WO2020059286A1

WO2020059286A1 - Substrate processing method and substrate processing device

Info

Publication number: WO2020059286A1
Application number: PCT/JP2019/028854
Authority: WO
Inventors: 正幸尾辻; 弘明 ▲高▼橋; 加藤　雅彦; 直澄藤原; 佑山口; 悠太佐々木
Original assignee: 株式会社Ｓｃｒｅｅｎホールディングス
Priority date: 2018-09-21
Filing date: 2019-07-23
Publication date: 2020-03-26
Also published as: JP2020047887A; KR20210045469A; KR102518117B1; TW202023696A; JP7198618B2; TWI722507B; CN112740370A

Abstract

This substrate processing method comprises processing a substrate that has a pattern on the surface thereof, the method including: a mixed drying auxiliary substance supply step in which a mixed drying auxiliary substance, in which a drying auxiliary substance that is non-polar and an amphiphilic solvent are mixed together, is supplied to the surface of the substrate, the mixed drying auxiliary substance having a lower freezing point than that of the drying auxiliary substance, and a liquid film of the mixed drying auxiliary substance being formed on the surface of the substrate; a frozen film formation step in which the drying auxiliary substance included in the liquid film of the mixed drying auxiliary substance is frozen, thereby forming a frozen film that includes the drying auxiliary substance; and a removal step in which the drying auxiliary substance included in the frozen film is changed to a gas without passing through a liquid state and is removed from the surface of the substrate. The frozen film formation step includes a supplied-liquid wetting step in which: a supplied liquid, which is a liquid of a different type than the drying auxiliary substance and the solvent and which is polar with respect to the liquid film of the mixed drying auxiliary substance, is brought into contact with the liquid film; and the drying auxiliary substance is precipitated by an increase in the concentration of the drying auxiliary substance in the liquid film, the increase accompanying the movement of the solvent blended into the mixed drying auxiliary substance from the mixed drying auxiliary substance to the supplied liquid, thereby forming the frozen film.

Description

Substrate processing method and substrate processing apparatus

<< The present invention relates to a substrate processing method and a substrate processing apparatus. Examples of substrates to be processed include semiconductor wafers, substrates for liquid crystal displays, substrates for flat panel displays (FPDs) such as organic EL (electroluminescence) displays, substrates for optical disks, substrates for magnetic disks, and substrates for magneto-optical disks. Substrates, photomask substrates, ceramic substrates, solar cell substrates and the like are included.

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

For example, etching residues, metal impurities, organic contaminants, and the like, which are reaction by-products, adhere to the surface (pattern forming surface) of the substrate on which a fine pattern having irregularities has been formed through a dry etching process or the like. Sometimes. In order to remove these substances from the surface of the substrate, a chemical treatment using a chemical (such as an etching liquid or a cleaning liquid) is performed. After the chemical treatment, a rinsing treatment for removing the chemical with a rinsing liquid is performed. A typical rinse solution is deionized water or the like. Thereafter, a drying process for drying the substrate by removing the rinsing liquid from the surface of the substrate is performed.

In recent years, with the miniaturization of the uneven pattern formed on the surface of the substrate, the aspect ratio (the ratio of the height to the width of the projection) of the projection tends to increase. Therefore, at the time of the drying process, adjacent convex portions are caused by surface tension acting on the liquid surface of the rinsing liquid (the interface between the rinsing liquid and the gas thereon) that has entered the concave portions between the convex portions of the pattern. May be pulled down and collapse.

In Patent Literature 1 below, a rinsing liquid present on the surface of a substrate inside a chamber is replaced with a liquid of tertiary butyl alcohol as a sublimable substance, and then a tertiary butyl alcohol film-like solidified film is formed. It is disclosed. Further, Patent Document 1 below discloses that the surface of a substrate is dried by changing tertiary butyl alcohol contained in a solidified film from a solid phase to a gas phase without passing through a liquid phase. .

Patent Document 1: Japanese Patent Application Laid-Open No. 2015-142069

However, the freezing point of tertiary butyl alcohol is slightly higher (about 25.6 ° C.) than room temperature used in general substrate processing (in the range of 22 ° C. to 25 ° C., for example, about 23 ° C.). Therefore, when a sublimable substance having a freezing point higher than room temperature, such as tertiary butyl alcohol, is used, it is necessary to apply heat to the sublimable substance in the pipe in order to prevent solidification in the pipe. Specifically, it is conceivable to provide a temperature control mechanism in the pipe. In this case, it is desirable to provide a temperature control mechanism in the entire area of the pipe through which the sublimable substance flows. Therefore, the cost may increase significantly. In addition, if the sublimable substance solidifies in the pipe due to a stop of the temperature control mechanism due to a trouble of the apparatus, a long time is required for recovery. That is, when a sublimable substance having a freezing point higher than room temperature, such as tertiary butyl alcohol, is used as it is for drying the substrate, there is a concern that the drying auxiliary substance (sublimable substance) solidifies in the piping.

取り除く To eliminate such concerns, it is conceivable to use a sublimable substance having a freezing point lower than room temperature for drying the substrate. However, sublimable materials having a freezing point below room temperature are generally very expensive. Therefore, when such a sublimable substance is used for drying the substrate, the cost may be greatly increased. Sublimable materials having a freezing point below room temperature do not solidify spontaneously at room temperature. Therefore, it is necessary to use a cooling device or the like inside the chamber to solidify the sublimable substance. Also in this case, the cost may increase significantly.

It is also required that the drying auxiliary substance (sublimable substance) supplied to the surface of the substrate be solidified well without a large increase in cost.

Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of satisfactorily processing the surface of a substrate while avoiding unintentional solidification of a drying auxiliary substance without a large increase in cost. It is.

Another object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of coagulating a drying auxiliary substance on a surface of a substrate without increasing the cost.

A first aspect of the present invention is a substrate processing method for processing a substrate having a pattern on a surface, the method comprising a non-polar drying auxiliary substance and an amphipathic solvent mixed with each other. A mixing / drying aid for supplying a mixed / drying auxiliary substance having a freezing point lower than the freezing point of the drying / auxiliary substance to the surface of the substrate to form a liquid film of the mixed / drying auxiliary substance on the surface of the substrate; A substance supply step, a coagulation film forming step of forming a coagulation film containing the drying auxiliary substance by coagulating the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance, and the coagulation film included in the coagulation film Removing the drying auxiliary substance from the surface of the substrate by changing the drying auxiliary substance into a gas without passing through a liquid state, wherein the coagulation film forming step differs in type from the drying auxiliary substance and the solvent. And the supply liquid which is a polar substance is brought into contact with the liquid film of the mixed drying auxiliary substance, and the solvent dissolved in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid. The present invention further provides a substrate processing method including a supply liquid contacting step of forming the solidified film by depositing the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film.

室温 In this specification, “room temperature” refers to a temperature in an air-conditioning environment in which a substrate processing apparatus is installed, regardless of whether it is in Japan or overseas. Generally, it is in the range of 22 ° C. to 25 ° C., for example about 23 ° C.

In this specification, the term “polar substance” refers to a substance containing a polar molecule.

In this specification, “non-polar substance” refers to a substance composed of non-polar molecules. The “non-polar substance” is intended to include not only a substance that is completely insoluble in a polar substance (polar solvent) but also a substance that is slightly soluble in a polar substance (polar solvent).

Further, in this specification, “having amphipathic properties” refers to including amphiphilic molecules.

According to this method, the mixed drying auxiliary substance in which the drying auxiliary substance and the solvent are mixed is supplied to the surface of the substrate. For example, when the drying auxiliary substance has a freezing point higher than room temperature, a part or the whole thereof may be in a solid state at room temperature. The freezing point of the mixed drying auxiliary substance is lower than the freezing point of the drying auxiliary substance due to the freezing point drop due to the mixing of the drying auxiliary substance and the solvent. That is, even when the freezing point of the mixed drying auxiliary substance is higher than room temperature, the freezing point of the mixed drying auxiliary substance is low. Therefore, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. As a result, it is possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying aid without increasing the cost.

{Circle around (2)} A liquid film of the mixed drying auxiliary substance in which the non-polar drying auxiliary substance and the amphiphilic solvent are mixed is formed on the surface of the substrate. Then, a supply liquid which is a polar substance is supplied to the liquid film of the mixed drying auxiliary substance. The feed liquid, which is a polar substance, is (almost) insoluble in the drying aid, which is a non-polar substance. Therefore, even if the supply liquid comes into contact with the mixed drying auxiliary substance, the drying auxiliary substance and the supply liquid do not mix with each other.

If the equilibrium state is reached in the state where the feed liquid is in contact with the liquid film of the mixed drying auxiliary substance (in a system in which the phase of the mixed drying auxiliary substance and the phase of the supply liquid are in contact), the solvent will be applied to the drying auxiliary substance and the supplied liquid. The melting ratio becomes a unique value (a value determined by the distribution coefficient). Therefore, for example, when the distribution coefficient of the solvent to the drying auxiliary substance and the supply liquid is small, when the supply liquid comes into contact with the liquid film of the mixed drying auxiliary substance, the solvent contained in the mixed drying auxiliary substance is changed from the mixed drying auxiliary substance to Move to feed. As the solvent moves, the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance increases. Then, as the concentration of the drying auxiliary substance increases, the freezing point of the mixed drying auxiliary substance increases, and when this freezing point reaches room temperature, the precipitation of the drying auxiliary substance contained in the mixed drying auxiliary substance present on the surface of the substrate is reduced. Be started. Thereby, a solidified film is formed. Since the drying auxiliary substance contained in the mixed drying auxiliary substance is solidified by utilizing the increase in the freezing point of the mixed drying auxiliary substance, it is not always necessary to cool the mixed drying auxiliary substance for coagulating the mixed drying auxiliary substance. Therefore, it is possible to satisfactorily solidify the drying auxiliary substance supplied to the surface of the substrate without increasing the cost.

As in one embodiment of the present invention, the drying auxiliary substance may include a sublimable substance having sublimability. In this case, the mixed drying auxiliary substance includes a mixed sublimation agent.

According to this method, since the drying auxiliary substance has sublimability, it can be removed from the surface of the substrate by sublimating the drying auxiliary substance contained in the solidified film.

In one embodiment of the present invention, the supply liquid contacting step includes a step of supplying the supply liquid to the surface of the substrate while maintaining a liquid film of the mixed and dried auxiliary substance in a film form.

According to this method, the supply liquid is supplied to the surface of the substrate while the liquid film of the mixed and dried auxiliary substance is kept in a film shape. Therefore, a coagulated film obtained by coagulation of the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance can be provided in a good film shape.

As a method of supplying the supply liquid to the surface of the substrate while maintaining the liquid film of the mixed drying auxiliary substance in a film form, a method of discharging the supply liquid from a large number of minute discharge ports in a shower shape with a weak discharge pressure, There is a method of supplying a supply liquid at a small flow rate to the surface of the substrate.

In one embodiment of the present invention, the substrate processing method further includes a supply liquid removing step of removing the supply liquid existing on the surface of the substrate before the removing step.

According to this method, before the removing step, the supply liquid existing on the surface of the substrate is removed from the surface of the substrate. The feed liquid to be removed also contains the solvent transferred from the mixed drying aid. Therefore, the mixed drying auxiliary substance and the solvent can be favorably removed from the surface of the substrate.

In one embodiment of the present invention, the supply liquid removing step comprises: rotating the substrate around a predetermined rotation axis to shake off the supply liquid present on the surface of the substrate; At least one of a gas blowing step of blowing a gas to the substrate.

According to this method, the supply liquid can be shaken off from the surface of the substrate by rotating the substrate around the rotation axis. Thereby, the supply liquid can be favorably removed from the surface of the substrate. By blowing gas on the surface of the substrate instead of / in conjunction with the rotation of the substrate, the supply liquid adhering to the surface of the substrate can be blown off. Thereby, the supply liquid can be favorably removed from the surface of the substrate.

In one embodiment of the present invention, in the substrate processing method, the supply liquid supplied to the surface of the substrate in the supply liquid contacting step has a liquid temperature lower than room temperature.

によ According to this method, the temperature of the supply liquid is lower than room temperature. Therefore, the surface of the substrate can be cooled by supplying the supply liquid to the surface of the substrate. Thereby, the temperature of the mixed drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance on the surface of the substrate can be lowered. When the temperature of the mixed drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance on the surface of the substrate falls below the freezing point of the mixed drying auxiliary substance, the drying auxiliary substance contained in the mixed drying auxiliary substance starts to solidify. Thereby, a solidified film is formed.

The coagulation of the mixed drying auxiliary substance is simultaneously performed by two mechanisms, that is, coagulation using an increase in the freezing point of the mixed drying auxiliary substance and coagulation due to a decrease in the temperature of the mixed drying auxiliary substance. Can be performed in a short period of time.

