulated, and dew condensation is prevented (sublimation promotion process and dew condensation prevention process).

Next, as shown in FIG. 11H, the controller 3 controls the blocking plate elevating mechanism 46 to hold the blocking plate 44 in a proximal position. Thereby, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W, specifically, the atmosphere between the blocking plate 44 and the board | substrate W is cut off from the surrounding atmosphere, and dew condensation is prevented (prevents dew condensation). fair).

Moreover, the controller 3 opens the valve 48 and supplies an inert gas to the center area | region of the pattern formation surface of the board | substrate W from the discharge port 45a of the lower end of the 1st inert gas nozzle 45. FIG. By the supplied inert gas, the atmosphere between the lower surface of the blocking plate 44 and the pattern formation surface of the substrate W is dehumidified to prevent condensation (condensation prevention step). In particular, when supplying a high temperature inert gas, the atmosphere of the vicinity of the pattern formation surface of the board | substrate W warms, and the effect which prevents dew condensation improves.

Moreover, sublimation of a coagulation body is accelerated | stimulated by the inert gas distribute | circulating on the surface of a coagulation body (sublimation promotion process). In particular, in the case of supplying the high temperature inert gas, the atmosphere in the vicinity of the pattern formation surface of the substrate W is warmed, and the sublimation of the coagulated body 59 is further promoted.

In this state, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined first sublimation speed. The first sublimation speed is, for example, 100 rpm to 500 rpm. Next, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined second sublimation speed which is the substrate rotation speed. The second sublimation speed is, for example, 500 rpm to 1500 rpm. Thereby, the solidified body 59 formed in the pattern formation surface of the board | substrate W is sublimed and removed, and the pattern formation surface of the board | substrate W is dried (sublimation process and sublimation promotion process).

As a result, similarly to the first embodiment, since the influence of the surface tension of the liquid can be eliminated, the pattern formation surface of the substrate W can be dried while suppressing collapse of the pattern.

Moreover, in 2nd Embodiment, a 2nd fruit supply process is performed after a 1st fruit supply process in a temperature maintenance process, and a board | substrate cooling process is performed in a subsequent solidification process. That is, in the solidification step, the treatment liquid film 57 is formed from the first temperature within the melting temperature range (the temperature range is equal to or higher than the melting point of the sublimable substance and less than the boiling point of the sublimable substance). Not rapidly cooled to a temperature within the temperature range below the freezing point (melting point), but in the temperature holding step, once cooled from the first temperature to a second temperature lower than the first temperature within the melting temperature range, In a solidification process, it cools to the temperature within the solidification temperature range. Thus, since the process liquid film 57 is cooled step by step, it can suppress that temperature nonuniformity arises in the process liquid film 57 at the time of cooling. Therefore, it can suppress that the part which does not solidify in the process liquid film 57 in a coagulation process can be suppressed, and generation | occurrence | production of the nonuniformity of the sublimation rate of the coagulation body 59 in the sublimation process after a coagulation process can be suppressed. .

13A and 13B are schematic cross-sectional views for explaining a modification of substrate processing by the processing unit 2P.

In the substrate processing described in FIGS. 11A to 11H, the processing liquid core 150 serving as the processing liquid film 57 is diffused and thinned in the thinning process (expansion thinning process). However, substrate processing without forming the processing liquid core 150 may be performed.

Specifically, in the modification of the substrate processing by the processing unit 2P, as shown in FIG. 13A, without forming the processing liquid core 150 (see FIG. 11D), the processing liquid film forming step of step S4 ( In the processing liquid supplying step), the processing liquid film 57 that is diffused to the periphery of the pattern formation surface of the substrate W is formed. At this time, the supply (refer FIG. 11C) of the 1st fruit 156 to the back surface of the board | substrate W disclosed in the pretreatment liquid supply process is continued. The controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined processing liquid supply speed which is a substrate rotation speed. The processing liquid supply speed is 100 rpm-500 rpm, for example.

Thereafter, as shown in FIG. 13B, the supply of the processing liquid to the pattern formation surface is stopped in the thinning step of step S6. And supply of the 1st fruit 156 to the back surface of the board | substrate W is stopped, and the 2nd fruit 157 is supplied to the back surface of the board | substrate W instead. Thereby, the process liquid film 57 is cooled in steps similarly to the substrate processing described in FIGS. 11A to 11H.

The controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined removal thinning speed which is a substrate rotation speed. The thin film formation speed is a few 10 rpm-100 rpm, for example. By the centrifugal force resulting from the rotation of the substrate W, a part of the processing liquid on the pattern formation surface is removed from the pattern formation surface. Thereby, the process liquid film 57 becomes thin (removing thin film formation process). Therefore, the processing liquid can be reliably evenly spread over the entire pattern formation surface, and the film thickness of the solidified body 59 formed in the solidification step can be appropriately reduced.

<Third embodiment>

FIG. 14: is a schematic cross section which shows schematic structure of the processing unit 2Q with which the substrate processing apparatus 1Q which concerns on 3rd Embodiment is equipped. In FIG. 14, the same members as those described above are denoted by the same reference numerals, and description thereof is omitted (the same also in FIGS. 15A to 15D described later).

The point that the processing unit 2Q according to the third embodiment is mainly different from the processing unit 2P according to the second embodiment is that the heater unit 130 can be lifted and lowered between the spin base 19 and the substrate W. FIG. This is the installed point.

The heater unit 130 has the form of a disc shaped hot plate. The heater unit 130 has an opposing surface 130a opposing the lower surface of the substrate W from below.

The heater unit 130 includes a plate body 131, a plurality of support pins 132, and a heater 133. The plate body 131 is slightly smaller than the substrate W in plan view. The plurality of support pins 132 protrude from the upper surface of the plate main body 131. The opposing surface 130a is formed by the upper surface of the plate body 131 and the surfaces of the plurality of support pins 132. The heater 133 may be a resistor incorporated in the plate main body 131. By energizing the heater 133, the opposing surface 130a is heated. And electric power is supplied to the heater 133 from the heater electricity supply mechanism 135 via the feeder line 134. FIG.

The heater unit 130 is disposed above the spin base 19. The processing unit 2Q includes a heater elevating mechanism 136 that elevates the heater unit 130 relative to the spin base 19. The heater lifting mechanism 136 includes, for example, a ball screw mechanism and an electric motor for imparting driving force thereto.

A lifting shaft 137 extending in the vertical direction along the rotation axis A1 is coupled to the bottom surface of the heater unit 130. The lifting shaft 137 passes through the through hole formed in the center of the spin base 19 and the hollow spin shaft 18. The feeder line 134 passes through the lifting shaft 137. The heater elevating mechanism 136 elevates the heater unit 130 via the elevating shaft 137, thereby placing the heater unit 130 at any intermediate position between the lower and upper teeth.

Since the heater unit 130 is elevated (moved) relative to the spin base 19, the distance between the lower surface of the substrate W and the upper surface of the heater unit 130 changes. That is, the heater elevating mechanism 136 functions as a distance change unit.

The back surface supply nozzle 36 passes through the hollow lifting shaft 137 and penetrates the heater unit 130. The discharge port 36a of the back surface supply nozzle 36 faces the center of the back surface of the substrate W. As shown in FIG. The process fluid supply pipe 90 and the third inert gas supply pipe 145 are connected to the back surface supply nozzle 36. The third inert gas supply pipe 145 is provided with a valve 146 that opens and closes the flow path. The valve 146 is opened and closed by the controller 3 (see FIG. 10). When the valve 146 is opened, an inert gas is supplied from the discharge port 36a of the back surface supply nozzle 36 to the center area | region of the back surface of the board | substrate W. As shown in FIG. The supplied inert gas diffuses outward from the central region of the rear surface of the substrate W to the outside in the atmosphere between the rear surface of the substrate W and the opposing surface 130a of the heater unit 130. From the leading edge of the back, it is discharged out of atmosphere.

The heater unit 130 may be comprised so that the board | substrate W may be lifted from the clamping member 19b, and the board | substrate W may be supported by the opposing surface 130a in the process of raising to an upper value. To this end, the plurality of holding members 19b are in a closed state in contact with the main end of the substrate W and holding the substrate W, and in an open state retracted from the main end of the substrate W. FIG. It can be opened and closed, and in the open state, it is necessary to be configured to release the gripping apart from the main end of the substrate W, and to contact the lower surface of the periphery of the substrate W to support the substrate W from below. There is.

As a structure which opens and closes the some clamping member 19b, the processing unit 2Q further includes the clamping member drive mechanism 140 which opens and closes the some clamping member 19b. The holding member drive mechanism 140 includes, for example, a link mechanism 141 embedded in the spin base 19 and a drive source 142 disposed outside the spin base 19. The drive source 142 includes a ball screw mechanism and an electric motor for imparting a driving force thereto, for example.

With reference to the portion shown by the dashed-dotted line in FIG. 10, the controller 3 according to the third embodiment includes a heater energization mechanism 135 and a heater in addition to the object controlled by the controller 3 according to the second embodiment. The lifting mechanism 136 and the holding member drive mechanism 140 are controlled.

In the processing unit 2Q according to the third embodiment, the same substrate processing as that in the flowchart shown in FIG. 4 is possible. Specifically, the substrate processing by the processing unit 2Q is performed except that the temperature adjustment (heating) of the substrate W in the temperature holding step (step S5) is performed using the heater unit 130. Is almost the same as the substrate processing by the processing unit 2P according to the second embodiment.

15A to 15D are schematic cross-sectional views for explaining a state of substrate processing performed by the processing unit 2Q.

In the temperature holding step of the substrate processing by the processing unit 2Q, instead of supplying the first and second fruits to the back surface of the substrate W, the relative position of the heater unit 130 with respect to the substrate W is determined. By changing, the temperature of the board | substrate W is adjusted (heater temperature adjustment process).

Specifically, as shown in FIG. 15A, in the core forming step, the controller 3 controls the heater elevating mechanism 136 to bring the heater unit 130 into close contact with the back surface of the substrate W in a non-contact manner. Located in the first heating position. Thereby, the whole board | substrate W is heated uniformly. In the core forming step, when it is not necessary to rotate the substrate W, the first heating position may be a position at which the heater unit 130 lifts the substrate W. As shown in FIG. In this case, the holding member 19b needs to be in an open state.