In one embodiment of the present invention, the solvent has a higher vapor pressure than the vapor pressure of the drying auxiliary substance. The supply liquid supplied to the surface of the substrate in the supply liquid contacting step has a liquid temperature higher than room temperature.

According to this method, since the solvent has a vapor pressure higher than the vapor pressure of the drying auxiliary substance, the solvent is preferentially evaporated from the mixed drying auxiliary substance present on the surface of the substrate in the supply liquid contacting step. Let me do. As the solvent evaporates from the mixed drying auxiliary substance, the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance increases. Accordingly, the freezing point of the mixed drying auxiliary substance increases, and when the solidification point reaches room temperature, solidification of the drying auxiliary substance contained in the mixed drying auxiliary substance present on the surface of the substrate is started. Thereby, in the supply liquid contacting step, the formation of the solidified film can be further promoted.

In one embodiment of the present invention, the solvent has a higher vapor pressure than the vapor pressure of the drying auxiliary substance. The coagulation film forming step further includes a solvent evaporation step of evaporating the solvent from the mixed and dried auxiliary substance present on the surface of the substrate before the coagulation film formation step.

According to this method, since the solvent has a vapor pressure higher than the vapor pressure of the drying auxiliary substance, the solvent is preferentially evaporated from the mixed drying auxiliary substance present on the surface of the substrate. As the solvent evaporates from the mixed drying auxiliary substance, the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance increases. Accordingly, the freezing point of the mixed drying auxiliary substance increases, and when the solidification point reaches room temperature, solidification of the drying auxiliary substance contained in the mixed drying auxiliary substance present on the surface of the substrate is started. Thereby, the formation of a solidified film can be further promoted.

In one embodiment of the present invention, the solvent evaporating step includes a heating step of heating the mixed drying auxiliary substance, a gas blowing step of blowing a gas to the mixed drying auxiliary substance, and reducing a space around the solidified film. The method includes at least one of a pressure reduction step and a substrate high rotation step of rotating the substrate around a predetermined rotation axis at a high speed without supplying a liquid to the surface of the substrate.

As in an embodiment of the present invention, the heating step may include a step of supplying a heating fluid to the back surface of the substrate.

As in an embodiment of the present invention, the solvent may have a vapor pressure equal to or lower than the vapor pressure of the drying auxiliary substance.

In one embodiment of the present invention, the supply liquid contacting step includes, in parallel with the supply of the supply liquid to the surface of the substrate, the supply position of the supply liquid on the surface of the substrate from the central portion of the substrate. A step of enlarging the formation position of the solidified film on the surface of the substrate from the center of the substrate to the periphery of the substrate by moving the solidified film to the periphery of the substrate.

According to this method, a solidified film can be formed on the entire surface of the substrate in a short period of time.

In one embodiment of the present invention, the removing step includes a sublimation step of sublimating the drying auxiliary substance contained in the coagulated film from a solid to a gas, and the drying included in the coagulated film by decomposition of the coagulated film. A decomposition step of changing the auxiliary substance into a gas without passing through a liquid state, and a reaction step of changing the drying auxiliary substance contained in the coagulated film into a gas without passing through a liquid state by a reaction of the coagulated film. , At least one of the following.

The sublimation step includes a gas blowing step of blowing gas to the solidified film, a heating step of heating the solidified film, a depressurizing step of reducing the space around the solidified film, and light for irradiating the solidified body with light. The method may include at least one of an irradiation step and an ultrasonic vibration applying step of applying ultrasonic vibration to the solidified body.

In one embodiment of the present invention, the mixed drying auxiliary substance supplying step includes a step of immersing the substrate in a first tank in which the mixed drying auxiliary substance is stored, and wherein the supply liquid contacting step includes the supply liquid contacting step. A step of immersing the substrate in a second tank storing a liquid.

According to this method, a solidified film can be favorably formed even in a batch method.

供給 As in one embodiment of the present invention, the supply liquid may contain water.

A second aspect of the present invention is a substrate processing method for processing a substrate having a pattern on a surface, the method comprising a non-polar drying auxiliary substance and an amphipathic solvent mixed with each other. A mixing / drying aid for supplying a mixed / drying auxiliary substance having a freezing point lower than the freezing point of the drying / auxiliary substance to the surface of the substrate to form a liquid film of the mixed / drying auxiliary substance on the surface of the substrate; A substance supply step, a coagulation film forming step of forming a coagulation film containing the drying auxiliary substance by coagulating the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance, and the coagulation film included in the coagulation film Removing the drying auxiliary substance from the surface of the substrate by changing the drying auxiliary substance into a gas without passing through a liquid state, wherein the coagulation film forming step includes a step of increasing the concentration of the drying auxiliary substance in the liquid film. By comprising a feed liquid contacting step of forming the solidified layer by precipitating the dried auxiliary substances, to provide a substrate processing method.

(4) The concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance is increased. Then, as the concentration of the drying auxiliary substance increases, the freezing point of the mixed drying auxiliary substance increases, and when this freezing point reaches room temperature, the precipitation of the drying auxiliary substance contained in the mixed drying auxiliary substance present on the surface of the substrate is reduced. Be started. Thereby, a solidified film is formed. Since the drying auxiliary substance contained in the mixed drying auxiliary substance is solidified by utilizing the increase in the freezing point of the mixed drying auxiliary substance, it is not always necessary to cool the mixed drying auxiliary substance for coagulating the mixed drying auxiliary substance. Therefore, it is possible to satisfactorily solidify the drying auxiliary substance supplied to the surface of the substrate without increasing the cost.

According to a third aspect of the present invention, there is provided a substrate holding unit for holding a substrate having a pattern on a surface thereof, a non-polar drying auxiliary substance on a surface of the substrate held by the substrate holding unit, A mixed drying auxiliary substance supply unit for supplying a mixed drying auxiliary substance having a lower freezing point than the freezing point of the drying auxiliary substance, and a mixed drying auxiliary substance mixed with a solvent having the following formula: A supply liquid supply unit for supplying a supply liquid, which is a liquid different in type from the drying auxiliary substance and the solvent, and a polar substance, on the surface of the substrate held by the substrate holding unit; A removing unit for removing the drying auxiliary substance from the surface of the substrate by converting the drying auxiliary substance into a gas without passing through a liquid state, and supplying the mixed drying auxiliary substance Knit, and a control device for controlling the feed supply unit and the removal unit. The control device supplies the mixed drying auxiliary substance to the surface of the substrate by the mixed drying auxiliary substance supply unit, and forms a liquid film of the mixed drying auxiliary substance on the surface of the substrate. A supply step, a coagulation film forming step of forming a coagulation film containing the drying auxiliary substance by coagulating the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance, and the drying included in the coagulation film Removing the auxiliary substance from the surface of the substrate by changing the auxiliary substance into a gas without passing through a liquid state by the removing unit, wherein the control device performs the mixing and drying assistance in the coagulated film forming step. The supply liquid is supplied to the liquid film of the substance by the supply liquid supply unit, and the solvent dissolved in the mixed drying auxiliary substance is supplied from the mixed drying auxiliary substance to the supply liquid. Provided is a substrate processing apparatus, which performs a supply liquid contacting step of forming the coagulated film by depositing the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film accompanying the transfer to a liquid. .

According to this configuration, the mixed drying auxiliary substance in which the drying auxiliary substance and the solvent are mixed is supplied to the surface of the substrate. For example, when the drying auxiliary substance has a freezing point higher than room temperature, a part or the whole thereof may be in a solid state at room temperature. The freezing point of the mixed drying auxiliary substance is lower than the freezing point of the drying auxiliary substance due to the freezing point drop due to the mixing of the drying auxiliary substance and the solvent. That is, even when the freezing point of the mixed drying auxiliary substance is higher than room temperature, the freezing point of the mixed drying auxiliary substance is low. Therefore, it is possible to reduce the heat energy for keeping the mixed drying auxiliary substance in a liquid state. As a result, it is possible to satisfactorily treat the surface of the substrate while avoiding unintentional solidification of the drying aid without increasing the cost.

The above or other objects, features, and effects of the present invention will be apparent from the following description of embodiments with reference to the accompanying drawings.

FIG. 1 is a schematic diagram of a substrate processing apparatus according to a first embodiment of the present invention as viewed from above. FIG. 2 is an illustrative sectional view for explaining a configuration example of a processing unit provided in the substrate processing apparatus. FIG. 3 is a state equilibrium diagram of a mixed sublimant containing a sublimable substance and a solvent. FIG. 4 is a block diagram for explaining an electrical configuration of a main part of the substrate processing apparatus. FIG. 5 is an enlarged sectional view showing the surface of a substrate to be processed by the substrate processing apparatus. FIG. 6 is a flowchart for explaining the contents of a substrate processing example executed in the processing unit. FIGS. 7A to 7C are schematic diagrams showing the state of the periphery of the substrate when the substrate processing example is executed. 7D and 7E are schematic views showing the next step of FIG. 7C. 7F and 7G are schematic views showing the next step of FIG. 7E. FIG. 8A is an illustrative sectional view for explaining a configuration example of a processing unit according to the second embodiment of the present invention. FIG. 8B is a schematic view showing a removing step (S10) performed in the processing unit. 9A and 9B are schematic diagrams showing a modification of the supply liquid contacting step (S8). FIG. 10 is a schematic diagram showing a modification of the supply liquid nozzle. FIG. 11 is a schematic diagram illustrating an example of a cooling unit. FIG. 12 is a schematic diagram illustrating an example of a cooling unit. FIG. 13 is a schematic diagram illustrating an example of a heating unit. FIG. 14 is a schematic diagram illustrating an example of a heating unit. FIG. 15 is a schematic diagram for explaining a wet processing unit and a dry processing unit. FIG. 16 is a schematic diagram for explaining the configuration of the substrate processing apparatus according to the third embodiment of the present invention. FIG. 17 is a schematic diagram showing a state of lifting in the substrate processing apparatus.

FIG. 1 is a schematic view of a substrate processing apparatus according to a first embodiment of the present invention as viewed from above. The substrate processing apparatus 1 is a single-wafer processing apparatus that processes a substrate W such as a silicon wafer one by one. In this embodiment, the substrate W is a disk-shaped substrate. In the substrate processing apparatus 1, a plurality of processing units 2 for processing a substrate W with a processing liquid including a chemical solution and a rinsing liquid, and a substrate container for storing a plurality of substrates W to be processed by the processing unit 2 are placed. It includes a load port LP, an indexer robot IR and a substrate transfer robot CR for transferring a substrate W between the load port LP and the processing unit 2, and a control device 3 for controlling the substrate processing apparatus 1. The indexer robot IR transports the substrate W between the substrate container and the substrate transport robot CR. The substrate transfer robot CR transfers the substrate W between the indexer robot IR and the processing unit 2. The plurality of processing units 2 have, for example, a similar configuration. The substrate processing apparatus 1 is installed under an environment of normal pressure (atmospheric pressure) and room temperature (for example, about 23 ° C.).

FIG. 2 is an illustrative sectional view for explaining a configuration example of the processing unit 2.

The processing unit 2 includes a box-shaped chamber 4 and a spin chuck that holds one substrate W in a horizontal position in the chamber 4 and rotates the substrate W about a vertical rotation axis A1 passing through the center of the substrate W. (Substrate holding unit) 5, a chemical solution supply unit 6 for supplying a chemical solution to the upper surface of substrate W (surface Wa of substrate W (see FIG. 5)) held by spin chuck 5, and a chemical solution supply unit 6 held by spin chuck 5. A rinsing liquid supply unit 7 for supplying a rinsing liquid to the upper surface of the substrate W (the surface Wa of the substrate W (see FIG. 5)), and the upper surface of the substrate W held by the spin chuck 5 (the surface Wa of the substrate W (see FIG. 5)). 5)), a replacement solvent supply unit 8 for supplying a replacement solvent (hereinafter, referred to as “substitution solvent”), and an upper surface of the substrate W held by the spin chuck 5 (a surface Wa ( (See Fig. 5)) A sublimation agent supply unit (mixing / drying auxiliary substance supply unit) 9 for supplying a mixed sublimation agent (mixing / drying auxiliary substance), and an upper surface of the substrate W held by the spin chuck 5 (a surface Wa of the substrate W (see FIG. 5) )), A supply liquid supply unit 10 for supplying a supply liquid, and a gas blowing unit (removal unit) for blowing gas onto the upper surface of the substrate W (the surface Wa of the substrate W (see FIG. 5)) held by the spin chuck 5. ) 11, a lower nozzle 12 for discharging a heating fluid toward the center of the lower surface of the substrate W (the rear surface Wb of the substrate W (see FIG. 7A and the like)) held by the spin chuck 5, and a side of the spin chuck 5. And a cylindrical processing cup 13 surrounding the other.

では In this embodiment, no blocking member is provided to block the space above the substrate W from the surrounding atmosphere. This is because it is not always necessary to supply the cooling fluid to the back surface Wb of the substrate W in the solidified film forming step (supplied liquid contacting step S8 described later). Since the cooling fluid rebounded by the peripheral members (the processing cup 13 and the like) does not contaminate the surface Wa of the substrate W, no blocking member is provided.

The chamber 4 includes a box-shaped partition 14 that accommodates the spin chuck 5 and the nozzle, and an FFU (fan filter filter) as a blowing unit that sends clean air (air filtered by a filter) into the partition 14 from above the partition 14. Unit) 15, an exhaust duct 16 for exhausting gas in the chamber 4 from below the partition 14, and an exhaust device 17 connected to the other end of the exhaust duct 16. 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 downward from the ceiling of the partition wall 14 into the chamber 4. The exhaust device 17 sucks the inside of the processing cup 13 via an exhaust duct 16 connected to the bottom of the processing cup 13. The FFU 15 and the exhaust device 17 form a downflow (downflow) in the chamber 4. The processing of the substrate W is performed in a state where a downflow is formed in the chamber 4.

挟 As the spin chuck 5, a clamping chuck that holds the substrate W horizontally while sandwiching the substrate W in the horizontal direction is employed. Specifically, the spin chuck 5 includes a spin motor (removal unit) 18, a spin shaft 19 integrated with a drive shaft of the spin motor 18, and a disk attached substantially horizontally to an upper end of the spin shaft 19. And a spin base 20 in the shape of a circle.

The spin base 20 includes a horizontal circular upper surface 20a having an outer diameter larger than the outer diameter of the substrate W. On the upper surface 20a, a plurality (three or more, for example, six) of holding members 21 are arranged on a peripheral portion thereof. The plurality of sandwiching members 21 are arranged at, for example, equal intervals on a circumference corresponding to the outer peripheral shape of the substrate W at a peripheral portion of the upper surface 20a.

As shown in FIG. 2, the chemical solution supply unit 6 includes a chemical solution nozzle 31, a nozzle arm 32 having the chemical solution nozzle 31 attached to a distal end thereof, and a nozzle movement for moving the chemical solution nozzle 31 by moving the nozzle arm 32. Unit 33 (see FIG. 4). The nozzle moving unit 33 horizontally moves the chemical liquid nozzle 31 by horizontally moving the nozzle arm 32 around the swing axis. The nozzle moving unit 33 has a configuration including a motor and the like. The nozzle moving unit 33 moves the chemical liquid nozzle between a processing position where the chemical liquid discharged from the chemical liquid nozzle 31 lands on the surface Wa of the substrate W and a retracted position set around the spin chuck 5 in plan view. 31 is moved horizontally. In other words, the processing position is a position where the chemical solution discharged from the chemical solution nozzle 31 is supplied to the front surface Wa of the substrate W. Furthermore, the nozzle moving unit 33 includes a central position where the chemical liquid discharged from the chemical liquid nozzle 31 lands on a central portion of the surface Wa of the substrate W, and a peripheral portion of the chemical liquid discharged from the chemical liquid nozzle 31 on the surface Wa of the substrate W. The chemical liquid nozzle 31 is moved horizontally between the peripheral position where the liquid is applied to the liquid. The center position and the peripheral position are both processing positions.

The chemical supply unit 6 includes a chemical pipe 34 for guiding the chemical to the chemical nozzle 31, and a chemical valve 35 for opening and closing the chemical pipe 34. When the chemical valve 35 is opened, the chemical from the chemical supply source is supplied from the chemical pipe 34 to the chemical nozzle 31. Thereby, the chemical solution is discharged from the chemical solution nozzle 31.

(4) The chemical supplied to the chemical piping 34 includes a cleaning liquid and an etching liquid. More specifically, the chemicals include sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, aqueous ammonia, aqueous hydrogen peroxide, organic acids (such as citric acid and oxalic acid), and organic alkalis (such as TMAH: tetramethylammonium hydrochloride). Liquid containing at least one of an oxide, a surfactant, and a corrosion inhibitor.

リン As shown in FIG. 2, the rinsing liquid supply unit 7 includes a rinsing liquid nozzle 36. The rinse liquid nozzle 36 is, for example, a straight nozzle that discharges the liquid in a continuous flow state, and is fixedly disposed above the spin chuck 5 with its discharge port facing the center of the upper surface of the substrate W. A rinse liquid pipe 37 to which a rinse liquid is supplied from a rinse liquid supply source is connected to the rinse liquid nozzle 36. A rinsing liquid valve 38 for switching between supplying / stopping the supply of the rinsing liquid from the rinsing liquid nozzle 36 is provided at an intermediate portion of the rinsing liquid pipe 37. When the rinsing liquid valve 38 is opened, the rinsing liquid supplied from the rinsing liquid pipe 37 to the rinsing liquid nozzle 36 is discharged from a discharge port set at the lower end of the rinsing liquid nozzle 36. When the rinse liquid valve 38 is closed, the supply of the rinse liquid from the rinse liquid nozzle 36 from the rinse liquid pipe 37 is stopped. The rinsing liquid is water. The water is, for example, deionized water (DIW), but is not limited to DIW, and may be any of carbonated water, electrolytic ionized water, hydrogen water, ozone water, ammonia water, and hydrochloric acid water having a dilute concentration (for example, about 10 ppm to 100 ppm). Or it may be.

In addition, the rinsing liquid supply unit 7 may include a rinsing liquid nozzle moving device that moves the rinsing liquid nozzle 36 to scan the rinsing liquid landing position on the upper surface of the substrate W within the surface of the substrate W. .

As illustrated in FIG. 2, the replacement solvent supply unit 8 includes a replacement solvent nozzle 41, a nozzle arm 42 having the replacement solvent nozzle 41 attached to a tip end thereof, and a nozzle arm 42 that is moved to thereby perform the replacement solvent nozzle 41. A nozzle moving unit 43 (see FIG. 4) for moving the solvent nozzle 41. The nozzle moving unit 43 horizontally moves the replacement solvent nozzle 41 by horizontally moving the nozzle arm 42 around the swing axis. The nozzle moving unit 43 has a configuration including a motor and the like. The nozzle moving unit 43 moves between the processing position where the replacement solvent discharged from the replacement solvent nozzle 41 lands on the surface Wa of the substrate W and the retreat position set around the spin chuck 5 in plan view. Then, the replacement solvent nozzle 41 is moved horizontally. In other words, the processing position is a position at which the replacement solvent discharged from the replacement solvent nozzle 41 is supplied to (for example, the center of) the surface Wa of the substrate W.

As shown in FIG. 2, the replacement solvent supply unit 8 includes a replacement solvent pipe 44 for guiding the replacement solvent to the replacement solvent nozzle 41, and a replacement solvent valve 45 for opening and closing the replacement solvent pipe 44. Including. When the replacement solvent valve 45 is opened, the replacement solvent from the replacement solvent supply source is supplied to the replacement solvent nozzle 41 from the replacement solvent pipe 44. As a result, the replacement solvent is discharged from the replacement solvent nozzle 41.

The replacement solvent supplied to the replacement solvent piping 44 has solubility (miscibility) with the mixed sublimation agent supplied by the mixed sublimation agent supply unit 9. That is, the replacement solvent has solubility (miscibility) with respect to the sublimable substance and the mixing solvent contained in the mixed sublimation agent. The replacement solvent is used as a pre-supply liquid to be supplied to the front surface Wa prior to the supply of the mixed sublimation agent to the front surface Wa of the substrate W.

In the substrate processing example described later, after the supply of the rinsing liquid to the surface Wa of the substrate W, the replacement solvent is supplied to the surface Wa prior to the supply of the mixed sublimation agent to the surface Wa of the substrate W. Therefore, it is desirable that the replacement solvent further has solubility (miscibility) in the rinsing liquid (water).

具体 A specific example of the replacement solvent supplied to the replacement solvent pipe 44 is an organic solvent represented by, for example, IPA (isopropyl alcohol). Examples of such organic solvents include, in addition to IPA, methanol, ethanol, acetone, EG (ethylene glycol), HFE (hydrofluoroether), n-butyl alcohol, t-butyl alcohol, isobutyl alcohol and 2-butyl alcohol. Can be illustrated. Further, the organic solvent is not limited to the case where the organic solvent is composed of only a single component, and may be a liquid mixed with another component. In addition, a solvent other than the organic solvent can be used as the replacement solvent.

As shown in FIG. 2, the mixed sublimation supply unit 9 moves and moves the mixed sublimation nozzle 46, the nozzle arm 47 having the mixed sublimation nozzle 46 attached to the tip, and the nozzle arm 47. A nozzle moving unit 48 (see FIG. 4) for moving the agent nozzle 46. The nozzle moving unit 48 horizontally moves the mixed sublimation agent nozzle 46 by horizontally moving the nozzle arm 47 around the swing axis. The nozzle moving unit 48 is configured to include a motor and the like. The nozzle moving unit 48 moves between the processing position where the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 lands on the surface Wa of the substrate W and the retreat position set around the spin chuck 5 in plan view. Then, the mixed sublimation agent nozzle 46 is moved horizontally. In other words, the processing position is a position where the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 is supplied to (for example, the center of) the surface Wa of the substrate W.

As shown in FIG. 2, the mixed sublimation supply unit 9 includes a mixed sublimation pipe 49 that guides the mixed sublimation agent to the mixing sublimation nozzle 46, and a mixed sublimation valve 50 that opens and closes the mixed sublimation pipe 49. In addition. When the mixed sublimation valve 50 is opened, the mixed sublimation from the mixed sublimation supply source is supplied from the mixed sublimation piping 49 to the mixed sublimation nozzle 46. Thereby, the mixed sublimation agent is discharged from the mixed sublimation agent nozzle 46.

The mixed sublimation agent supplied to the mixed sublimation pipe 49 is a mixed substance in which a sublimable substance having a sublimability (drying auxiliary substance) and a solvent for mixing (solvent) are mixed. The sublimable substance has a freezing point T _F1 (see FIG. 3) equal to or higher than room temperature (RT). The room temperature (RT) is not necessarily constant but is generally set to 23 ° C. because it is affected by the temperature of the outside air. In the mixed sublimation agent, the sublimable substance and the solvent for mixing are in a state of being mutually dissolved. Therefore, in the mixed sublimation agent, the sublimable substance and the mixing solvent are uniformly mixed without bias.

昇 Sublimable substances that sublimate preferentially among substances contained in the mixed sublimation agent are non-polar substances. “Non-polar substance” refers to a substance composed of non-polar molecules. Camphor (freezing point under atmospheric pressure: about 175 ° C. to 180 ° C., vapor pressure under atmospheric pressure at room temperature: 120 Pa) as a sublimable substance, cyclohexanol (freezing point under atmospheric pressure: about 24 ° C., vapor under atmospheric pressure at room temperature) Pressure: 0.13 kPa), room temperature tertiary butyl alcohol (freezing point under atmospheric pressure: about 25.6 ° C .: vapor pressure under room temperature and atmospheric pressure: 5.4 kPa), 1,3,5-Trioxane (under atmospheric pressure) Freezing point: about 60 ° C to 62 ° C, vapor pressure at room temperature and atmospheric pressure: 0.75 kPa), naphthalene (freezing point at atmospheric pressure: about 80 ° C, vapor pressure at room temperature and atmospheric pressure: 7.9 Pa), iodine (large) Solidification point under atmospheric pressure: about 113 ° C., vapor pressure under atmospheric pressure at room temperature: 0.04 kPa), methanol, n-butanol and the like.

混合 The mixing solvent contained in the mixed sublimation agent has amphiphilicity. "Having amphipathic" refers to including amphiphilic molecules. The solvent for mixing is, for example, an organic solvent represented by IPA (isopropyl alcohol). Examples of the organic solvent used as the solvent for mixing include, for example, ethanol and acetone in addition to IPA. In addition, the organic solvent used as the mixing solvent is not limited to the case where the organic solvent includes only a single component, and may be a liquid mixed with another component. In addition, a solvent other than the organic solvent can be used as the mixing solvent.

In this embodiment, examples of suitable combinations of the sublimable substance and the solvent for mixing include camphor and IPA, cyclohexanol and IPA, and 1,3,5-Trioxane and IPA, respectively.

(4) When the mixing solvent is IPA, its vapor pressure is 6.05 kPa at room temperature and atmospheric pressure. Camphor, cyclohexanol and 1,3,5-Trioxane have a significantly lower vapor pressure than IPA. In other words, camphor, cyclohexanol, 1,3,5-Trioxane or the like is used as a sublimable substance, and when IPA is used as a solvent for mixing, the mixing solvent contained in the mixed sublimation agent is more than the sublimation substance. Has a high vapor pressure.

Further, when employing the combination of camphor and IPA as a combination of sublimable material and the mixing solvent, the freezing point T _F1 sublimable substance (camphor) is at atmospheric pressure, for example about 175 ° C. ~ about 180 ° C.. Further, the freezing point T _F2 of the mixed solvent is at atmospheric pressure is less than or equal to about -80 ° C..