Although not shown, in the pretreatment liquid supplying step, the temperature holding step may be started earlier than the start of the processing liquid supplying step (processing liquid film forming step) by placing the heater unit 130 at the first heating position.

And as shown in FIG. 15B, in the enlarged thin film formation process, the controller 3 controls the heater lifting mechanism 136, and spaces the heater unit 130 from the back surface of the board | substrate W rather than a 1st heating position. To the second heating position.

And as shown in FIG. 15C, in the solidification process after completion | finish of a temperature holding process, the controller 3 controls the heater lifting mechanism 136, and moves the heater unit 130 to a lower value. Then, the controller 3 opens the valves 120 and 124. Thereby, supply of the coolant 58 from the back surface supply nozzle 36 to the back surface of the board | substrate W similarly to the board | substrate process in 2nd Embodiment is started. And the process liquid film 57 formed in the pattern formation surface of the board | substrate W solidifies, and the solidified body 59 is formed.

In addition, when not heating the board | substrate W by the heater unit 130, as shown in FIG. 15D, the controller 3 controls the heater lifting mechanism 136, and the heater unit 130 is lowered. Place it in place. Then, the controller 3 opens the valve 146. Thereby, an inert gas is supplied from the back surface supply nozzle 36 between the back surface of the board | substrate W and the opposing surface 130a of the heater unit 130. FIG. Since the atmosphere between the back surface of the board | substrate W and the opposing surface 130a of the heater unit 130 and the board | substrate W are cooled by this, heating of the board | substrate W by the heater unit 130 is carried out. Can be stopped.

In the substrate processing of the third embodiment, the controller 3 preferably controls the heater energization mechanism 135 so that the temperature of the heater unit 130 is kept constant.

In detail, the time required for the temperature change of the heater unit 130 is long compared with the time required for the temperature change of the board | substrate W. FIG. Therefore, when heating the board | substrate W by changing the temperature of the heater unit 130 in a heating process, unless it waits for the heater unit 130 to change to a desired temperature, the board | substrate W will be at the desired temperature. It is not early. Therefore, there is a fear that the time required for substrate processing becomes long.

The amount of heat transferred from the heater unit 130 to the substrate W varies depending on the distance between the bottom surface of the substrate W and the heater unit 130. Therefore, the temperature of the substrate can be changed to a desired temperature by changing the distance between the lower surface of the substrate W and the heater unit 130 while the temperature of the heater unit 130 is kept constant. Thereby, time required for the temperature change of the heater unit 130 can be reduced. Furthermore, the time required for substrate processing can be reduced.

<4th embodiment>

FIG. 16: is a schematic cross section which shows schematic structure of the processing unit 2R with which the substrate processing apparatus 1R which concerns on 4th Embodiment is equipped. In FIG. 16, the same code | symbol is attached | subjected to the same member as the member demonstrated so far, and the description is abbreviate | omitted (the same also in FIGS.

The processing unit 2R according to the fourth embodiment mainly differs from the processing unit 2Q according to the third embodiment in that the processing unit 2R supplies the holding layer forming liquid instead of the chemical liquid supply nozzle 20. It is the point that the nozzle 160 and the peeling liquid supply nozzle 161 are included. The holding layer forming liquid supply nozzle 160 is contained in the holding layer forming liquid supply unit which supplies a holding layer forming liquid to the pattern formation surface of the board | substrate W. As shown in FIG. The peeling liquid supply nozzle 161 is contained in the peeling liquid supply unit which supplies a peeling liquid to the pattern formation surface of the board | substrate W. As shown in FIG.

The holding layer forming liquid supply nozzle 160 and the peeling liquid supply nozzle 161 are the rinse liquid supply nozzle 24, the pretreatment liquid supply nozzle 28, the treatment liquid supply nozzle 32, and the first inert gas nozzle 45. ) Is housed in the nozzle housing member 80.

The holding layer forming liquid supply nozzle 160 supplies (discharges) the holding layer forming liquid toward the center region of the upper surface of the substrate W. As shown in FIG. The holding layer forming liquid supply pipe 162 is connected to the holding layer forming liquid supply nozzle 160. The holding layer forming liquid supply pipe 162 is provided with a valve 163 that opens and closes the flow path. The valve 163 is opened and closed by the controller 3 (see FIG. 10).

The holding layer forming liquid contains a solute and a solvent having volatility. At least a part of the solvent volatilizes and solidifies or hardens | cures the holding layer forming liquid, and forms the particle holding layer which isolate | separates and holds the particle adhering to the pattern formation surface of the board | substrate W from the said board | substrate W.

Here, "solidification" means that a solute becomes hard by the force acting between an intermolecular molecule and an atom, for example with volatilization of a solvent. "Hardening" means that a solute becomes hard by chemical changes, such as superposition | polymerization and crosslinking, for example. Therefore, "solidification or hardening" has shown that the solute "hardens" by various factors.

The resin used as the solute of the holding layer-forming liquid is, for example, a resin that is poorly soluble to insoluble in water before heating to a predetermined alteration temperature or higher, and has a property of being altered and water-soluble by heating above the alteration temperature (hereinafter, It may describe as "heat-sensitive water-soluble resin."

The heat-sensitive water-soluble resin is decomposed by heating to a predetermined alteration temperature or more (for example, 200 ° C. or more), and expresses water solubility by exposing a polar functional group.

As a solvent of the oil-retaining layer forming liquid, the solvent which has solubility with respect to the thermosensitive water-soluble resin before alteration, and has volatility can be used. Here, "having volatility" means that the volatility is higher than water. As a solvent of the holding layer forming liquid, PGEE (propylene glycol monoethyl ether) is used, for example.

The peeling liquid supply nozzle 161 supplies (discharges) a peeling liquid toward the center area | region of the upper surface of the board | substrate W. As shown in FIG. A peeling liquid is a liquid for peeling the particle holding layer which the holding layer forming liquid forms from the pattern formation surface of the board | substrate W. FIG. It is preferable to use the liquid which has compatibility with the solvent contained in a maintenance layer forming liquid as a peeling liquid.

A peeling liquid is an aqueous peeling liquid, for example. As the aqueous stripping solution, the stripping solution is not limited to DIW, and may include carbonated water, electrolytic ion water, hydrogen water, ozone water, hydrochloric acid water at a dilute concentration (for example, about 10 ppm to 100 ppm), aqueous alkali solution, and the like. . As aqueous alkali solution, aqueous solution of quaternary ammonium hydroxides, such as SC1 liquid (ammonia hydrogen peroxide mixed liquid), ammonia aqueous solution, tetramethylammonium hydroxide, aqueous solution of choline, etc. are mentioned.

The peeling liquid supply pipe 164 is connected to the peeling liquid supply nozzle 161. The peeling liquid supply pipe 164 is provided with the valve 165 which opens and closes the flow path. The valve 165 is opened and closed by the controller 3 (see FIG. 10).

17 is a flowchart for explaining an example of substrate processing by the processing unit 2R according to the fourth embodiment. 18A to 18E are schematic cross-sectional views for explaining the state of substrate processing by the processing unit 2R. The substrate process shown in FIG. 17 differs from the substrate process shown in FIG. 4 in that the holding layer forming liquid supplying step (step S11), the holding layer forming step (step S12), and the holding instead of the chemical liquid processing step (step S1). The layer removal process (step S13) is performed in this order.

In the substrate processing by the processing unit 2R, as shown in FIG. 18A, the holding layer forming liquid supplying step is performed (step S11). In the holding layer forming liquid supplying step, first, the substrate W is held horizontally in the spin chuck 5 (substrate holding step). The controller 3 drives the spin motor 17 to rotate the spin base 19 to start the rotation of the substrate W (substrate rotation step).

In the holding layer forming liquid supplying step, the spin base 19 is rotated at a predetermined holding layer forming liquid supplying speed, which is a substrate rotational speed. The holding layer forming liquid supply speed is 10 rpm, for example.

In the holding layer forming liquid supplying process, the controller 3 controls the blocking plate elevating mechanism 46 to arrange the blocking plate 44 at a processing position, for example. In the holding layer forming liquid supplying process, the controller 3 controls the heater elevating mechanism 136 to arrange the heater unit 130 at a lower value.

The substrate holding step and the substrate rotating step are continued until the substrate processing is completed. However, when the heater unit 130 lifts the board | substrate W, rotation of the board | substrate W is stopped.

After the blocking plate 44 is disposed at the processing position, the controller 3 opens the valve 163. Thereby, the holding layer forming liquid 170 is supplied from the holding layer forming liquid supply nozzle 160 toward the pattern forming surface which is the upper surface of the board | substrate W of a rotating state. The supplied holding layer forming liquid 170 spreads evenly over substantially the entire surface of the pattern formation surface of the substrate W by the action of centrifugal force.

18B and 18C, after the holding layer forming liquid is supplied to the substrate W for a predetermined time, the holding layer forming liquid is solidified or cured, and the particle holding layer 200 is formed on the pattern forming surface of the substrate W. As shown in FIG. ) (See FIG. 18C) is performed (step S12). In the holding layer forming step, the valve 163 is first closed. As a result, the supply of the holding layer forming liquid 170 from the holding layer forming liquid supply nozzle 160 is stopped.

Referring to FIG. 18B, in the holding layer forming step, first, in order to set the thickness of the liquid film of the holding layer forming liquid on the substrate W to an appropriate thickness, the holding layer forming liquid is removed from the pattern forming surface of the substrate W by centrifugal force. A spinoff process is performed that excludes part of. In the spin off step, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined spin off speed, which is the substrate rotation speed. Spin-off speed is 300 rpm-1500 rpm, for example. In the spin off step, the blocking plate 44 is held at the processing position, and the heater unit 130 is held at the lower level.

Referring to FIG. 18C, in the holding layer forming step, the substrate W is heated (heating to the substrate W) in order to volatilize a part of the solvent of the holding layer forming liquid on the substrate W after the spin off step. Substrate heating process is performed.