In the above-described combination example of the sublimable substance and the mixing solvent, the case where the mixing solvent is IPA having a freezing point _TF2 lower than room temperature has been described as an example. However, the freezing point T _F2 of the mixed solvent may be higher than room temperature.

FIG. 3 is a state equilibrium diagram of a mixed sublimant containing a sublimable substance and a mixing solvent. The freezing point T _FM of the mixed sublimation agent is lower than the freezing point T _F1 of the sublimable substance due to the freezing point drop due to the mixing of the sublimable substance and the mixing solvent. The freezing point _TFM of the mixed sublimation agent depends on the concentration of the sublimable substance in the mixed sublimation agent. FIG. 3 shows a freezing point curve FPC of the mixed sublimation agent. The concentration of the sublimable substance in the mixed sublimation agent, freezing point T _FM mixtures sublimation agent decreases to a temperature below room temperature (RT), mix sublimation agent forms a liquid at room temperature environment.

The concentration of the sublimable substance in the mixed sublimation agent, freezing point T _FM mixtures sublimation agent is appropriately set in a range to a temperature below room temperature (RT). However, since the original purpose of using the mixed sublimant is to sublimate the sublimable substance (S10 in FIG. 6: removal step), the concentration of the mixing solvent in the mixed sublimant is not too high, that is, the mixed sublimant is used. It is necessary that the concentration of the sublimable substance is not too low.

薬 Outside the chamber 4, a chemical solution supply device is provided integrally with the substrate processing apparatus 1 or separately from the substrate processing apparatus 1. This chemical supply device is also installed in an environment of room temperature and normal pressure (atmospheric pressure). This chemical solution supply device is provided with a storage tank for storing the mixed sublimation agent. The mixed sublimation agent is in a liquid state at room temperature. Therefore, a heating device or the like for keeping the sublimable substance in a liquid state is unnecessary. Even when such a heating device is provided, it is not necessary to constantly heat the mixed sublimation agent. Therefore, the required heat amount can be reduced, and as a result, the cost can be reduced.

As shown in FIG. 2, the supply liquid supply unit 10 controls the supply liquid nozzle 51 by moving the supply liquid nozzle 51, the nozzle arm 52 having the supply liquid nozzle 51 attached to the distal end thereof, and the nozzle arm 52. And a nozzle moving unit 53 (see FIG. 4) for moving. The nozzle moving unit 53 horizontally moves the supply liquid nozzle 51 by horizontally moving the nozzle arm 52 around the swing axis. The nozzle moving unit 53 has a configuration including a motor and the like. The nozzle moving unit 53 moves between the processing position where the mixed sublimation agent discharged from the supply liquid nozzle 51 lands on the surface Wa of the substrate W and the retracted position set around the spin chuck 5 in plan view. Then, the supply liquid nozzle 51 is moved horizontally. In other words, the processing position is a position where the supply liquid discharged from the supply liquid nozzle 51 is supplied to (for example, a central portion of) the surface Wa of the substrate W.

As shown in FIG. 2, the supply liquid supply unit 10 further includes a supply liquid pipe 54 for guiding the mixed sublimation agent to the supply liquid nozzle 51, and a supply liquid valve 55 for opening and closing the supply liquid pipe 54. When the supply liquid valve 55 is opened, the supply liquid from the supply liquid supply source is supplied from the supply liquid pipe 54 to the supply liquid nozzle 51. Thereby, the supply liquid is discharged from the supply liquid nozzle 51.

供給 The supply liquid supplied to the supply liquid pipe 54 is a liquid different from the above-described sublimable substance and the mixing solvent. The supply liquid supplied to the supply liquid pipe 54 is a polar substance. “Polar substance” refers to a substance containing a polar molecule. The supply liquid supplied to the supply liquid pipe 54 has a liquid temperature lower than room temperature. In this embodiment, the liquid temperature of the supply liquid is set to be 5 ° C. to 10 ° C. lower than room temperature. That is, the supply liquid also functions as a cooling liquid.

具体 A specific example of the supply liquid supplied to the supply liquid pipe 54 is a water-containing liquid containing water. A representative example of a water-containing liquid is water, such as deionized water (DIW). Such a water-containing liquid is not limited to DIW, and examples thereof include carbonated water, electrolytic ionic water, hydrogen water, ozone water, ammonia water, and hydrochloric acid water.

有機 Also, an organic solvent can be used as the supply liquid. Examples of such an organic solvent include methanol, ethanol, acetone, methanol, n-butanol and the like.

As shown in FIG. 2, the gas blowing unit 11 includes a gas nozzle 56, a nozzle arm 57 having the gas nozzle 56 attached to a distal end thereof, and a nozzle movement for moving the gas nozzle 56 by moving the nozzle arm 57. A unit 58 (see FIG. 4). The nozzle moving unit 58 horizontally moves the gas nozzle 56 by horizontally moving the nozzle arm 57 around the swing axis. The nozzle moving unit 53 has a configuration including a motor and the like. The nozzle moving unit 58 is provided between a processing position where the mixed sublimation agent discharged from the gas nozzle 56 lands on the surface Wa of the substrate W and a retreat position set around the spin chuck 5 in a plan view. The gas nozzle 56 is moved horizontally. In other words, the processing position is a position where the gas blown from the supply liquid nozzle 51 is supplied to the surface Wa of the substrate W. Specifically, the processing position is a central position where the gas blown out from the gas nozzle 56 lands on the center of the upper surface of the substrate W.

As shown in FIG. 2, the gas blowing unit 11 further includes a gas pipe 59 for guiding the gas to the gas nozzle 56, and a gas valve 60 for opening and closing the gas pipe 59. When the gas valve 60 is opened, gas from the gas supply source is supplied from the gas pipe 59 to the gas nozzle 56. Thereby, gas is blown out from the gas nozzle 56.

気体 The gas supplied to the gas pipe 59 is a dehumidified gas, particularly an inert gas. The inert gas includes, for example, nitrogen gas and argon gas. The gas may be an active gas such as air.

The gas nozzle 56 has a cylindrical nozzle body 64 having a flange 63 at the lower end. An upper gas discharge port 65 and a lower gas discharge port 66 are formed in the outer peripheral surface, which is the side surface of the flange portion 63, and open outward in a ring shape. On the lower surface of the nozzle body 64, a central gas discharge port 67 is arranged. Therefore, the radial gas flow formed by the inert gas discharged from the center gas discharge port 67 and the two-layer radial gas flow discharged from the upper gas discharge port 65 and the lower gas discharge port 66 are combined into three layers. Is formed above the substrate W.

As shown in FIG. 2, the lower surface nozzle 12 has a single discharge port 12 a facing the center of the lower surface of the substrate W held by the spin chuck 5. The discharge port 12a discharges the liquid vertically upward. The discharged liquid is incident almost perpendicularly to the center of the lower surface of the substrate W held by the spin chuck 5. A lower surface supply pipe 71 is connected to the lower surface nozzle 12. The lower surface supply pipe 71 is inserted into the inside of a spin shaft 19 composed of a hollow shaft arranged vertically.

As shown in FIG. 2, a heating fluid pipe 72 is connected to the lower surface supply pipe 71. The heating fluid pipe 72 is provided with a heating fluid valve 73 for opening and closing the heating fluid pipe 72. The heating fluid may be a heating liquid such as hot water or a heating gas. Heating fluid has a higher liquid temperature than the freezing point T _FM mixtures sublimation agent.

When the heating fluid valve 73 is opened, the heating fluid from the heating fluid supply source is supplied to the lower nozzle 12 via the heating fluid pipe 72 and the lower supply pipe 71. The heating fluid supplied to the lower nozzle 12 is discharged almost vertically upward from the discharge port 12a. The heating liquid discharged from the lower surface nozzle 12 is incident on the substrate W held by the spin chuck 5 substantially perpendicularly to the center of the lower surface. In this embodiment, a heating unit is configured by the lower nozzle 12, the lower supply pipe 71, the heating fluid pipe 72, and the heating fluid valve 73.

(2) As shown in FIG. 2, the processing cup 13 is disposed outside (in a direction away from the rotation axis A1) the substrate W held by the spin chuck 5. The processing cup 13 surrounds the spin base 20. When a liquid such as a processing liquid, a rinsing liquid, a replacement solvent, or a mixed sublimation agent is supplied to the substrate W while the spin chuck 5 is rotating the substrate W, the liquid supplied to the substrate W Shake off around. When these liquids are supplied to the substrate W, the upper end 13 a of the processing cup 13 is disposed above the spin base 20. Therefore, the liquid discharged around the substrate W is received by the processing cup 13. Then, the liquid received by the processing cup 13 is sent to a not-shown recovery device or waste liquid device.

FIG. 4 is a block diagram for explaining an electrical configuration of a main part of the substrate processing apparatus 1.

The control device 3 is configured using, for example, a microcomputer. The control device 3 has an arithmetic unit such as a CPU, a fixed memory device, a storage unit such as a hard disk drive, and an input / output unit. The storage unit stores a program executed by the arithmetic unit.

{Circle around (3)} The control device 3 is connected with the spin motor 18, the nozzle moving units 33, 43, 48, 53, 58, etc. as control objects. The control device 3 controls the operations of the spin motor 18, the nozzle moving units 33, 43, 48, 53, 58 and the like according to a predetermined program.

The control device 3 also controls the gas valve 225, the chemical liquid valve 35, the rinsing liquid valve 38, the replacement solvent valve 45, the mixed sublimator valve 50, the supply liquid valve 55, the gas valve 60, and the heating fluid according to a predetermined program. The valve 73 and the like are opened and closed.

Hereinafter, a case will be described in which the substrate W on which the pattern 100 is formed on the front surface Wa, which is the pattern forming surface, is processed.

FIG. 5 is an enlarged cross-sectional view showing the surface Wa of the substrate W to be processed by the substrate processing apparatus 1. The substrate W to be processed is, for example, a silicon wafer, and a pattern 100 is formed on a surface Wa, which is a pattern forming surface thereof. The pattern 100 is, for example, a fine pattern. In the pattern 100, as shown in FIG. 5, the structures 101 having a convex shape (column shape) may be arranged in a matrix. In this case, the line width W1 of the structure 101 is set to, for example, about 3 nm to 45 nm, and the gap W2 of the pattern 100 is set to, for example, about 10 nm to several μm. The height T of the pattern 100 is, for example, about 0.2 μm to 1.0 μm. Further, pattern 100 may have, for example, an aspect ratio (ratio of height T to line width W1) of, for example, about 5 to 500 (typically about 5 to 50).

{Circle around (4)} The pattern 100 may be a pattern in which linear patterns formed by fine trenches are repeatedly arranged. The pattern 100 may be formed by providing a plurality of fine holes (voids or pores) in a thin film.

Pattern 100 includes, for example, an insulating film. Further, the pattern 100 may include a conductive film. More specifically, the pattern 100 is formed of a stacked film in which a plurality of films are stacked, and may further include an insulating film and a conductive film. The pattern 100 may be a pattern composed of a single layer film. The insulating film may be a silicon oxide film (SiO2 film) or a silicon nitride film (SiN film). Further, the conductor film may be an amorphous silicon film into which an impurity for lowering the resistance is introduced, or a metal film (for example, a TiN film).

パターン The pattern 100 may be a hydrophilic film. Examples of the hydrophilic film include a TEOS film (a type of silicon oxide film).

FIG. 6 is a flowchart for explaining an example of substrate processing by the processing unit 2. 7A to 7G are schematic diagrams showing the state of the periphery of the substrate W when this substrate processing example is being executed.

When the substrate processing example is performed on the substrate W by the processing unit 2, the unprocessed substrate W is loaded into the chamber 4 (Step S1 in FIG. 6).

(4) The control device 3 causes the hand H of the substrate transfer robot CR (see FIG. 1) holding the substrate W to enter the inside of the chamber 4 with all the nozzles and the like retracted from above the spin chuck 5. As a result, the substrate W is transferred to the spin chuck 5 with the surface Wa facing upward, and is held by the spin chuck 5.

After the substrate W is held by the spin chuck 5, the control device 3 controls the spin motor 18 to increase the rotation speed of the spin base 20 to a predetermined liquid processing speed (for example, within a range of about 10 rpm to about 1500 rpm, for example, about 500 rpm) to maintain the liquid processing speed.

(4) When the rotation speed of the substrate W reaches the liquid processing speed, the control device 3 starts executing the chemical liquid process (Step S2 in FIG. 6). Specifically, the control device 3 controls the nozzle moving unit 33 to move the chemical liquid nozzle 31 from the retracted position to the processing position. The control device 3 opens the chemical liquid valve 35. As a result, the chemical is supplied to the chemical nozzle 31 through the chemical pipe 34, and the chemical discharged from the discharge port of the chemical nozzle 31 lands on the surface Wa of the substrate W.

Further, in the chemical solution process (S2), the control device 3 controls the nozzle moving unit 23 to move the chemical solution nozzle 31 to a peripheral position facing the peripheral portion of the front surface Wa of the substrate W and a central portion of the upper surface of the substrate W. May be moved between a central position facing the camera. In this case, the liquid landing position on the upper surface of the substrate W is scanned over the entire surface Wa of the substrate W. Thus, the entire surface Wa of the substrate W can be uniformly processed.

制御 When a predetermined period elapses from the start of the discharge of the chemical, the control device 3 closes the chemical valve 35 and stops the discharge of the chemical from the chemical nozzle 31. Thus, the chemical solution step (S2) ends. Further, the control device 3 returns the chemical liquid nozzle 31 to the retracted position.

Next, the control device 3 executes a rinsing step (step S3 in FIG. 6) in which the chemical solution on the substrate W is replaced with a rinsing liquid and the surface Wa of the substrate W is washed away. Specifically, control device 3 opens rinse liquid valve 38. Thus, the rinsing liquid is discharged from the rinsing liquid nozzle 36 toward the center of the rotating surface Wa. The rinsing liquid supplied to the front surface Wa of the substrate W receives the centrifugal force due to the rotation of the substrate W, moves to the peripheral edge of the substrate W, and is discharged from the peripheral edge of the substrate W to the side of the substrate W. Thereby, the chemical liquid adhering on the substrate W is washed away by the rinse liquid.

When a predetermined period has elapsed since the opening of the rinsing liquid valve 38, the control device 3 closes the rinsing liquid valve 38. Thus, the rinsing step (S3) ends.

Next, the control device 3 executes a replacement step (step S4 in FIG. 6). The substitution step (S4) is a step of replacing the rinsing liquid on the substrate W with a substitution solvent having an affinity for both the rinsing liquid (water) and the mixed sublimation agent (in this example, an organic solvent such as IPA). is there.

Specifically, the control device 3 controls the nozzle moving unit 43 to move the replacement solvent nozzle 41 from the retracted position on the side of the spin chuck 5 to above the center of the surface Wa of the substrate W. . Then, the control device 3 opens the replacement solvent valve 45 and discharges the liquid replacement solvent from the replacement solvent nozzle 41 toward the center of the upper surface (front surface Wa) of the substrate W. The replacement solvent supplied to the surface Wa of the substrate W receives the centrifugal force due to the rotation of the substrate W and spreads over the entire surface Wa. Thus, the rinsing liquid adhering to the front surface Wa of the entire surface Wa of the substrate W is replaced by the replacement solvent. The replacement solvent that moves on the surface Wa of the substrate W is discharged from the periphery of the substrate W to the side of the substrate W.

The replacement step (S4) may be performed while rotating the substrate W at the above-described liquid processing speed. Further, the replacement step (S4) may be performed while rotating the substrate W at a liquid filling speed lower than the above-described liquid processing speed or while stopping the substrate W.

(4) When a predetermined period has elapsed from the start of the replacement solvent discharge, the control device 3 closes the replacement solvent valve 45 and stops the replacement solvent nozzle 41 from discharging the replacement solvent. Thus, the replacement step (S4) ends. Further, the control device 3 returns the replacement solvent nozzle 41 to the retracted position.

Next, the control device 3 executes a mixed sublimation agent supply step (Step S5 in FIG. 6; a mixed drying auxiliary substance supply step).

Specifically, the control device 3 controls the nozzle moving unit 48 to move the mixed sublimation agent nozzle 46 from the retracted position on the side of the spin chuck 5 to above the center of the surface Wa of the substrate W. . Then, the control device 3 opens the mixed sublimation agent valve 50 and discharges the mixed sublimation agent from the mixed sublimation nozzle 46 toward the center of the upper surface (front surface Wa) of the substrate W, as shown in FIG. 7A. As mentioned above, mixing sublimation agent supplied to the mixing sublimation agent nozzle 46, the freezing point T _FM is to be less than room temperature under atmospheric pressure, the concentration of the sublimable substance in the mixed sublimation agent is defined . Therefore, the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 maintains a liquid state.

{Circle around (4)} The mixed sublimant that has landed on the center of the surface Wa of the substrate W flows toward the peripheral edge of the surface Wa of the substrate W under the centrifugal force generated by the rotation of the substrate W. Thus, a liquid film 81 of the mixed sublimant is formed on the surface Wa of the substrate W so as to cover the entire surface Wa of the substrate W. Since the mixed sublimation agent discharged from the mixed sublimation agent nozzle 46 maintains a liquid state, the liquid film 81 can be formed favorably. In the mixed sublimation agent supply step (S5), the height of the thickness W11 of the mixed sublimation liquid film 81 formed on the surface Wa of the substrate W is sufficiently larger than the height T of the pattern 100 (see FIG. 5). High.

(4) The mixed sublimation agent supply step (S5) may be performed while rotating the substrate W at the liquid processing speed described above. In the mixed sublimation agent supplying step (S5), the substrate W is subjected to a liquid filling speed lower than the liquid processing speed (the centrifugal force acting on the mixed sublimation liquid film 81 on the upper surface of the substrate W is mixed with the mixed sublimation agent). While rotating at a speed lower than the surface tension acting on the upper surface of the substrate W, or at a speed at which the centrifugal force and the surface tension substantially oppose each other (for example, about 5 rpm), or It may be performed while stopping.

{Circle around (3)} When a predetermined period has elapsed since the start of the discharge of the mixed sublimation agent, the control device 3 closes the mixed sublimation valve 50. Thereby, the supply of the mixed sublimation agent to the surface Wa of the substrate W is stopped. Further, the control device 3 returns the mixed sublimation agent nozzle 46 to the retracted position.

Next, a film thickness reducing step (step S6 in FIG. 6) of reducing the film thickness of the mixed sublimant liquid film 81 is performed.

Specifically, the film thickness reduction step (S6) includes a substrate high rotation step (spin-off; substrate rotation step). The controller 3 controls the spin motor 18 without supplying the mixed sublimation agent to the surface Wa of the substrate W to rotate the spin base 20 at a predetermined high rotation speed (for example, a predetermined speed of about 100 rpm to about 2500 rpm). Rotate. Thereby, the substrate W is rotated at this high rotation speed. As a result, a large centrifugal force is applied to the surface Wa of the substrate W, the mixed sublimation agent contained in the liquid film 81 is eliminated from the surface Wa of the substrate W, and the film thickness of the liquid film 81 decreases. As a result, as shown in FIG. 7B, a thin film 82 of the mixed sublimation agent is formed on the surface Wa of the substrate W. The thickness W12 of the thin film 82 is thinner, that is, lower than the thickness W11 of the liquid film 81. The thickness W12 of the thin film 82 is on the order of several hundred nanometers to several micrometers. The upper surface of the thin film 82 is located above the upper end of each pattern 100 (see FIG. 5) formed on the surface Wa. The thickness W12 of the thin film 82 is adjusted by adjusting the rotation speed of the substrate W.

(4) The larger the thickness of the liquid film (thin film 82) before solidification, the larger the internal stress (strain) remaining in the solidified film 83 formed in the liquid supply step (S8). By reducing the thickness of the liquid film (thin film 82) immediately before the start of the supply liquid contact step (S8), the internal stress remaining in the solidified film 83 formed in the supply liquid contact step (S8) is reduced as much as possible. Can be smaller.

Further, the thinner the film thickness of the solidified film 83 is, the smaller the amount of residue remaining on the surface Wa of the substrate W after the removing step (S10) described later. By reducing the thickness of the coagulated film 83 before the start of the supply liquid contacting step (S8), the thickness of the coagulated film 83 can be adjusted to be small. Thereby, generation of residues after the removal step (S10) can be suppressed.

Also, in this embodiment, the thin film 82 of the mixed sublimation agent is solidified to form a solidified film 83 containing a sublimable substance on the surface Wa of the substrate W (coagulated film forming step). The coagulation film forming step includes a solvent evaporation step of evaporating the mixing solvent contained in the mixed sublimation agent, and a supply liquid contacting step (S8) described later. If the mixing solvent contained in the mixed sublimation agent has a higher vapor pressure than the sublimable substance contained in the mixed subliming agent, the mixing solvent is preferentially evaporated from the mixed sublimation agent present on the surface Wa of the substrate W. Thus, the mixed sublimation agent can be solidified by a mechanism described below. Then, the film thickness reduction step (S6) of rotating the substrate W at a relatively high speed is included in the solvent evaporation step.

Specifically, in the film thickness decreasing step (S6), the liquid film 81 (thin film 82) and the gas contained in the atmosphere around the surface Wa of the substrate W are generated by rotating the substrate W at a high rotation speed. Increases the number of collisions per unit time. This promotes the vaporization of the molecules of the sublimable substance contained in the mixed sublimation agent.

In this embodiment, a heating step (S7) for heating the surface Wa of the substrate W is performed in parallel with the film thickness reducing step (S6). The heating step (S7) is also included in the solvent evaporation step. In the heating step (S7), the control device 3 opens the heating fluid valve 73. Thereby, as shown in FIG. 7B, the heating fluid is supplied from the lower surface nozzle 12 to the central portion of the back surface Wb of the substrate W in the rotating state. The heating fluid supplied to the back surface Wb of the substrate W receives the centrifugal force generated by the rotation of the substrate W and spreads toward the outer peripheral portion of the substrate W. Thus, the heating fluid is supplied to the entire area of the back surface Wb of the substrate W, and the thin film 82 of the mixed sublimation agent is heated over the entire area of the front surface Wa of the substrate W. By heating the mixed sublimant thin film 82, the mixed solvent having a high vapor pressure among the mixed sublimants contained in the thin film 82 is preferentially evaporated. As the mixing solvent evaporates from the mixed sublimation agent, the concentration of the sublimable substance in the mixed sublimation thin film 82 increases. Accordingly, the solidification point T _FM of the mixed sublimation agent increases, and when the solidification point T _FM reaches room temperature, solidification of the sublimable substance contained in the mixed sublimation agent present on the surface Wa of the substrate W is started. Thereby, the formation of the solidified film 83 can be further promoted.

As the mixed solvent evaporates from the mixed sublimation agent in the film thickness reduction step (S6) and the heating step (S7), as shown by the white arrow in FIG. )), The concentration of the sublimable substance increases. Accordingly, the solidification point T _FM of the mixed sublimation agent increases, and when the solidification point T _FM reaches room temperature, solidification of the mixed sublimation agent present on the surface Wa of the substrate W is started.

(4) When a predetermined period has elapsed from the start of the film thickness reduction step (S6) and the heating step (S7), the supply of the heating fluid to the back surface Wb of the substrate W is stopped.

{Circle around (4)} The control device 3 reduces the rotation speed of the spin base 20 to the liquid processing speed or the liquid processing speed, and maintains the rotation speed.

Next, the supply liquid contacting step (S8) is performed. In the supply liquid contacting step (S8), the control device 3 controls the nozzle moving unit 53 to move the supply liquid nozzle 51 from the retracted position on the side of the spin chuck 5 to the center of the front surface Wa of the substrate W. Move upward. Then, the control device 3 opens the supply liquid valve 55 and discharges the supply liquid from the supply liquid nozzle 51 toward the center of the upper surface (front surface Wa) of the substrate W, as shown in FIG. 7C. The supply liquid is supplied from the supply liquid nozzle 51 at a small flow rate (for example, about 150 mL / min). Therefore, regardless of the supply liquid to the surface Wa of the substrate W, the thin film 82 of the mixed sublimation agent can be maintained in a film shape. Then, the supply liquid is supplied to the surface Wa of the substrate W without breaking the thin film 82 of the mixed sublimation agent while the thin film 82 of the mixed sublimation agent is kept in a film shape. The coagulated film 83 obtained by coagulation of the conductive substance can be provided in a good film shape.

(4) The supply liquid that has landed on the central portion of the surface Wa of the substrate W receives the centrifugal force due to the rotation of the substrate W and flows toward the peripheral portion of the surface Wa of the substrate W. As a result, on the surface Wa of the substrate W, a liquid film 84 of the supply liquid is formed on the thin film 82 of the mixed sublimation agent so as to cover the entire upper surface of the thin film 82. Thus, the mixed sublimant and the supply liquid can be brought into contact with each other over the entire upper surface of the mixed sublimant thin film 82. Therefore, the mixed sublimation agent can be brought into contact with the supply liquid over a wide contact area. Thereby, the solvent for mixing can be more favorably removed from the mixed sublimation agent. Therefore, the sublimable substance can be more solidified.

(4) The temperature of the supply liquid supplied to the surface Wa of the substrate W in the supply liquid contacting step (S8) is lower than room temperature. Therefore, the surface Wa of the substrate W is cooled by the supply of the supply liquid to the surface Wa of the substrate W. Thus, the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 can be lowered.

供給 Furthermore, the supply liquid as a polar substance and the sublimable substance as a nonpolar substance are (almost) insoluble in each other (strictly speaking, camphor is only slightly soluble in water). Therefore, even if the supply liquid is brought into contact with the mixed sublimation agent, the sublimable substance and the supply liquid do not mix with each other.