In the substrate heating step, the heater elevating mechanism 136 arranges the heater unit 130 at the third heating position. The third heating position is, for example, the same position as the first heating position described in the third embodiment. As a result, the holding layer forming liquid on the substrate W is heated. In the substrate heating step, the controller 3 controls the blocking plate elevating mechanism 46 to arrange the blocking plate 44 in a proximal position. In the substrate heating step, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined substrate heating rate, which is the substrate rotation speed. The speed | rate at the time of board | substrate heating is 1000 rpm, for example.

In the substrate heating step, the substrate W is preferably heated so that the temperature of the holding layer forming liquid on the substrate W is less than the boiling point of the solvent. By heating the holding layer forming liquid to a temperature below the boiling point of the solvent, as described above, the solvent can be left in the particle holding layer 200. The particle holding layer 200 can be easily peeled from the pattern formation surface of the substrate W by the interaction between the solvent remaining in the particle holding layer 200 and the peeling liquid.

In the substrate heating step, in addition to the temperature of the holding layer forming liquid on the substrate W being lower than the boiling point of the solvent, the substrate (so that the temperature of the holding layer forming liquid on the substrate W is lower than the alteration temperature of the thermosensitive water-soluble resin). It is preferable that W) be heated. By heating the holding layer forming liquid to a temperature below the altering temperature, the thermally water-soluble resin is not changed to water solubility, and on the pattern formation surface of the substrate W, a poorly soluble to insoluble particle holding layer ( 200).

By carrying out the substrate heating step, the holding layer forming liquid is solidified or cured to form the particle holding layer 200 on the substrate W. As shown in FIG. As shown in FIG. 19A, when the particle holding layer 200 is formed, the particle 201 adhered to the pattern forming surface of the substrate W is separated from the substrate W to form the particle holding layer 200. Is maintained.

The holding layer forming liquid may be solidified or cured to such an extent that the particle 201 can be held. The solvent of the holding layer forming liquid does not need to be completely volatilized. In addition, the "solute component" which forms the particle holding layer 200 may be the solute contained in the holding layer forming liquid itself, or may be derived from the solute, for example, obtained as a result of chemical change. .

As shown in FIG. 18D and FIG. 18E, after the holding layer forming step, the peeling liquid is supplied to the pattern forming surface of the substrate W to peel off and remove the particle holding layer 200 from the pattern forming surface of the substrate W. FIG. The holding layer removing step is performed (step S13).

In the holding layer removing step, a first peeling liquid supplying step in which a rinse liquid such as DIW, which also functions as a peeling liquid, is supplied to the pattern forming surface of the substrate W, and a second in which a peeling liquid such as SC1 is supplied to the pattern forming surface. A peeling liquid supply process is performed.

Referring to FIG. 18D, in the first peeling liquid supplying step, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined first peeling liquid speed which is a substrate rotational speed. The 1st peeling liquid speed is 800 rpm, for example. In the 1st peeling liquid supply process, the controller 3 controls the blocking plate elevating mechanism 46, and moves the blocking plate 44 to a processing position. In the 1st peeling liquid supply process, the controller 3 controls the heater lifting mechanism 136, and moves the heater unit 130 to a lower value. Then, the controller 3 opens the valve 27. Thereby, the rinse liquid is supplied from the rinse liquid supply nozzle 24 toward the pattern formation surface of the board | substrate W of a rotating state. The rinse liquid 171 supplied to the pattern formation surface of the board | substrate W spreads evenly over the whole pattern formation surface of the board | substrate W by centrifugal force. The rinse liquid 171 supplied to the pattern formation surface of the board | substrate W is removed to radial direction outward from the board | substrate W by centrifugal force.

Referring to FIG. 18E, in the second peeling liquid supplying step, the spin motor 17 changes the rotational speed of the spin base 19 to a predetermined second peeling liquid speed. The 2nd peeling liquid speed is 800 rpm, for example. Therefore, in the 2nd peeling liquid supply process, the rotational speed of the board | substrate W in a 1st peeling liquid supply process is maintained. Then, the controller 3 closes the valve 23 and opens the valve 166. Thereby, peeling liquids, such as SC1 liquid, are supplied from the peeling liquid supply nozzle 161 to the pattern formation surface of the board | substrate W. As shown in FIG. The peeling liquid 172 supplied to the pattern formation surface spreads evenly over the whole pattern formation surface of the board | substrate W by centrifugal force, and replaces the rinse liquid 171 on the board | substrate W. As shown in FIG. The peeling liquid supplied to the pattern formation surface is excluded from radial direction outward from the board | substrate W by centrifugal force. In the 2nd peeling liquid supply process, the heater unit 130 is hold | maintained in the lower value.

Aqueous peeling liquids, such as DIW and SC1 liquid used as peeling liquid, have compatibility with PGEE as a solvent. In addition, the particle holding layer 200 formed by heating the thermosensitive water-soluble resin below its alteration temperature is poorly soluble to insoluble in DIW or SC1 liquid, which is an aqueous stripping solution. Therefore, these peeling liquids penetrate into the particle holding layer 200 without dissolving the solute component forming the particle holding layer 200 by interaction with PGEE remaining in the particle holding layer 200. do. And the peeling liquid reaches | attains the interface with the board | substrate W. As shown in FIG. Thereby, as shown to FIG. 19B, the particle holding layer 200 of the state which hold | maintained the particle 201 floats and peels from the pattern formation surface of the board | substrate W. As shown in FIG.

The particle holding layer 200 peeled from the pattern formation surface of the board | substrate W has the pattern formation surface of the board | substrate W with a rinse liquid and a peeling liquid by the effect of the centrifugal force by the rotation of the board | substrate W. Ejected from the cast. That is, the peeled particle holding layer 200 is removed from the pattern formation surface of the board | substrate W. As shown in FIG.

The effect of the rinse liquid as the peeling liquid is lower than that of the SC1 liquid. However, the rinse liquid is supplied in advance of the SC1 liquid to penetrate into the particle holding layer 200, thereby replacing at least a part of the PGEE remaining in the particle holding layer 200. The DIW serves to assist the penetration of the SC1 liquid into the particle holding layer 200 supplied in the next step. Therefore, although it is preferable to supply a rinse liquid before supply of a peeling liquid, supply of a rinse liquid (1st peeling liquid supply process) may be abbreviate | omitted.

After the holding layer removing step (step S13), the rinse liquid treatment step (step S2) to the sublimation promotion step (step S10) are performed similarly to the substrate treatment shown in FIG.

In the pretreatment liquid supplying process after a holding layer removal process, IPA is supplied to the pattern formation surface of the board | substrate W as a pretreatment liquid, for example. IPA has the property of dissolving the solute component which forms the particle holding layer 200. Therefore, IPA dissolves the residue of the particle holding layer 200 (the particle holding layer 200 which has not been peeled off by the peeling liquid), and before supplying the processing liquid to the pattern formation surface of the substrate W, the substrate ( It functions as a residue removal liquid (pretreatment liquid) which removes a residue from the pattern formation surface of W). Thereby, the pattern formation surface of the board | substrate W can be dried in the state which reduced the quantity of the particle 201 of the pattern formation surface of the board | substrate W further.

According to the fourth embodiment, the holding layer forming liquid on the substrate W is heated by the heater unit 130 in the holding layer forming step. Thereby, the holding layer forming liquid 170 solidifies or hardens, and the particle holding layer 200 is formed in the pattern formation surface of the board | substrate W. As shown in FIG. When the holding layer forming liquid is solidified or cured, the particles 201 are separated from the substrate W. As shown in FIG. The separated particles 201 are retained in the particle holding layer 200. Therefore, in the holding layer removal step, the release liquid is supplied to the pattern forming surface of the substrate W to form the particle holding layer 200 in the state where the particles 201 are held. It can peel off and can remove from.

By the above, the particle 201 can be removed favorably from the pattern formation surface of the board | substrate W, and the surface of the board | substrate W can be dried favorably.

In the holding layer forming step, the substrate W is heated so that the temperature of the holding layer forming liquid 170 supplied to the pattern forming surface of the substrate W is lower than the altering temperature.

According to this method, in the holding layer forming step, the substrate W is heated so that the temperature of the holding layer forming liquid is lower than the altering temperature, so that the particle holding layer 200 is formed. Therefore, although the particle holding layer 200 is poorly soluble to insoluble with respect to a peeling liquid, peeling is possible with the said peeling liquid. Therefore, in the holding layer removing step, the particle holding layer 200 formed on the pattern forming surface of the substrate W is removed from the pattern forming surface of the substrate W while the particle 201 is held therein without being dissolved therein. It can be removed by peeling.

As a result, the particle 201 can be removed at a high removal rate by peeling the particle holding layer 200 in the state where the particle 201 is held from the pattern formation surface of the substrate W. As shown in FIG. In addition, the residue resulting from the dissolution of the particle holding layer 200 in the stripping solution 172 can be suppressed from remaining or reattached on the pattern formation surface of the substrate W. FIG.

In 4th Embodiment, the thermosensitive water-soluble resin was used as the solute of a holding layer forming liquid. However, the resin used as the solute of the holding layer forming liquid may be a resin other than the thermosensitive water-soluble resin.

Resin other than the heat-soluble water-soluble resin used as a solute contained in a holding layer forming liquid is acrylic resin, a phenol resin, an epoxy resin, melamine resin, urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane, a poly Mid, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, polyamide, polyacetal, polycarbonate, polyvinyl alcohol, modified Polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polysulfone, polyether ether ketone, polyamideimide and the like. In the holding layer forming liquid, when any one of these resins is used, any solvent capable of dissolving the resin used as the solute can be used.

Since a resin other than the thermosensitive water-soluble resin does not have a deterioration temperature as the solute of the oil-retaining layer-forming liquid, in the substrate heating step of the oil-retaining layer-forming step, the formation of the oil-retaining layer is performed as in the case of using the heat-sensitive water-soluble resin as the solute of the oil-retaining layer forming liquid. The temperature of the liquid does not need to be lower than the alteration temperature of the thermosensitive water-soluble resin, and the substrate W may be heated so that the temperature of the holding layer forming liquid on the substrate W is less than the boiling point of the solvent.