When an equilibrium state is established in a state where the supply liquid is in contact with the mixed sublimant thin film 82 (in a system in which the mixed sublimate phase and the supply liquid phase are in contact), the mixing solvent is used for the sublimable substance and the supply liquid. Is a unique value (a value determined by the distribution coefficient).

When the sublimable substance is camphor and the feed solution is water, the partition coefficient of the mixing solvent for camphor and water is small (that is, it is remarkably easily distributed to water). In this case, when the supply liquid comes into contact with the mixed sublimation thin film 82, the mixing solvent contained in the mixed sublimation agent moves from the mixed sublimation agent to the supply liquid, and the mixing solvent dissolves in the supply liquid. As the mixing solvent moves, the concentration of the sublimable substance in the mixed sublimant thin film 82 increases. Then, as the concentration of the sublimable substance increases, the freezing point T _FM of the mixed sublimation agent increases, and when the freezing point T _FM reaches room temperature, precipitation of the mixed sublimation agent present on the surface Wa of the substrate W is started. You. By the precipitation of the mixed sublimation agent, a solidified film 83 containing a sublimable substance is formed.

Further, as described above, since the temperature of the supply liquid supplied to the surface Wa of the substrate W is lower than room temperature (for example, the supply liquid is a cooling liquid), the supply of the supply liquid to the surface Wa of the substrate W is performed. Thereby, the temperature of the mixed sublimation agent contained in the mixed sublimation thin film 82 can be lowered. Then, the temperature of the mixed sublimation agent contained in the thin film 82 of the mixing sublimation agent falls below the freezing point T _FM mixing sublimation agent, mixing sublimation agent initiates coagulation. Thus, a solidified film 83 is formed.

In other words, coagulation of the mixed sublimation agent, coagulation and using an increase in freezing point T _FM mixing sublimation agent, coagulation and with temperature decrease of the mixed sublimation agent, to be done at the same time on two mechanisms, the coagulation of the mixed sublimation agent Can be performed in a short period of time.

When a period sufficient for the supply liquid to spread over the entire surface Wa of the substrate W has elapsed from the start of the supply of the supply liquid, the control device 3 closes the supply liquid valve 55 to supply the supply liquid to the surface Wa of the substrate W. Stop supplying.

After that, when a processing time sufficient for all of the sublimable substances contained in the thin film 82 of the mixed sublimation agent on the surface Wa of the substrate W to coagulate has elapsed, the supply liquid contacting step (S8) ends. Next, a supply liquid removing step (S9) for removing the supply liquid from the surface Wa of the substrate W is performed. Specifically, the control device 3 controls the spin motor 18 to accelerate the rotation speed of the substrate W to a swing-off rotation speed at which the supply liquid can be shaken off from the surface Wa of the substrate W. As a result, the supply liquid containing the mixing solvent transferred from the mixed sublimation agent is shaken off from the entire surface Wa of the substrate W. At this time, the supply liquid to be removed also contains the mixing solvent transferred from the sublimable substance. Thereby, the mixing solvent and the supply liquid can be satisfactorily removed from the entire surface Wa of the substrate W. After the supply liquid removing step (S9), only the solidified film 83 is formed on the surface Wa of the substrate W, as shown in FIG. 7E.

後 After the formation of the solidified film 83, the sublimator substance contained in the solidified film 83 sublimates from a solid to a gas. In this embodiment, the removal step (S10) of removing the sublimable substance contained in the solidified film 83 without liquefaction by sublimation of the sublimable substance is realized.

{Circle around (4)} In order to promote sublimation of the solidified film 83, a gas blowing step of blowing gas to the surface Wa of the substrate W is performed in parallel with the removing step (S10).

Specifically, prior to the start of the removing step (S10), the control device 3 controls the nozzle moving unit 58 to move the gas nozzle 56 from the retracted position set around the spin chuck 5 to the position shown in FIG. As shown in the figure, the gas nozzle 56 is moved to the processing position (above the central portion of the surface Wa of the substrate W), and the gas nozzle 56 is lowered to the proximity position where the gas nozzle 56 approaches the substrate W at the processing position. In a state where the gas nozzle 56 is disposed at the processing position (including the above-described proximity position), the central axis of the gas nozzle 56 coincides with the rotation axis A1.

Thereafter, the control device 3 opens the gas valve 60 to start discharging gas from each of the three gas discharge ports (the upper gas discharge port 65, the lower gas discharge port 66, and the center gas discharge port 67) of the gas nozzle 56. . The dehumidified gas is blown to the entire area of the solidified film 83 by the three-layered annular airflow. By blowing such a gas, sublimation of the sublimable substance contained in the solidified film 83 is promoted.

Thereby, in the removal step (S10), all of the sublimable substances contained in the solidified film 83 can be sublimated. Since the sublimable substance is removed from the surface Wa of the substrate W by evaporating without passing through the liquid state, the surface Wa of the substrate W can be dried while effectively suppressing or preventing the pattern 100 from collapsing. .

Next, as shown in FIG. 7G, a final spin-drying step (S11) of drying the substrate W is performed. Specifically, the control device 3 controls the spin motor 18 to rotate the substrate up to a drying rotation speed (for example, several thousand rpm) higher than the rotation speed in each step from the chemical solution step (S2) to the removal step (S10). W is accelerated, and the substrate W is rotated at the drying rotation speed. Thereby, a large centrifugal force is applied on the substrate W. The liquid adhering to the back surface Wb of the substrate W is shaken off around the substrate W. Thus, the liquid is removed from the substrate W, and the back surface Wb of the substrate W is dried.

(4) When a predetermined period has elapsed from the acceleration of the substrate W, the control device 3 controls the spin motor 18 to stop the rotation of the substrate W by the spin chuck 5. Thereafter, the substrate W is carried out of the chamber 4 (Step S12 in FIG. 6). Specifically, the control device 3 causes the hand H of the substrate transfer robot CR to enter the inside of the chamber 4. Then, the control device 3 causes the hand H of the substrate transport robot CR to hold the substrate W on the spin chuck 5. After that, the control device 3 retreats the hand H of the substrate transfer robot CR from the inside of the chamber 4. Thus, the processed substrate W is carried out of the chamber 4.

As described above, according to this embodiment, the mixed sublimation agent in which the sublimable substance and the mixing solvent are mixed is supplied to the surface Wa of the substrate W. Since the sublimable substance has a freezing point T _F1 equal to or higher than room temperature, a part or the whole of the sublimable substance may be in a solid state at room temperature. The freezing point T _FM of the mixed sublimation agent is lower than the freezing point T _F1 of the sublimable substance due to the freezing point drop due to the mixing of the sublimable substance and the mixing solvent. That is, even when the freezing point T _FM mixtures sublimation agent is even above room temperature, the freezing point T _FM mixtures sublimation agent is low. Therefore, it is possible to reduce heat energy for keeping the mixed sublimation agent in a liquid state. Accordingly, it is possible to satisfactorily treat the surface Wa of the substrate W while avoiding unintended solidification of the sublimable substance without significantly increasing the cost.

{Circle around (4)} A liquid film (liquid film 81) of the mixed sublimation agent in which the nonpolar sublimable material and the amphiphilic mixing solvent are mixed is formed on the surface Wa of the substrate W. Then, a supply liquid as a polar substance is supplied to the liquid film (thin film 82) of the mixed sublimation agent. The feed liquid, which is a polar substance, is (almost) insoluble in the sublimable substance, which is a non-polar substance. Therefore, even when the supply liquid comes into contact with the mixed sublimation agent, the sublimable substance and the supply liquid do not mix with each other.

When an equilibrium state is established in a state in which the supply liquid is in contact with the liquid film (thin film 82) of the mixed sublimation agent (in a system in which the phase of the mixed sublimation agent and the supply liquid are in contact), the sublimable substance and the supply liquid are The ratio at which the mixing solvent dissolves becomes a unique value (a value determined by the distribution coefficient). Therefore, for example, when the distribution coefficient of the mixing solvent to the sublimable substance and the supply liquid is small, when the supply liquid comes into contact with the liquid film of the mixed sublimation agent, the mixing solvent contained in the mixed sublimation agent becomes From to the feed. As the mixing solvent moves, the concentration of the sublimable substance in the liquid film of the mixed sublimation agent increases. Then, as the concentration of the sublimable substance increases, the freezing point T _FM of the mixed sublimation agent increases, and when the freezing point T _FM reaches room temperature, the sublimability contained in the mixed sublimation agent present on the surface Wa of the substrate W is increased. The deposition of the substance starts. Thus, a solidified film 83 is formed. Since solidifying the sublimable substance contained in the mixed sublimation agent mixed sublimation agent by utilizing the increase in freezing point T _FM of, thereby cooling the mixture sublimation agent for coagulation of the mixed sublimation agent is not always necessary. Therefore, the sublimable substance supplied to the surface Wa of the substrate W can be solidified well without a large increase in cost.

Further, in the supply liquid contacting step (S8), the supply liquid is supplied to the surface Wa of the substrate W without breaking the mixed sublimant thin film 82 and keeping the mixed sublimate thin film 82 in a film shape. The solidified film 83 obtained by solidifying the sublimable substance contained in the thin film 82 of the mixed sublimation agent can be provided in a good film shape.

In the supply liquid contacting step (S8), the liquid temperature of the supply liquid supplied to the surface Wa of the substrate W is lower than room temperature. Therefore, the surface Wa of the substrate W can be cooled by supplying the supply liquid to the surface Wa of the substrate W. Thus, the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 can be lowered. Then, the temperature of the mixed sublimation agent contained in the thin film 82 of the mixing sublimation agent falls below the freezing point T _FM mixing sublimation agent, sublimable substance contained in the mixed sublimation agent initiates coagulation. Thus, a solidified film 83 is formed.

Further, since the vapor pressure of the mixing solvent is higher than the vapor pressure of the sublimable substance, the mixing solvent is preferentially evaporated from the mixed sublimation agent present on the surface Wa of the substrate W. As the mixing solvent evaporates from the mixed sublimation agent, the concentration of the sublimable substance in the mixed sublimation thin film 82 increases. Accordingly, the freezing point T _FM of the mixed sublimation agent increases, and when the freezing point T _FM reaches room temperature, solidification of the sublimable substance contained in the mixed sublimation agent present on the surface Wa of the substrate W is started. Thereby, the formation of the solidified film 83 can be further promoted.

(4) Further, (cooling water) is supplied to the front surface Wa of the substrate W in the supply liquid contacting step (S8), and the heating fluid is supplied to the back surface Wb of the substrate W in the heating step (S7). Therefore, the temperature range can be divided between the front surface Wa of the substrate W and the rear surface Wb of the substrate W. Therefore, on each of the front surface Wa side and the rear surface Wb side of the substrate W, the execution time and the like of each process can be set without considering the influence of the heat history.

FIG. 8A is an illustrative sectional view for explaining a configuration example of the processing unit 202 according to the second embodiment of the present invention.

において In the second embodiment, the same reference numerals as those in FIGS. 1 to 7 denote the same parts in the first embodiment, and a description thereof will be omitted.

The difference between the processing unit 202 according to the second embodiment and the processing unit 2 according to the first embodiment (see FIG. 2) is that the processing unit 202 faces the upper surface of the substrate W held by the spin chuck 5 and The point is that a blocking member 210 for blocking the space above W from the surrounding atmosphere is provided. Another difference is that a gas blowing unit 211 is provided instead of the gas blowing unit 11. In this embodiment, the upper surface nozzle 221, the gas pipe 224 and the gas valve 225 constitute a gas blowing unit 211.

The blocking member 210 includes the blocking plate 220 and an upper surface nozzle 221 that vertically passes through a central portion of the blocking plate 220. A blocking plate rotating unit (not shown) having a configuration including an electric motor and the like is connected to the blocking plate 220. This blocking plate rotation unit rotates the blocking plate 220 around a rotation axis (not shown) coaxial with the rotation axis A1.

The blocking plate 220 has a circular substrate facing surface 220a on the lower surface facing the entire upper surface of the substrate W. At the center of the substrate facing surface 220a, there is formed a cylindrical through hole 220b vertically penetrating the blocking plate 220. The upper surface nozzle 221 is inserted through the through hole 220b. A cylindrical portion projecting downward over the entire area may be formed on the outer peripheral edge of the substrate facing surface 220a.

The upper surface nozzle 221 is attached to the blocking plate 220 so as to be able to move up and down integrally. The upper surface nozzle 221 has, at its lower end, a discharge port 221a facing the center of the upper surface of the substrate W held by the spin chuck 5.

遮断 A blocking member elevating unit (not shown) configured to include an electric motor, a ball screw, and the like is connected to the blocking member 210. The blocking member elevating unit (not shown) vertically moves the blocking plate 220 and the upper surface nozzle 221 vertically.

The blocking member elevating unit retracts the blocking plate 220 to a blocking position (the position shown in FIG. 8B) where the substrate facing surface 220 a is close to the upper surface of the substrate W held by the spin chuck 5, and retreats significantly higher than the blocking position. Up and down between the retracted positions (the positions shown in FIG. 2). The blocking member elevating unit can hold the blocking plate 220 at both the blocking position and the retracted position. The blocking position is a position where the substrate facing surface 220a forms a blocking space 230 (see FIG. 8B) between the substrate facing surface 220a and the surface Wa of the substrate W. Although the isolation space 230 is not completely isolated from the surrounding space, no gas flows into the isolation space 230 from the surrounding space. That is, the cutoff space 230 is substantially cut off from the surrounding space.

気体 A gas pipe 224 is connected to the upper surface nozzle 221. The gas pipe 224 is provided with a gas valve 225 that opens and closes the gas pipe 224. The gas applied to the gas pipe 224 is a dehumidified gas, particularly an inert gas. The inert gas includes, for example, nitrogen gas and argon gas. The gas may be an active gas such as air. When the gas valve 225 is opened, an inert gas is supplied to the upper surface nozzle 221. As a result, the gas is discharged downward from the discharge port 221a, and the discharged gas is sprayed on the surface Wa of the substrate W. In this embodiment, the upper surface nozzle 221, the gas pipe 224, and the gas valve 225 form a gas blowing unit.

Furthermore, the rinsing liquid supply unit 7 may include the upper surface nozzle 221 as a rinsing liquid nozzle. That is, the rinsing liquid from the rinsing liquid pipe 37 may be supplied to the upper surface nozzle 221.

FIG. 8B is a schematic view showing the removing step (S10) performed in the processing unit 202. Prior to the start of the removal step (S10), the control device 3 controls the blocking member lifting / lowering unit, and as shown in FIG. 8B, lowers the blocking member 210 and arranges it in the blocking position.

制御 In the gas blowing step, the control device 3 opens the gas valve 225. Thus, as shown in FIG. 8B, the dehumidified gas is discharged from the discharge port 221a of the upper surface nozzle 221 toward the center of the front surface Wa of the substrate W in the rotating state. The gas from the upper surface nozzle 221 is blown to the center of the surface Wa of the substrate W. Further, the gas from the upper surface nozzle 221 moves in the blocking space 230 toward the outer peripheral portion of the substrate W. Thereby, gas is blown over the entire surface Wa of the substrate W. By blowing such a gas, sublimation of the sublimable substance contained in the solidified film 83 is promoted.

Although the two embodiments of the present invention have been described above, the present invention can be embodied in other forms.

For example, in the supply liquid contacting step (S8), the supply position of the supply liquid on the surface Wa of the substrate W may be moved within the surface Wa of the substrate W.

As shown in FIGS. 9A and 9B, the nozzle moving unit 53 (see FIG. 4) is configured such that the supply liquid discharged from the supply liquid nozzle 51 lands on the center of the upper surface of the substrate W, The supply liquid nozzle 51 is moved horizontally between the peripheral position where the discharged supply liquid lands on the upper peripheral part of the substrate W. The center position and the peripheral position are both processing positions. A gas nozzle 301 for discharging gas downward is attached to the nozzle arm 52. Therefore, when the nozzle arm 52 is moved, the supply liquid nozzle 51 and the gas nozzle 301 move while keeping the positional relationship between the supply liquid nozzle 51 and the gas nozzle 301 constant. The gas nozzle 301 is attached to the nozzle arm 52 such that the gas blowing area on the surface Wa of the substrate W is located radially inside the supply position of the supply liquid on the surface Wa of the substrate W.

気体 A gas pipe 302 for guiding gas to the gas nozzle 301 is connected to the gas nozzle 301. The gas pipe 302 is provided with a gas valve 303. When the gas valve 303 is opened, gas from a gas supply source is supplied from the gas pipe 302 to the gas nozzle 301. Thereby, gas is blown downward from the gas nozzle 301.

The gas supplied to the gas pipe 302 is a dehumidified gas, particularly an inert gas. The inert gas includes, for example, nitrogen gas and argon gas. The gas may be an active gas such as air.

Then, in the supply liquid contacting step (S8), the control device 3 controls the nozzle moving unit 53 to change the supply liquid nozzle 51 discharging the supply liquid and the gas nozzle 301 discharging the gas. The substrate W is horizontally moved from the center to the periphery of the substrate W.

凝固 At the supply position PS of the supply liquid on the surface Wa of the substrate W, solidification is performed immediately after the supply, and a solidified body 83A is formed. Further, at the gas blowing position PB on the surface Wa of the substrate W, the supplied liquid is blown off by the gas. Thus, the supply liquid contributes to the solidification on the surface Wa of the substrate W, and is then quickly removed from the surface Wa.

By moving the supply position PS from the center of the substrate W to the peripheral edge while suitably adjusting the moving speed of the supply position PS so that the solidified body 83A of the supply liquid can be formed satisfactorily at each supply position PS, The formation position of the body 83A extends from the central portion of the substrate W to the peripheral portion of the substrate W. Thus, the solidified film 83 can be formed on the entire surface Wa of the substrate W.

Since the solidified film 83 can be formed over the entire surface Wa of the substrate W by moving the supply liquid nozzle 51 from the center position to the peripheral position, the solidified film 83 covering the entire surface Wa of the substrate W can be formed in a short time. be able to.

{Circle around (4)} Since the supply liquid supplied to the surface Wa of the substrate W is removed by the gas blown from the gas nozzle 301, there is no need to perform a separate supply liquid removal step (S9). Therefore, the processing time can be reduced, and the throughput can be improved.

In the supply liquid contacting step (S8), the supply liquid nozzle 51 supplies a continuous supply liquid to the surface Wa of the substrate W. However, as shown in FIG. The supply liquid may be discharged in a shower form from the supply liquid nozzle 451 having the lower surface 451a. The shower-like supply liquid discharged from the supply liquid nozzle 451 is supplied to the entire surface Wa of the substrate W. The discharge pressure of the supply liquid discharged from the supply liquid nozzle 451 is weak. Since the shower-like supply liquid having a low discharge pressure is supplied to the surface Wa of the substrate W, in the supply liquid contacting step (S8), the supply of the supply liquid does not disturb the film shape of the mixed sublimation thin film 82. Therefore, the supply liquid can be supplied to the surface Wa of the substrate W while maintaining the film shape of the mixed sublimation thin film 82.

In the example of FIG. 10, the supply range of the supply liquid from the supply liquid nozzle 451 is the entire surface Wa of the substrate W, but the supply range of the supply liquid from the supply liquid nozzle 451 is It may be a part of the surface Wa. In this case, the supply liquid nozzle 451 may be moved in the horizontal direction to scan the supply range so as to cover the entire surface Wa of the substrate W.

基板 In addition, for example, in the supply liquid contacting step (S8), the substrate W may be cooled. As a method of cooling the substrate W in this manner, a method of supplying a cooling fluid to the back surface Wb of the substrate W, a method of disposing a cooling plate 501 as shown in FIG.

The cooling plate 501 as a cooling unit is provided instead of the lower surface nozzle 12. The cooling plate 501 is arranged above the spin base 20 and below the substrate W held by the holding member 21. The cooling plate 501 has an upper surface 501a facing the entire rear surface Wb of the substrate W. Even if the spin chuck 5 rotates, the cooling plate 501 does not rotate. The temperature of the cooling plate 501 is changed by the control device 3. The temperature of the upper surface 501a of the cooling plate 501 is uniform in the plane. The control device 3 lowers the temperature of the cooling plate 501 so that the entire surface Wa of the substrate W is uniformly cooled. In addition, the cooling plate 501 may be used for cooling a cooling fluid or a heating fluid.

Another example of the cooling unit that cools the surface Wa of the substrate W includes a configuration in which a cooler is built in the blocking member 210.

内蔵 As shown in FIG. 12, the built-in cooler 601 is disposed inside the blocking plate 220 of the blocking member 210. The built-in cooler 601 moves up and down together with the blocking member 210. The substrate W is disposed below the built-in cooler 601. Built-in cooler 601 is, for example, a piezo element. The temperature of built-in cooler 601 is changed by control device 3. The temperature of the substrate facing surface 220a is uniform within the surface.

In the supply liquid contacting step (S8), the controller 3 may cool the surface Wa of the substrate W by lowering the temperature of the built-in cooler 601 to a temperature lower than room temperature. Thereby, the mixed sublimation agent on the surface Wa of the substrate W can be cooled.

In the supply liquid contacting step (S8), the supply liquid supplied to the supply liquid pipe 54 may have a liquid temperature higher than room temperature. In this embodiment, the temperature of the supply liquid is 50 ° C. to 60 ° C. When the mixing solvent has a vapor pressure higher than the vapor pressure of the sublimable substance, in the supply liquid contact step (S8), the mixing solvent is removed from the mixed sublimation agent present on the surface Wa of the substrate W. Is preferentially evaporated. As the mixing solvent evaporates from the mixed sublimation agent, the concentration of the sublimable substance in the liquid film of the mixed sublimation agent increases. Accordingly, the freezing point T _FM of the mixed sublimation agent increases, and when the freezing point T _FM reaches room temperature, solidification of the sublimable substance contained in the mixed sublimation agent present on the surface Wa of the substrate W is started. Thereby, the formation of the solidified film 83 can be further promoted in the supply liquid contacting step (S8).

In the above-described embodiment, the coagulated film forming step includes the supply liquid contacting step (S8) and the solvent evaporating step, and the solvent evaporating step includes the film thickness decreasing step (S6: substrate rotating step) and the heating step (S7). It was described as including. The heating step (S7) and the film thickness reducing step (S6) are not performed in parallel with each other, but may be performed separately.

The heating unit that heats the front surface Wa of the substrate W in the heating step (S7) is not limited to the configuration that supplies the heating fluid to the rear surface Wb of the substrate W as in the above-described embodiment. As shown in FIG. 13, a hot plate 701 disposed below and opposed to the back surface Wb of the substrate W can be used as a heating unit. The hot plate 701 is provided instead of the lower surface nozzle 12. The hot plate 701 has a built-in heater 702 built therein. The built-in heater 702 is, for example, a heating wire that generates heat when energized. The hot plate 701 is arranged above the spin base 20 and below the substrate W held by the holding member 21. The hot plate 701 has an upper surface 701a that faces the entire rear surface Wb of the substrate W. Even if the spin chuck 5 rotates, the hot plate 701 does not rotate. The temperature of the hot plate 701 is changed by the control device 3. The temperature of the upper surface 701a of the hot plate 701 is uniform in the plane. When the controller 3 raises the temperature of the hot plate 701, the entire surface Wa of the substrate W is uniformly heated.

In this case, in the heating step (S7), instead of supplying a heating fluid to the back surface Wb of the substrate W, the control device 3 raises the temperature of the hot plate 701 to a temperature higher than room temperature, so that the substrate W The surface Wa may be heated. Alternatively, the fluid at room temperature may be heated to a temperature higher than room temperature by the hot plate 701 and then supplied to the substrate W. Further, the heating fluid may be supplied to the substrate W after being raised to a higher temperature by the hot plate 701. This makes it possible to favorably evaporate the mixing solvent contained in the mixed sublimation agent on the surface Wa of the substrate W.

As another example of the heating unit for heating the surface Wa of the substrate W, a configuration in which a heater is built in the blocking member 210 as shown in FIG.

内蔵 As shown in FIG. 14, the built-in heater 801 is arranged inside the blocking plate 220 of the blocking member 210. The built-in heater 801 moves up and down together with the blocking member 210. The substrate W is disposed below the built-in heater 801. The built-in heater 801 is, for example, a heating wire that generates heat when energized. The temperature of the built-in heater 801 is changed by the control device 3. The temperature of the substrate facing surface 220a is uniform within the surface.

In the heating step (S7), the control device 3 raises the temperature of the built-in heater 801 to a temperature higher than room temperature while arranging the blocking member 210 at the blocking position as shown in FIG. Wa may be heated. Thereby, the mixing solvent contained in the mixed sublimation agent on the surface Wa of the substrate W can be favorably evaporated.

{Circle around (4)} The solvent evaporation step may include at least one of four steps in which a gas blowing step and a depressurization step are added to the film thickness reducing step (S6) and the heating step (S7). The gas blowing step is a step equivalent to the above-described gas blowing step executed in parallel with the removing step (S10).

The pressure reduction step is performed as follows. The exhaust device 17 (see FIG. 2) is provided so that its exhaust force (suction force) can be adjusted. The exhaust device 17 is provided with an exhaust power adjustment unit (decompression unit) 901 (shown by a two-dot chain line in FIG. 2). The exhaust power adjustment unit 901 is, for example, a regulator or an opening adjustment valve. By adjusting the exhaust force of the exhaust device 17 by the exhaust force adjusting unit 901, the pressure inside the chamber 4 is changed. That is, the pressure inside the chamber 4 is changed by the control device 3.