When using resins other than the thermosensitive water-soluble resin as the solute of the holding layer forming liquid, any liquid having solubility in the resin can be used as the residue removing liquid. In the case of using a resin other than the thermosensitive water-soluble resin as the solute of the holding layer forming liquid, examples of the residue removing liquid include organic solvents such as thinner, toluene, acetate esters, alcohols, glycols, acetic acid, formic acid, hydroxyacetic acid, and the like. An acidic solution of can be used.

As the solute of the holding layer forming liquid, in addition to the various resins described above, for example, an organic compound other than the resin, or a mixture different from the organic compound may be used. Alternatively, compounds other than organic compounds may be used.

As a peeling liquid, you may use other peeling liquid other than aqueous system. In that case, it has compatibility with the solute which forms the poorly insoluble or insoluble particle holding layer 200 in the said peeling liquid, the peeling liquid, and it has compatibility with the solvent which has solubility with respect to a solute, and a peeling liquid, What is necessary is just to combine the residue removal liquid etc. which have solubility with respect to a solute.

<5th embodiment>

FIG. 20: is a schematic cross section which shows schematic structure of the processing unit 2S with which the substrate processing apparatus 1S which concerns on 5th Embodiment is equipped. In FIG. 20, the same code | symbol is attached | subjected to the same member as the member demonstrated so far, and the description is abbreviate | omitted (the same also in FIGS. 21-24 mentioned later).

The processing unit 2S according to the fifth embodiment is different from the processing unit 2Q according to the third embodiment in the following points. The main difference between the processing unit 2S and the processing unit 2Q is that the processing unit 2S includes the cooler unit 180 instead of the heater unit 130.

The cooler unit 180 has the form of a disk shaped cooler plate. The cooler unit 180 has an opposing surface 180a which faces the lower surface of the substrate W from below.

The cooler unit 180 includes a plate body 181 and a built-in refrigerant pipe 182 built in the plate body 181. The plate body 181 is slightly smaller than the substrate W in plan view. The opposing surface 180a is configured by the upper surface of the plate main body 181.

The built-in coolant tube 182 is connected to a coolant supply pipe 183 for supplying a coolant to the built-in coolant tube 182 and a coolant discharge pipe 184 for discharging the coolant from the built-in coolant tube 182. A hollow lifting shaft 185 extending along the rotation axis A1 in the vertical direction is coupled to the bottom surface of the cooler unit 180. The lifting shaft 185 passes through the through hole formed in the center portion of the spin base 19 and the hollow spin shaft 18.

The refrigerant supply pipe 183 and the refrigerant discharge pipe 184 pass through the lifting shaft 185. The valve 186 is interposed in the coolant supply pipe 183. By opening the valve 186, the coolant is supplied to the built-in coolant pipe 182. The cooler unit 180 is cooled by supplying a coolant to the built-in coolant pipe 182.

The cooler unit 180 is disposed above the spin base 19. The processing unit 2S includes a cooler elevating mechanism 187 that raises and lowers the cooler unit 180 relative to the spin base 19. The cooler elevating mechanism 187 includes, for example, a ball screw mechanism and an electric motor for imparting a driving force thereto.

The cooler elevating mechanism 187 can arrange the cooler unit 180 at any intermediate position between the lower and upper teeth by raising and lowering the cooler unit 180 via the lifting shaft 185.

The cooler unit 180 may be comprised so that the board | substrate W may be lifted from the holding member 19b and the board | substrate W may be supported by the opposing surface 180a in the process of raising to an upper level. When located at a lower value, the cooler unit 180 is most spaced apart from the substrate W in the movable range of the cooler unit 180.

The back surface supply nozzle 36 passes through the hollow lifting shaft 185 and penetrates the cooler unit 180. The discharge port 36a of the back surface supply nozzle 36 faces the center of the back surface of the substrate W. As shown in FIG. In 5th Embodiment, the fruit supplied from the back surface supply nozzle 36 to the back surface of the board | substrate W is gas, such as nitrogen gas and air.

Fig. 21 is a block diagram showing the electrical configuration of the main part of the substrate processing apparatus 1S. The controller 3 of the substrate processing apparatus 1S includes the FFU 15, the exhaust device 16, the spin motor 17, the blocking plate lifting mechanism 46, the guard lifting mechanism 74, the heater 99, It is programmed to control the valves 23, 27, 31, 35, 48, 83, 146, 186, the clamping member drive mechanism 140, and the cooler elevating mechanism 187.

In the processing unit 2S according to the fifth embodiment, the same substrate processing as that in the flowchart shown in FIG. 4 is possible. Specifically, the substrate treatment by the processing unit 2S is carried out in the third embodiment except that the cooling of the substrate W in the solidification step (step S7) is performed using the cooler unit 180. It is almost the same as the substrate processing by the processing unit 2Q according to the form.

22A to 22C are schematic cross-sectional views for explaining a state of substrate processing performed by the processing unit 2S.

In the temperature maintenance process (step S5) of the substrate processing by the processing unit 2S, a gas such as nitrogen gas having a high temperature (for example, the first temperature) is used as the first fruit (see FIG. 22A), and the first fruit Lower temperature (e.g., second temperature) nitrogen gas is used as the second fruit (see Figure 22B). In the temperature holding step, the controller 3 controls the cooler elevating mechanism 187 to arrange the cooler unit 180 at a lower value.

In the solidification process (step S7), the controller 3 opens the valve 186 and starts supply of the coolant to the built-in coolant pipe 182. And the controller 3 controls the cooler elevating mechanism 187, and arrange | positions the cooler unit 180 in a cooling position. A cooling position is a position between a lower value and an upper value.

When the cooler unit 180 is located at the cooling position, the cooler unit 180 is in close contact with the back surface of the substrate W in a non-contact manner. As a result, heat is transferred (taken away) from the substrate W to the cooler unit 180, and the substrate W is cooled (substrate cooling step). Therefore, the processing liquid film 57 is cooled through the substrate W to a temperature below the freezing point of the sublimable material. Therefore, the heat of the part which opposes the opposing surface of the cooler unit 180 in the back surface of a board | substrate is equally deprived by the cooler unit 180, and the process liquid film 57 is cooled uniformly. Unlike the fifth embodiment, the cooler unit 180 may be in contact with the substrate W when positioned at the cooling position.

Unlike the fifth embodiment, the cooling of the substrate W may be controlled only by the presence or absence of supply of the coolant (switching of the valve 186) without raising and lowering the cooler unit 180 in the substrate processing. In addition, unlike the fifth embodiment, the valve 186 is always open during the substrate processing, and may control the cooling of the substrate W only by lifting and lowering the cooler unit 180.

Although not shown, when the substrate W is not cooled by the cooler unit 180, the controller 3 opens the valve 146 and the back surface of the substrate W and the cooler unit (from the back supply nozzle 36). You may supply an inert gas of the temperature above 1st normal temperature between the opposing surface 180a of 180). As a result, the atmosphere between the back surface of the substrate W and the opposing surface 180a of the cooler unit 180 and the substrate W are heated, so that the temperature of the substrate W is returned to the first normal temperature. The cooling of the substrate W is stopped.

In the fifth embodiment, the cooler unit 180 includes the plate body 181 and the built-in refrigerant pipe 182. However, the cooler unit 180 may have a structure different from 5th Embodiment. For example, as shown in FIG. 23, the cooler unit 180 may include a plate body 181 and a Peltier element 188 incorporated in the plate body 181. By energizing the Peltier element 188, the opposing surface 180a is cooled. The Peltier element 188 is supplied with electric power from the cooler energizing mechanism 190 via the feed line 189. The cooler energizing mechanism 190 is controlled by the controller 3 (see the dashed-dotted line in FIG. 21). The Peltier element 188 does not need to be built in the plate main body 181, and may be attached to the surface (for example, lower surface) of the plate main body 181, as shown in FIG.

Also in the configuration in which the Peltier element 188 is provided, the same substrate processing as in the fifth embodiment can be performed. However, cooling of the board | substrate W is performed by at least one of the raising and lowering of the cooler unit 180, and switching of electricity supply of the Peltier element 188. FIG.

In addition, when using the melt of a sublimable substance as a process liquid, if the solidification point of a sublimable substance is below the temperature of the atmosphere in the chamber 4 (refer FIG. 1), it is not necessary to use a fruit in order to maintain a dissolved state, The use of fruit can be omitted. In this case, in 5th Embodiment, a temperature process can be abbreviate | omitted and substrate processing can be performed.

<Treatment liquid>

As the treatment liquid used in the above embodiments (first embodiment to fifth embodiment) and the modified examples, as described above, the sublimable substance such as the melt of the sublimable substance is contained in the molten state, Alternatively, a solution obtained by dissolving a sublimable substance as a solute in a solvent can be used.

As the sublimable substance, various substances which have a high vapor pressure at the first normal temperature (5 ° C. to 35 ° C.) and change in the gas phase without passing through the liquid phase in the solid phase are used as described above. As a sublimable substance, for example, hexamethylenetetramine, 1,3,5-trioxane, 1-pyrrolidine carbodithiommonium, metaaldehyde, paraffin of about 20 to 48 carbon atoms, t-butanol, paradichloro Benzene, naphthalene, L-menthol, hydrocarbon fluoride compounds and the like are used. In particular, a fluorohydrocarbon compound can be used as a sublimable substance.

Compound (A): Fluoroalkane having 3 to 6 carbon atoms, or a derivative thereof

Compound (B): fluorocycloalkane having 3 to 6 carbon atoms, or a derivative thereof

Compound (C): Fluorobicycloalkane having 10 carbon atoms or a derivative thereof

Compound (D): Fluoro tetracyanoquinomethane, or a derivative thereof

Compound (E): Fluorocyclophosphazene or derivatives thereof having three or more phosphazene units

<Compound (A)>

As a compound (A), Formula (1):

C _m H _n F _{2m + 2-n} (1)

[In formula, m represents the number of 3-6, n represents the number of 0 <= n <= 2m + 1. ]

C3-C6 fluoroalkane or its derivative (s) represented by these are mentioned.

Specifically, as the fluoroalkane having 3 carbon atoms, for example, CF ₃ CF ₂ CF ₃ , CHF ₂ CF ₂ CF ₃ , CH ₂ FCF ₂ CF ₃ , CH ₃ CF ₂ CH ₃ , CHF ₂ CF ₂ CH ₃ , CH ₂ FCF ₂ CH ₃ , CH ₂ FCF ₂ CH ₂ F, CHF ₂ CF ₂ CHF ₂ , CF ₃ CHFCF ₃ , CH ₂ FCHFCF ₃ , CHF ₂ CHFCF ₃ , CH ₂ FCHFCH ₂ F, CHF ₂ CHFCHF ₂ , CH _{3 CHFCH 3, CH 2 FCHFCH 3} , CHF 2 CHFCH 3, CF 3 CH 2 CF 3, CH 2 FCH 2 CF 3, CHF 2 CH 2 CF 3, CH 2 FCH 2 CH 2 F, CH 2 FCH 2 CHF 2, CHF ₂ CH ₂ CHF ₂ , CH ₃ CH ₂ CH ₂ F, CH ₃ CH ₂ CHF ₂ and the like.

Examples of the fluoroalkane having 4 carbon atoms include CF ₃ (CF ₂ ) ₂ CF ₃ , CF ₃ (CF ₂ ) ₂ CH ₂ F, CF ₃ CF ₂ CH ₂ CF ₃ , CHF ₂ (CF ₂ ) ₂ CHF ₂ , CHF ₂ CHFCF ₂ CHF ₂ , CF ₃ CH ₂ CF ₂ CHF ₂ , CF ₃ CHFCH ₂ CF ₃ , CHF ₂ CHFCHFCHF ₂ , CF ₃ CH ₂ CF ₂ CH ₃ , CF ₃ CF ₂ CH ₂ CH ₃ , CF ₃ CHFCF ₂ CH ₃ , CHF ₂ CH ₂ CF ₂ CH ₃ and the like.

Examples of the fluoroalkane having 5 carbon atoms include CF ₃ (CF ₂ ) ₃ CF ₃ , CF ₃ CF ₂ CF ₂ CHFCF ₃ , CHF ₂ (CF ₂ ) ₃ CF ₃ , CHF ₂ (CF ₂ ) ₃ CHF ₂ , CF ₃ CH (CF ₃ ) CH ₂ CF ₃ , CF ₃ CHFCF ₂ CH ₂ CF ₃ , CF ₃ CF (CF ₃ ) CH ₂ CHF ₂ , CHF ₂ CHFCF ₂ CHFCHF ₂ , CF ₃ CH ₂ CF ₂ CH ₂ CF ₃ , CHF ₂ (CF ₂ ) ₂ CHFCH ₃ , CHF ₂ CH ₂ CF ₂ CH ₂ CHF ₂ , CF ₃ (CH ₂ ) ₃ CF ₃ , CF ₃ CHFCHFCF ₂ CF ₃ and the like.

Examples of the fluoroalkane having 6 carbon atoms include CF ₃ (CF ₂ ) ₄ CF ₃ , CF ₃ (CF ₂ ) ₄ CHF ₂ , CF ₃ (CF ₂ ) ₄ CH ₂ F, CF ₃ CH (CF ₃ ) CHFCF ₂ CF ₃ , CHF ₂ (CF ₂ ) ₄ CHF ₂ , CF ₃ CF ₂ CH ₂ CH (CF ₃ ) CF ₃ , CF ₃ CF ₂ (CH ₂ ) ₂ CF ₂ CF ₃ , CF ₃ CH ₂ (CF ₂ ) ₂ CH ₂ CF ₃ , CF ₃ (CF ₂ ) ₃ CH ₂ CF ₃ , CF ₃ CH (CF ₃ ) (CH ₂ ) ₂ CF ₃ , CHF ₂ CF ₂ (CH ₂ ) ₂ CF ₂ CHF ₂ , CF ₃ (CF ₂ ) ₂ (CH ₂ ) ₂ CH ₃ and the like.

Moreover, as a derivative of a C3-C6 fluoroalkane, halogen (specifically, chlorine, bromine, iodine) other than fluorine, a hydroxyl group, an oxygen atom, an alkyl group, a carboxyl group, and a perfluoro to any one of said fluoroalkanes The compound etc. which the at least 1 sort (s) of substituent selected from the group which consists of a roalkyl group are substituted are mentioned.

As an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group etc. are mentioned, for example.

As a perfluoroalkyl group, a saturated perfluoroalkyl group and unsaturated perfluoroalkyl group are mentioned, for example. Moreover, any of a linear structure or a branched structure may be sufficient as a perfluoroalkyl group. As a perfluoroalkyl group, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, a perfluoro-n-butyl group, a perfluoro-sec -Butyl group, perfluoro-tert-butyl group, perfluoro-n-amyl group, perfluoro-sec-amyl group, perfluoro-tert-amyl group, perfluoroisoamyl group, perfluoro- n-hexyl group, perfluoroisohexyl group, perfluoro neohexyl group, perfluoro-n-heptyl group, perfluoroisoheptyl group, perfluoro neoheptyl group, perfluoro-n-octyl group , Perfluoroisooctyl group, perfluoro neooctyl group, perfluoro-n-nonyl group, perfluoroneonyl group, perfluoroisononyl group, perfluoro-n-decyl group, perfluoroisodecyl group , Perfluoro neodecyl group, perfluoro-sec-decyl group, perfluoro-tert-decyl group, and the like.

<Compound (B)>

As a compound (B), Formula (2):

C _m H _n F _2m-n (2)

[In formula, m shows the number of 3-6, n shows the number of 0 <= n <= 2m-1. ]

C3-C6 fluorocycloalkane or its derivative (s) represented by these are mentioned.

Specifically, as a C3-C6 fluorocycloalkane, for example, monofluorocyclohexane, dodecafluorocyclohexane, 1,1,4-trifluorocyclohexane, 1,1,2, 2-tetrafluorocyclobutane, 1,1,2,2,3-pentafluorocyclobutane, 1,2,2,3,3,4-hexafluorocyclobutane, 1,1,2,2, 3,3-hexafluorocyclobutane, 1,1,2,2,3,4-hexafluorocyclobutane, 1,1,2,2,3,3-hexafluorocyclopentane, 1,1, 2,2,3,4-hexafluorocyclopentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,2,2,3,4,5-heptafluoro Locyclopentane, 1,1,2,2,3,3,4,4-octafluorocyclopentane, 1,1,2,2,3,3,4,5-octafluorocyclopentane, 1, 1,2,2,3,4,5,6-octafluorocyclohexane, 1,1,2,2,3,3,4,4-octafluorocyclohexane, 1,1,2,2, 3,3,4,5-octafluorocyclohexane, 1,1,2,2,3,4,4,5,6-nonafluorocyclohexane, 1,1,2,2,3,3, 4,4,5-nonafluorocyclohexane, 1,1,2,2, 3,3,4,5,6-nonafluorocyclohexane, 1,1,2,2,3,3,4,5,5,6-decafluorocyclohexane, 1,1,2,2, 3,3,4,4,5,6-decafluorocyclohexane, 1,1,2,2,3,3,4,4,5,5-decafluorocyclohexane, 1,1,2, 2,3,3,4,4,5,6-decafluorocyclohexane, perfluorocyclopropane, perfluorocyclobutane, perfluorocyclopentane, perfluorocyclohexane, etc. are mentioned.

Moreover, as a derivative of a C3-C6 fluorocycloalkane, the compound etc. which the at least 1 sort (s) of substituent which were disclosed by the compound (A) are substituted by any one of said fluorocycloalkanes are mentioned.

As a specific example of a derivative of a fluorocycloalkane of 3 to 6 carbon atoms, for example, 1,2,2,3,3-tetrafluoro-1-trifluoromethylcyclobutane, 1,2,4,4- Tetrafluoro-1-trifluoromethylcyclobutane, 2,2,3,3-tetrafluoro-1-trifluoromethylcyclobutane, 1,2,2-trifluoro-1-trimethylcyclobutane, 1,4,4,5,5-pentafluoro-1,2,2,3,3-pentamethylcyclopentane, 1,2,5,5-tetrafluoro-1,2-dimethylcyclopentane, 3 , 3,4,4,5,5,6,6-octafluoro-1,2-dimethylcyclohexane, 1,1,2,2-tetrachloro-3,3,4,4-tetrafluorocyclo Butane, 2-fluorocyclohexanol, 4,4-difluorocyclohexanone, 4,4-difluorocyclohexanecarboxylic acid, 1,2,2,3,3,4,4,5,5 , 6,6-Undecafluoro-1- (nonafluorobutyl) cyclohexane, perfluoromethylcyclopropane, perfluorodimethylcyclopropane, perfluorotrimethylcyclopropane, perfluorome Cyclobutane, perfluorodimethylcyclobutane, perfluorotrimethylcyclobutane, perfluoromethylcyclopentane, perfluorodimethylcyclopentane, perfluorotrimethylcyclopentane, perfluoromethylcyclohexane, perfluorodimethylcyclo Hexane, perfluoro trimethyl cyclohexane, etc. are mentioned.

<Compound (C)>

Examples of the fluorobicycloalkane having 10 carbon atoms of the compound (C) include fluorobicyclo [4.4.0] decane, fluorobicyclo [3.3.2] decane, perfluorobicyclo [4.4.0] decane, Perfluoro bicyclo [3.3.2] decane, etc. are mentioned.

Moreover, as a compound (C), the derivative which the substituent couple | bonded with the said C10 fluoro bicyclo alkane is also mentioned. Examples of the substituent include halogens other than fluorine (specifically, chlorine, bromine and iodine), a cycloalkyl group which may have a halogen atom, or an alkyl group having a cycloalkyl group which may have a halogen atom.

In the cycloalkyl group which may have a halogen atom, fluorine, chlorine, bromine, and iodine are mentioned as a halogen atom. Moreover, as a cycloalkyl group which may have a halogen atom, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a perfluorocyclopropyl group, a perfluorocyclobutyl group, a perfluoro cyclo A pentyl group, a perfluorocyclohexyl group, a perfluorocycloheptyl group, etc. are mentioned.

In the alkyl group which has a cycloalkyl group which may have the said halogen atom, a halogen atom is mentioned fluorine, chlorine, bromine, and iodine. Moreover, in the alkyl group which has a cycloalkyl group which may have a halogen atom, as a cycloalkyl group which may have a halogen atom, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a perfluorocyclo A propyl group, a perfluorocyclobutyl group, a perfluorocyclopentyl group, a perfluorocyclohexyl group, a perfluorocycloheptyl group, etc. are mentioned. As a specific example of the alkyl group which has a cycloalkyl group which may have a halogen atom, a difluoro (undecafluorocyclohexyl) methyl group etc. are mentioned, for example.

As a specific example of the compound (C) which the substituent couple | bonded with the fluoro bicyclo alkane of C10, For example, 2- [difluoro (undecafluorocyclohexyl) methyl] -1,1,2,3,3, 4,4,4a, 5,5,6,6,7,7,8,8,8a-heptadecafluorodecahydronaphthalene etc. are mentioned.

<Compound (D)>

As a fluoro tetracyano quinomethane of a compound (D), tetrafluoro tetracyano quinomdimethane etc. are mentioned, for example.

In addition, examples of the compound (D) include derivatives in which at least one halogen (specifically chlorine, bromine or iodine) other than fluorine is bonded to fluorotetracyanoquinomethane.

<Compound (E)>

Examples of the fluorocyclophosphazene of the compound (E) include hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, decafluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene and the like.

In addition, examples of the compound (E) include derivatives in which a substituent is bonded to fluorocyclophosphazene. As a substituent, halogen (specifically, chlorine, bromine, iodine) other than fluorine, a phenoxy group, an alkoxy group (-OR group), etc. are mentioned. As R of an alkoxy group, aromatic groups, such as alkyl groups, such as a methyl group and an ethyl group, fluoroalkyl groups, such as a trifluoromethyl group, and a phenyl group, etc. are mentioned, for example.

Examples of the compound (E) in which a substituent is bonded to fluorocyclophosphazene include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, and hexaphenoxy. Cycyclo triphosphazene etc. are mentioned.

As a sublimable substance, 1,1,2,2,3,3,4-heptafluorocyclopentane is especially preferable. This compound has a vapor pressure of about 8266 Pa at 20 ° C, a melting point of 20.5 ° C and a boiling point of 82.5 ° C. Therefore, what is necessary is just to set the temperature of the fruit used for a temperature holding process, the temperature of the refrigerant used for a coagulation process, etc. according to these data.

<Solvent>

When mix | blending the sublimable substance of a molten state, as a solvent, the solvent which shows compatibility with the sublimable substance of a molten state is preferable. Moreover, when dissolving a sublimable substance as a solute, the solvent which shows solubility with respect to the said sublimable substance is preferable.

Examples of the solvent include at least one selected from the group consisting of DIW, pure water, aliphatic hydrocarbons, aromatic hydrocarbons, esters, alcohols, ethers, and the like.

Specifically, for example, DIW, pure water, methanol, ethanol, IPA, butanol, ethylene glycol, propylene glycol, NMP (N-methyl-2-pyrrolidone), DMF (N, N-dimethylformamide), DMA (dimethylacetamide), DMSO (dimethylsulfoxide), hexane, toluene, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), PGPE (propylene glycol monopropyl ether), PGEE (propylene glycol Monoethyl ether), GBL (γ-butyrolactone), acetylacetone, 3-pentanone, 2-heptanone, ethyl lactate, cyclohexanone, dibutyl ether, HFE (hydrofluoroether), ethyl nonafluoro And at least one selected from the group consisting of isobutyl ether, ethyl nonafluorobutyl ether, and m-xylene hexafluoride.

Content of the sublimable substance in a process liquid is not specifically limited, It can set suitably.

<6th embodiment>

FIG. 25: is a schematic cross section which shows schematic structure of the processing unit 2T of the substrate processing apparatus 1T which concerns on 6th Embodiment of this invention.

In 6th Embodiment, it is a part corresponding to each part shown to 1st Embodiment-5th Embodiment, and the process equivalent to the board | substrate processing example which concerns on 1st Embodiment-5th Embodiment is shown in FIGS. The same reference numerals as in the case are denoted, and the description is omitted.

The processing unit 2T differs from the processing unit 2 (see FIG. 1) according to the first embodiment in that the mixed processing liquid supply unit 309 is provided in place of the processing liquid supply unit 9. to be. In the processing unit 2T, unlike the processing unit 2, the fluid supplied from the back surface supply unit 10 to the back surface of the substrate W does not contain fruit.

The mixed processing liquid supply unit 309 mixes a mixed processing liquid in which a sublimable substance (first sublimable substance) and a solvent as a first additive are mixed on the surface of the substrate W held by the spin chuck 5. Supply.

The mixed processing liquid supply unit 309 includes a mixed processing liquid supply nozzle 332 accommodated in the nozzle accommodation member 80. The mixed processing liquid supply nozzle 332 moves between a center position facing the rotational center position of the pattern forming surface (surface) of the substrate W and a retracted position not facing the pattern forming surface of the substrate W. As shown in FIG. You can.

The mixed processing liquid supply pipe 334 is connected to the mixed processing liquid supply nozzle 332. The mixed processing liquid supply pipe 334 is provided with a valve 335 that opens and closes the flow path.

The mixed treatment liquid is a mixed liquid obtained by mixing a sublimable substance (first sublimable substance) and a solvent (a solvent having no sublimability) as the first additive. A small amount of solvent is dispersed in the sublimable substance in the molten state with respect to the sublimable substance. The solvent mixing ratio with respect to the mixed process liquid is about several%-several ten% by volume ratio, for example. The sublimation substance has a slightly higher solidification point than the second normal temperature. 2nd normal temperature is the temperature in the clean room in 6th Embodiment of the state which is not in temperature control, and is the temperature in the processing unit 2 in 6th Embodiment of the state which is not in temperature control. 2nd normal temperature is 23 degreeC, for example. The sublimable substance is tertiary butyl alcohol (solidification point about 25.6 ° C.), for example. The solvent is an alcohol, for example. As an example of alcohol, IPA can be exemplified. The freezing point of IPA is lower than the freezing point of a sublimable substance (tertiary butyl alcohol).

The solidification point of the mixed process liquid is lower than the 2nd normal temperature (about 23 degreeC) by the solidification point fall by mixing of a sublimable substance (tertiary butyl alcohol) and IPA. That is, at 2nd normal temperature, a mixed process liquid does not solidify and maintains a liquid phase.

It is a figure which shows the relationship between the density | concentration (IPA mixing ratio of IPA with respect to a mixed process liquid) contained in the mixed process liquid, and the freezing point of the said mixed process liquid.

It can be seen from FIG. 26 that when the concentration of IPA exceeds 3%, the solidification point of the mixed treatment liquid is lower than the second normal temperature. Therefore, when the mixing ratio of IPA with respect to a mixed process liquid is 3% or more, it turns out that a mixed process liquid does not solidify but maintains a liquid state at 2nd normal temperature.

In addition, the heat supply pipe 37 (refer FIG. 2) and the valves 38 and 39 are not provided in the processing unit 2T. That is, although the back surface supply unit 10 supplies a refrigerant | coolant to the back surface of the board | substrate W, it does not supply a fruit to the back surface of the board | substrate W. In the sixth embodiment, in the mixed processing liquid supplying step (step S24 of FIG. 28 to be described later), the mixed processing liquid maintains the liquid phase at the second normal temperature, and therefore, it is necessary to supply the fruit to the back surface of the substrate W. FIG. none. Therefore, since it is not necessary to provide the apparatus (fruit supply pipe 37 and valves 38 and 39) for supplying a fruit, cost reduction can be aimed at.

FIG. 27 is a block diagram showing the electrical configuration of main parts of the substrate processing apparatus 1T.

The controller 3 is further programmed to control the fifth nozzle movement mechanism 333 and the valve 335.

28 is a flowchart for explaining an example of substrate processing by the processing unit 2T. 29A to 29C are schematic sectional views for explaining the state of the substrate processing.

Hereinafter, the substrate processing will be described with reference to FIGS. 1, 25, 27, and 28. Refer to FIGS. 29A to 29C as appropriate.

When the substrate W is processed by the processing unit 2T, a substrate loading step of carrying the unprocessed substrate W into the chamber 4 is performed. Before the board | substrate loading process, the controller 3 arrange | positions the blocking plate 44 in a retracted position, and also retracts all the nozzles from above the spin chuck 5. The hand of the transfer robot CR holding the substrate W is entered into the chamber 4. In the board | substrate loading process, the controller 3 makes the conveyance robot CR exchange the board | substrate W to the spin chuck 5, with the surface (pattern formation surface) facing upward, and spin chuck 5 ), The substrate W is held in a horizontal position by the plurality of holding members 19b. The controller 3 passes the substrate W to the spin chuck 5 and then withdraws the hand of the transfer robot CR from inside the chamber 4.

In the substrate processing by the processing unit 2T, the controller 3 first executes the chemical liquid processing step (step S1 in FIG. 28. See FIG. 5A). When a predetermined period has elapsed since the discharge of the chemical liquid, the controller 3 ends the chemical liquid processing process and starts the rinse processing process (step S2 in FIG. 28. See FIG. 5B). When a predetermined period has elapsed from the start of discharging the rinse liquid, the controller 3 ends the rinse processing process and starts the pretreatment liquid supply process (see step S3 in FIG. 28. FIG. 5C). When a predetermined period has elapsed from the start of discharging the pretreatment liquid, the controller 3 ends the pretreatment liquid supplying step.

Next, the controller executes the mixed processing liquid supply process (step S24. Mixed liquid film forming process in FIG. 28) for supplying the mixed processing liquid on the pattern formation surface of the substrate W. Next, as shown in FIG. In the mixed processing liquid supply step, the controller 3 controls the spin motor 17 to rotate the spin base 19 at a predetermined mixed processing liquid supply speed. The mixed process liquid supply speed is 100 rpm-500 rpm, for example.

The controller 3 supplies the mixed processing liquid to the pattern formation surface of the substrate W while maintaining the rotational speed of the spin base 19 at the mixed processing liquid supplying speed.

Specifically, the controller 3 controls the fifth nozzle moving mechanism 333 to arrange the mixed processing liquid supply nozzle 332 at the center position above the substrate W. As shown in FIG. Then, the controller 3 opens the valve 335. Thereby, as shown to FIG. 29A, the mixed process liquid is supplied from the mixed process liquid supply nozzle 332 toward the pattern formation surface of the board | substrate W of a rotation state (mixed process liquid supply process). The supplied mixed processing liquid is spread evenly over substantially the entire surface of the pattern formation surface of the substrate W while being mixed with the pretreatment liquid by the action of centrifugal force, thereby replacing the pretreatment liquid. And the mixed process liquid film 357 is formed in the pattern formation surface of the board | substrate W. As shown in FIG.

The solidification point of the mixed processing liquid is lower than the second normal temperature (about 23 ° C). Therefore, the mixed treatment liquid does not solidify and maintains the liquid phase. Therefore, in the mixed processing liquid supplying step performed under the second normal temperature environment, the mixed processing liquid film 357 is formed well. After the mixed processing liquid film 357 is spread over the entire area of the substrate W, the supply of the mixed processing liquid to the pattern formation surface of the substrate W is stopped.

After formation of the mixed process liquid film 357, the controller 3 opens the valve 41 and, as shown in FIG. 29B, the refrigerant (3) into the refrigerant path (the refrigerant supply pipe 40 and the back surface supply nozzle 36). 358) is started. Thereby, a refrigerant | coolant is supplied toward the back surface of the board | substrate W of rotation state from the discharge port 36a of the upper end of the back surface supply nozzle 36 via a refrigerant | coolant path | route.

In FIG. 29B, after the supply stop of the mixed processing liquid to the pattern formation surface, the refrigerant 358 is supplied from the back surface supply nozzle 36 to the back surface of the substrate W. The supply of the mixed processing liquid to the pattern formation surface is stopped. At the same time, the coolant 358 may be supplied to the rear surface of the substrate W. As shown in FIG.

The coolant supplied to the rear surface of the substrate W is spread evenly over substantially the entire rear surface of the substrate W by the action of centrifugal force. Thereby, cooling of the mixed process liquid film 357 formed in the pattern formation surface of the board | substrate W is started. Since the substrate W has a predetermined heat capacity, the temperature of the mixed processing liquid film 357 formed on the pattern formation surface of the substrate W gradually decreases.

Therefore, after the valve 41 is opened and a little after the start of supply of the refrigerant to the refrigerant path, the solidification of the mixed processing liquid film 357 formed on the pattern formation surface of the substrate W (solidification step, step in FIG. 28). S7) starts.

As shown in FIG. 29C, in the solidification step (step S7), the controller 3 controls the spin motor 17 while continuing to supply the coolant 358 to the back surface of the substrate W, thereby providing a predetermined value. The spin base 19 is rotated at the speed of solidification. The speed at the time of solidification is 100 rpm-500 rpm, for example.

Thereby, as shown in FIG. 29C, the process liquid film formed in the pattern formation surface of the board | substrate W solidifies, and the solidified body 359 is formed.

Next, the sublimation process (step S8 of FIG. 28) which sublimes the formed solidified body 359 and removes from the pattern formation surface of the board | substrate W is performed. Further, in parallel with the sublimation step, a condensation prevention step (step S9 in FIG. 28) that prevents condensation on the pattern formation surface of the substrate W and a sublimation promotion step for promoting sublimation of the coagulation body 359 (FIG. Step S10) of 28 is executed. By performing the sublimation step and the sublimation promotion step, the influence of the surface tension of the liquid can be eliminated, so that the pattern formation surface of the substrate W can be dried while suppressing collapse of the pattern.

Here, in the case where a solidification point uses a sublimable substance having a higher temperature than the second normal temperature, as shown in the second embodiment of FIG. 8, the pipe (processing liquid supply nozzle 32 and processing liquid supply pipe 34) through which the sublimable substance flows. In order to prevent solidification of the processing liquid remaining in the chamber), a temperature regulating mechanism such as a heater 99 may be provided. Therefore, there exists a possibility that the cost required for a substrate processing apparatus may greatly increase. In addition, the sublimable substance may solidify in the pipe due to the stop of the temperature control mechanism due to the trouble of the apparatus. In this case, there is also a problem that a huge time is required for recovery. In other words, when the sublimable substance having a solidification point higher than the second normal temperature is used for drying the substrate as it is, there is a fear of solidification of the sublimable substance in the pipe.

On the other hand, it is conceivable to use a sublimable material having a solidification point lower than the second room temperature for drying the substrate. However, sublimable materials having a freezing point lower than the second room temperature are very expensive. Therefore, when such a sublimable substance is used for substrate drying, there exists a possibility that cost may increase greatly.

That is, it is desired to be able to suppress or prevent unintentional solidification of the processing liquid having sublimation while suppressing the increase in cost, and to treat the surface of the substrate satisfactorily.

Moreover, in order to solidify the sublimable substance which has a low solidification point, it is necessary to also lower the temperature of the refrigerant | coolant used in a solidification process (step S7). If the temperature of the coolant is lowered, condensation may occur in the substrate processing apparatus depending on the installation condition of the coolant piping. Since dew condensation generated in the substrate processing apparatus may cause a failure of the substrate processing apparatus, a heat insulating material or the like is required to prevent the occurrence of condensation. Then, a surplus cost arises.

According to the sixth embodiment, rather than using a sublimable substance having a lower solidification point than the second normal temperature (about 23 ° C.), the solidification point is lowered by mixing the sublimable substance (for example, tertiary butyl alcohol) with IPA, The freezing point of the mixed processing liquid is lower than the second normal temperature. That is, at the second normal temperature, the mixed treatment liquid is maintained in the liquid phase without solidifying. Therefore, even when the mixed process liquid supplying step is performed in a second normal temperature environment, the mixed process liquid film 357 can be formed satisfactorily. And the solidification body 359 can be formed in the solidification process after a mixed process liquid supply process. In the subsequent sublimation step, the sublimable substance contained in the coagulated body 359 can be sublimed to remove the coagulated body 359 from the pattern formation surface of the substrate W. As shown in FIG.

Therefore, under the second normal temperature environment, unintentional solidification of the mixed treatment liquid can be avoided while suppressing the increase in cost, and the pattern forming surface of the substrate W can be treated well.

<Collapse test>

In the substrate processing (see FIG. 28) according to the sixth embodiment, the concentration of IPA contained in the mixed processing liquid supplied from the mixed processing liquid supply unit 309 is changed and formed on the pattern formation surface of the substrate W. FIG. The change of the collapse rate of the pattern to be examined was investigated. The result is shown in FIG.

30, it turned out that the collapse rate of a pattern falls gently with the raise of IPA density | concentration (solvent mixing ratio with respect to a mixed process liquid) contained in a mixed process liquid. In other words, even when the concentration of IPA was increased, it was found that the collapse of the pattern did not adversely affect.

31 is a diagram illustrating a modification example according to the sixth embodiment.

The first point in which the modified example shown in FIG. 31 differs from the sixth embodiment is that the mixed processing liquid prepared in advance is not used in the substrate processing apparatus 1T, but the mixed processing liquid is prepared in the substrate processing apparatus 1T. (Generated).

Specifically, the mixing portion 361 for mixing the sublimable substance and the solvent is connected to the mixed processing liquid supply pipe 334. The mixing unit 361 is connected to a sublimable substance pipe 362 for supplying a sublimable substance and an additive branch pipe 363 for supplying an additive (first additive) such as IPA. Sublimable material piping 362 is supplied with a sublimable material from a sublimable material supply source. In order to maintain the liquid phase in the sublimable material pipe 362, the sublimable material pipe 362 may be provided with a heat source such as a heater.

The sublimable substance pipe 362 includes a valve 364 for opening and closing the flow path and a valve 365 for adjusting the flow rate of the sublimable substance flowing through the sublimable substance pipe 362.

The additive branch pipe 363 is branched from the additive pipe 366. The additive pipe 366 is supplied with an additive (for example, IPA) from an additive source. The additive pipe 366 is provided with a valve 367 for adjusting the flow rate of the additive flowing through the additive pipe 366. The additive branch pipe 363 is provided with a valve 368 that opens and closes the flow path.

When the valve 364 and the valve 368 are opened with the valve 376 described below closed, the sublimable substance from the sublimable substance pipe 362 and the additive from the additive branch pipe 363 are mixed portions. 361 flows in, and they flow out from the mixing portion 361 to the mixed processing liquid supply pipe 334. The sublimable substance and the additive are sufficiently mixed with each other during the flow of the mixing portion 361 and / or the mixed treatment liquid supply pipe 334. The mixed treatment liquid thus produced is supplied to the mixed treatment liquid supply nozzle 332.

A second point that the modification shown in FIG. 31 differs from the sixth embodiment is to use a mixed refrigerant in which a refrigerant and an additive (second additive) are mixed as the refrigerant to be supplied to the rear surface of the substrate W. As shown in FIG. The freezing point of the mixed refrigerant is lower than the freezing point of the refrigerant before mixing with the additive. The additive includes a solvent (solvent that does not have sublimation). The solvent is an alcohol, for example. As an example of alcohol, IPA can be exemplified.

That is, as another characteristic of this modified example, the additive (second additive) contained in a mixed refrigerant | coolant has the point where the additive and liquid type which are contained in a mixed process liquid are common.

As another feature of this modified example, the mixed refrigerant prepared in advance is not used in the substrate processing apparatus 1T, but the mixed refrigerant is prepared (generated) in the substrate processing apparatus 1T.

Moreover, as another characteristic of this modification, the point where the supply source of the additive (1st additive) for creating a mixed process liquid, and the additive (2nd additive) for creating a mixed refrigerant is common.

Specifically, the mixed refrigerant pipe 370 is connected to the back surface supply nozzle 36 via the shared pipe 43. The mixing section 371 for mixing the refrigerant and the additive is connected to the mixed refrigerant pipe 370. The mixing unit 371 is connected to a refrigerant pipe 372 for supplying a refrigerant and an additive branch pipe 373 for supplying an additive (second additive) such as IPA.

The coolant is supplied to the coolant pipe 372 from a coolant supply source. The refrigerant pipe 372 includes a valve 374 for opening and closing the flow path and a valve 375 for adjusting the flow rate of the refrigerant flowing through the refrigerant pipe 372. The additive branch pipe 373 which is branched from the additive pipe 366 joins the refrigerant pipe 372. The additive branch pipe 373 is provided with a valve 376 for opening and closing the flow path.

When the valve 374 and the valve 376 are opened with the valve 368 closed, the refrigerant from the refrigerant pipe 372 and the additive from the additive branch pipe 373 flow into the mixing portion 371, and they It flows out from the mixing part 371 to the mixed refrigerant piping 370. The coolant and the additive are sufficiently mixed in the middle of circulating the mixing unit 371 and / or the mixed refrigerant pipe 370, and as a result, the mixed refrigerant is generated. In the process of circulating the mixed refrigerant pipe 370, the mixed refrigerant is further cooled using the cooler 380.

The solidification point of the mixed refrigerant is lower than the solidification point of the refrigerant due to the drop of the solidification point due to the mixing of the refrigerant and the additive. That is, the mixed refrigerant is maintained in the liquid phase even at a temperature lower than the freezing point of the refrigerant. Therefore, the liquid mixed refrigerant maintained at a temperature lower than the freezing point of the refrigerant can be supplied to the rear surface of the substrate. When water is used as the refrigerant, the cooler 380 can lower the temperature of the mixed refrigerant to a temperature lower than that of the water. Thereby, in the solidification process, the mixed process liquid film 357 can be cooled to less than 0 degreeC by supplying the mixed refrigerant lower than the freezing point (0 degreeC) of water to the back surface of the board | substrate W. As shown in FIG.

In the modification of FIG. 31, it demonstrated as having a common supply source of the additive (1st additive) for creating a mixed process liquid, and the additive (2nd additive) for creating a mixed refrigerant. However, these sources may be separate.

In addition, in the modification of FIG. 31, the additive (2nd additive) contained in mixed refrigerant | coolant demonstrated as common thing with the additive (1st additive) contained in mixed process liquid, and a liquid type. However, these liquid species may differ from each other.

In addition, in the modification of FIG. 31, it demonstrated as mixing refrigerant | coolant in 1T of substrate processing apparatus which concerns on 6th Embodiment. However, the mixed refrigerant may be prepared in advance.

In addition, in the modification of FIG. 31, the additive (2nd additive) contained in a mixed refrigerant is alcohol, such as IPA. Unlike the modification of FIG. 31, the additive (2nd additive) contained in a mixed refrigerant | coolant may be alcohol other than IPA, and solvent other than alcohol may be sufficient as it.

Moreover, in 6th Embodiment and its modification, the solvent (solvent which does not have sublimability) as an additive (1st additive) contained in a mixed process liquid is alcohol, such as IPA. Unlike 6th Embodiment and its modification, the solvent (solvent which does not have sublimation) as an additive (1st additive) contained in a mixed process liquid can be used suitably even if it is water, such as DIW. As a solvent contained in a mixed process liquid, the solvent illustrated as a solvent contained in the process liquid concerning 1st Embodiment-5th embodiment can be used.

Moreover, in 6th Embodiment and its modification, it is not limited to the solvent which does not have sublimability as an additive (1st additive) contained in a mixed process liquid, and is a kind with the sublimable substance contained in a mixed process liquid. Different sublimable substances may be employed.

Moreover, although the case where the sublimable substance used by 6th Embodiment and its modified example is tertiary butyl alcohol was mentioned as the example, cyclohexanol (coagulation point) as another sublimable substance suitable for use by 6th Embodiment and its modified example is mentioned. About 24 ° C), or 1,3,5-trioxane (solidification point about 63 ° C). Moreover, in the sublimable material used by 6th Embodiment and its modification, although the solidification point of a sublimable material was higher than 2nd normal temperature, and the solidification point of the mixed process liquid was lower than 2nd normal temperature, the solidification point of a sublimable material was demonstrated. It may be lower than this second normal temperature, and the solidification point of the mixed process liquid may be higher than 2nd normal temperature. In addition to these, among the sublimable substances exemplified as the sublimable substances included in the treatment liquids according to the first to fifth embodiments, the mixed treatment liquid contains a sublimable substance having a solidification point drop caused by mixing with an additive. It can be used as a sublimable substance.

This invention is not limited to embodiment described above, It can implement in another form. For example, embodiment mentioned above can be combined suitably.

In addition, in the first embodiment, the chemical liquid, the rinse liquid, the pretreatment liquid and the treatment liquid are substantially simultaneously on the entire surface of the pattern formation surface of the substrate W, for example, from a plurality of nozzle holes arranged in a line shape. You may supply. Similarly, the fruit and the coolant may be supplied to the rear surface of the substrate W almost simultaneously from, for example, a plurality of nozzle holes arranged in a line shape.

Moreover, in 1st Embodiment, in order to maintain the temperature of a process liquid in the temperature range more than melting | fusing point of a sublimable substance and below the boiling point of a sublimable substance, the fruit 56 is supplied to the back surface of the board | substrate W. Instead, heat from a heat source such as a lamp or an electric heater may be used. In addition, in order to cool and solidify the processing liquid, instead of supplying the coolant 58 to the back surface of the substrate W, a cooled inert gas may be supplied, or a Peltier element or the like may be used.

Moreover, in each embodiment mentioned above, in order to promote the sublimation of a solidified body, a pressure reduction piping is provided in the blocking plate 44, and the atmosphere between the blocking plate 44 and the board | substrate W is reduced in pressure, The blocking plate 44 may be heated.

Moreover, another process may be added to the process shown by embodiment to each process of the substrate processing by the substrate processing apparatus 1, 1P, 1Q, 1R, 1S, 1T.

For example, you may perform the substrate processing shown in FIG. 32 using the substrate processing apparatus 1T which concerns on 6th Embodiment. That is, you may perform a thin film formation process (step S6) after a mixed process liquid supply process (step S24). The thin film formation process is performed in a 2nd normal temperature environment similarly to the mixed process liquid supply process. Therefore, in the thin film formation process, the temperature of the mixed process liquid film 357 is in the temperature range above the freezing point of the mixed process liquid and below the boiling point of the mixed process liquid. By carrying out the substrate treatment shown in FIG. 32, the film thickness of the solidified body formed in the solidification step can be reduced in the thinning step. Moreover, since the solidification point of the mixed process liquid is lower than 2nd normal temperature, it is not necessary to perform temperature holding process (step S5 shown in FIG. 4). Therefore, substrate processing can be simplified.

Although embodiments of the present invention have been described in detail, these are merely specific examples used to clarify the technical contents of the present invention, and the present invention should not be construed as being limited to these specific examples. It is limited only by the appended claims.

This application is for Japanese Patent Application No. 2017-182551, filed with Japan Patent Office on September 22, 2017, Japanese Patent Application 2018-002992, filed with Japan Patent Office on January 11, 2018, and May 2018. It corresponds to Japanese Patent Application No. 2018-105412, which was submitted to the Japan Patent Office on March 31, and the entire disclosure of this application is incorporated herein by reference.

Claims (10)

A mixed treatment liquid in which a first sublimable substance and a first additive different from the first sublimable substance are mixed, the mixed treatment liquid having a lower solidification point than the first sublimable substance is supplied to the surface of the substrate, and the mixture is mixed. A mixed liquid film forming step of forming a liquid film of a processing liquid on the surface of the substrate,
A solidification step of solidifying the liquid film of the mixed treatment liquid to form a solidified body,
And a sublimation step of subliming and removing the first sublimable substance contained in the coagulated body from the surface of the substrate. The method according to claim 1,
The solidification point of the said 1st sublimable substance is higher than normal temperature, and the solidification point of the said mixed process liquid is lower than normal temperature. The method according to claim 1 or 2,
The substrate processing method of the said 1st additive containing the solvent which does not have a sublimability. The method according to claim 1 or 2,
And said first additive comprises a second sublimable material. The method according to claim 1 or 2,
And a solidification point of the first additive is lower than a solidification point of the first sublimable material. The method according to claim 1 or 2,
And a mixed liquid preparation step of mixing the first sublimable substance and the first additive to form the mixed treatment liquid,
The said mixed liquid film formation process includes the process of supplying the said mixed process liquid created by the said mixed liquid preparation process to the surface of the said board | substrate. The method according to claim 1 or 2,
The solidification step is a step of supplying a mixed refrigerant in which a refrigerant and a second additive are mixed on the rear surface opposite to the surface of the substrate so as to cool the liquid film of the mixed processing liquid and having a lower solidification point than the refrigerant. It includes a substrate processing method. The method according to claim 7,
The said 2nd additive is common with the said 1st additive, The substrate processing method. The method according to claim 1 or 2,
Further comprising a thinning process of thinning the liquid film of the mixed processing liquid while the temperature of the liquid film of the mixed processing liquid is within a temperature range equal to or higher than the freezing point of the mixed processing liquid and below the boiling point of the mixed processing liquid,
The said solidification process includes the process of solidifying the said liquid film of the said mixed process liquid thinned by the said thin film formation process. The mixed processing liquid which mixed the 1st sublimable substance and the 1st additive different from the said 1st sublimable substance, and supplies the mixed processing liquid which has a freezing point lower than the said 1st sublimable substance to the surface of a board | substrate. Supply unit,
A solidification unit for solidifying the liquid film of the mixed treatment liquid,
A controller for controlling the mixed processing liquid supply unit and the coagulation unit,
The controller,
A mixed liquid film forming step of supplying the mixed processing liquid to the surface of the substrate by the mixed processing liquid supply unit to form the liquid film of the mixed processing liquid on the surface of the substrate;
A solidification step of solidifying the liquid film of the mixed treatment liquid by the coagulation unit to form a coagulation body,
And a sublimation process is executed to sublimate and remove the first sublimable material contained in the coagulated body from the surface of the substrate.

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