In the coagulation film forming step, the control device 3 can satisfactorily evaporate the second sublimable substance contained in the mixed sublimation agent on the surface Wa of the substrate W by reducing the pressure inside the chamber 4. Further, it is sufficient that a pipe communicating with the exhaust power adjusting unit (decompression unit) 901 is provided in the chamber 4, and it is not always necessary to provide the exhaust device 17 with a pipe.

In addition, the solvent evaporation step is performed in combination with at least one of the film thickness reduction step (S6), the heating step (S7), the gas blowing step, and the pressure reduction step, or in place of these steps, or by natural drying or substrate drying. By applying ultrasonic vibration to the mixed sublimation agent on the surface Wa of W, the mixing solvent contained in the mixed sublimation agent on the surface Wa of the substrate W may be evaporated.

{Circle around (4)} The coagulation film forming step only needs to include the supply liquid contact step (S8), and does not necessarily need to include the solvent evaporation step.

In particular, when the mixing solvent has the same vapor pressure as the sublimable substance or is lower than the vapor pressure of the sublimable substance, the mixing solvent contained in the mixed sublimation agent does not evaporate preferentially. There is no point in doing.

供給 Further, the supply liquid removing step (S9) has been described as the shaking off step of rotating the substrate W about the rotation axis A1 to shake off the supply liquid existing on the surface Wa of the substrate W. Instead of / in conjunction with this shaking-off step, a gas blowing step of blowing gas onto the surface Wa of the substrate W may be performed as the supply liquid removing step (S9). The gas blowing step is a step equivalent to the above-described gas blowing step executed in parallel with the removing step (S10).

{Also, it has been described that the gas blowing step is performed in parallel with the removing step (S10) to promote the sublimation of the mixed subliming agent. The step for promoting sublimation may include at least one of three steps in which the substrate blowing step and the heating step are added to the gas blowing step. The heating step is the same step as the above-described heating step (S7) and its modification. The substrate high rotation step is equivalent to the substrate high rotation step (spin-off) performed in the film thickness reduction step (S6).

In the case where the substrate high rotation step is performed in the removing step (S10), since the back surface Wb of the substrate W after the removing step (S10) has already been dried, it is not necessary to shake off and dry after the removing step (S10). It is. Therefore, the final spin dry step (S11) may be omitted.

In the case where a water-containing liquid is used as the supply liquid, the supply liquid supply unit 10 may be provided as a unit shared with the rinse liquid supply unit 7. When an organic solvent is used as the supply liquid, the supply liquid supply unit 10 may be provided as a unit shared with the replacement solvent supply unit 8.

In addition, in each of the aforementioned substrate processing examples, the replacement step (S4) is performed between the rinsing step (S3) and the mixed sublimation agent supply step (S5). However, when the mixed sublimation agent has miscibility with the rinsing liquid (that is, water), the substitution step (S4) may be omitted. In this case, the configuration of the replacement solvent supply unit 8 of the processing unit 2 may be omitted.

Further, the freezing point T _FM mixtures sublimation agent supplied from the mixing sublimation agent supply unit 9 may be above room temperature and not less than room temperature. In this case, a device (temperature control device) for maintaining the mixed sublimation agent in a liquid state inside the mixed sublimation agent supply unit 9 is required. However, since the freezing point T _FM of the mixed sublimation agent is lower than the freezing point T _F1 of the sublimable substance due to freezing point depression, the amount of heat for maintaining the mixed sublimation agent in a liquid state can be reduced.

Further, as shown in FIG. 15, the removing step (S10) of changing the sublimable substance contained in the solidified film 83 into a gas without passing through a liquid state is not a sublimation step, but a plasma that irradiates the substrate W with plasma. It may be an irradiation step. That is, in the removal step, the sublimable substance contained in the solidified film 83 may be changed to a gas without passing through a liquid by decomposition by an oxygen radical or the like or by a chemical reaction. Further, a removal step such as a plasma irradiation step may be performed in another processing unit.

FIG. 15 is a schematic diagram for explaining the transfer of the substrate W from the wet processing unit 2W to the dry processing unit 2D that changes the sublimable substance contained in the solidified film 83 into a gas without passing through a liquid state. . In FIG. 15, the same components as those shown in FIGS. 1 to 14 are denoted by the same reference numerals as those in FIG. 1 and the like, and description thereof is omitted.

The processing unit 2 includes a dry processing unit 2D for processing the substrate W without supplying the processing liquid to the substrate W, in addition to the wet processing unit 2W for supplying the processing liquid to the substrate W. FIG. 15 shows that the dry processing unit 2D includes a processing gas pipe 1001 that guides a processing gas into a chamber (second chamber) 4D, and a plasma generator 1002 that changes the processing gas in the chamber 4D into plasma. An example is shown. The plasma generator 1002 includes an upper electrode 1003 arranged above the substrate W, and a lower electrode 1004 arranged below the substrate W.

工程 The steps from the loading of the substrate W (S1) to the supply liquid removing step (S9) shown in FIG. 15 are performed in the chamber 4 of the wet processing unit 2W. Thereafter, as shown in FIG. 15, the substrate W is carried out of the chamber 4 of the wet processing unit 2W by the substrate transfer robot CR, and is carried into the chamber 4D of the dry processing unit 2D. The sublimable substance contained in the solidified film 83 remaining on the surface Wa of the substrate W changes into a gas without passing through a liquid by a chemical reaction and a physical reaction caused by the plasma in the chamber 4D. Thus, the solidified film 83 is removed from the substrate W. In the example of FIG. 15, since the formation of the coagulation film 83 and the removal of the coagulation film 83 are performed in the

chambers

4 and 4D, respectively, the structures in the

chambers

4 and 4D can be simplified, and the

chambers

4 and 4D can be downsized. it can.

The present invention can also be applied to a batch type substrate processing apparatus.

FIG. 16 is a schematic diagram for explaining a configuration of a substrate processing apparatus 1101 according to the third embodiment of the present invention. FIG. 17 is a schematic diagram showing a state of lifting in the substrate processing apparatus 1101.

The substrate processing apparatus 1101 is a batch-type substrate processing apparatus that processes a plurality of substrates W at a time. The substrate processing apparatus 1101 includes a chemical liquid storage tank 1102 for storing a chemical liquid, a rinse liquid storage tank 1103 for storing a rinse liquid (for example, water), and a mixed sublimate storage tank (first tank) 1104 for storing a mixed sublimate. And a supply liquid storage tank 1105 (second tank) for storing a supply liquid (for example, a water-containing liquid).

The substrate processing apparatus 1101 further includes a lifter 1106 for immersing the substrate W in the supply liquid stored in the supply liquid storage tank 1105, and a lifter elevating unit 1107 for raising and lowering the lifter 1106. The lifter 1106 supports each of the plurality of substrates W in a vertical posture. The lifter elevating unit 1107 includes a processing position (a position indicated by a solid line in FIG. 16) in which the substrate W held by the lifter 1106 is located in the supply liquid storage tank 1105, and a supply position of the substrate W held by the lifter 1106. The lifter 1106 is moved up and down between a retreat position (a position shown by a two-dot chain line in FIG. 16) to retreat upward from the storage tank 1105.

In a series of processes in the substrate processing apparatus 1101, a plurality of substrates W carried into the processing unit of the substrate processing apparatus 1101 are immersed in the chemical stored in the chemical storage tank 1102. As a result, chemical processing (cleaning processing or etching processing) is performed on each substrate W (chemical processing). When a predetermined period elapses from the start of immersion in the chemical, a plurality of substrates W are lifted from the chemical storage tank 1102 and moved to the rinse liquid storage tank 1103. Next, the plurality of substrates W are immersed in the rinsing liquid stored in the rinsing liquid storage tank 1103. Thereby, a rinsing process is performed on the substrate W (rinsing step). When a predetermined period elapses from the start of immersion in the rinsing liquid, the plurality of substrates W are lifted from the rinsing liquid storage tank 1103 and moved to the mixed sublimation agent storage tank 1104. Next, the plurality of substrates W are immersed in the mixed sublimation agent stored in the mixed sublimation agent storage tank 1104. Thereby, the mixed sublimation agent processing is performed on the substrate W (mixed sublimation agent supply step). When a predetermined period elapses from the start of immersion in the mixed sublimation agent, the plurality of substrates W are lifted from the mixed sublimation agent storage tank 1104 and moved to the supply liquid storage tank 1105.

液 A liquid film of the mixed sublimation agent is formed on the entire surface of the surface Wa of each substrate W transferred to the supply liquid storage tank 1105. Then, the lifter elevating unit 1107 is controlled to move the lifter 1106 from the retracted position to the processing position, so that the plurality of substrates W held by the lifter 1106 are immersed in the supply liquid. Thereby, the supply liquid is supplied to the surface Wa of each substrate W, and the supply liquid comes into contact with the liquid film of the mixed sublimation agent formed on the surface Wa of the substrate W (supply liquid contact step).

When the supply liquid comes into contact with the liquid film of the mixed sublimation agent, the mixing solvent contained in the mixed sublimation agent moves from the mixed sublimation agent to the supply liquid, and the mixing solvent dissolves in the supply liquid. As the mixing solvent moves, the concentration of the sublimable substance in the liquid film of the mixed sublimation agent increases. Then, as the concentration of the sublimable substance increases, the freezing point T _FM of the mixed sublimation agent increases, and when the freezing point T _FM reaches room temperature, precipitation of the mixed sublimation agent present on the surface Wa of the substrate W is started. You. By the precipitation of the mixed sublimation agent, a solidified film 83 containing a sublimable substance is formed.

When the liquid temperature of the supply liquid stored in the supply liquid storage tank 1105 is lower than room temperature, the supply of the supply liquid to the surface Wa of the substrate W causes the mixed sublimation contained in the liquid film of the mixed sublimation agent. The agent can be cooled. Then, the temperature of the mixed sublimation agent contained in the liquid film of the mixed sublimation agent falls below the freezing point T _FM mixing sublimation agent, mixing sublimation agent initiates coagulation. Thus, a solidified film 83 is formed.

In other words, coagulation of the mixed sublimation agent, coagulation and using an increase in freezing point T _FM mixing sublimation agent, coagulation and with temperature decrease of the mixed sublimation agent, for simultaneously as two mechanisms, the coagulation membrane 83, It can be formed in a short time.

(4) When a predetermined period has elapsed from the start of immersion of the substrate W in the supply liquid, the lifter elevating unit 1107 is controlled, and the lifter 1106 is moved from the processing position to the retreat position. Thereby, the plurality of substrates W immersed in the supply liquid are pulled up from the supply liquid.

時には When the substrate W is pulled up from the supply liquid, pull-up drying (supply liquid removal step) is performed. As shown in FIG. 17, the pull-up drying is performed while blowing a gas (for example, an inert gas such as nitrogen gas) onto the surface Wa of the substrate W pulled up from the supply liquid storage tank 1105, and at a relatively low speed (for example, several times). (mm / sec). Thereby, the supply liquid is removed from the entire surface Wa of the substrate W.

After that, the sublimator substance contained in the solidified film 83 sublimates from a solid to a gas. Thereby, the sublimable substance can be removed from the surface Wa of the substrate W by evaporating without passing through the liquid state, so that the surface Wa of the substrate W is dried while effectively suppressing or preventing the pattern 100 from collapsing. be able to.

Further, in each of the above-described embodiments, the case where the

substrate processing apparatuses

1 and 1101 are apparatuses for processing a substrate W made of a semiconductor wafer has been described, but the substrate processing apparatus is a substrate for a liquid crystal display device, an organic EL (electroluminescence). An apparatus for processing a substrate such as a substrate for an FPD (Flat Panel Display) such as a display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, and a substrate for a solar cell. Is also good.

In addition, various design changes can be made within the scope of the matters described in the claims.

This application corresponds to Japanese Patent Application No. 2018-177377 filed with the Japan Patent Office on September 21, 2018, and the entire disclosure of this application is incorporated herein by reference.

1: substrate processing apparatus 2: processing unit 3: control apparatus 4: chamber 5: spin chuck (substrate holding unit)
9: Mixed sublimation agent supply unit (mixed drying auxiliary substance supply unit)
10: Supply liquid supply unit 11: Gas blowing unit (removal unit)
18: Spin motor (removal unit)
81: liquid film 82: thin film 83: solidified film 100: pattern 1104: mixed sublimant storage tank (first tank)
1105: Supply liquid storage tank (second tank)
A1: Rotation axis T _F1 : Freezing point of sublimable substance (freezing point of auxiliary drying substance)
T _FM : Freezing point of mixed sublimation agent (freezing point of mixed drying auxiliary substance)
W: Substrate Wa: Surface

Claims

A substrate processing method for processing a substrate having a pattern on a surface,
A non-polar drying auxiliary substance and a solvent having amphipathic properties are mixed dry auxiliary substances mixed with each other, wherein the mixed drying auxiliary substance having a freezing point lower than the freezing point of the drying auxiliary substance is mixed with the substrate. Supplying to the surface, a mixed drying auxiliary substance supplying step of forming a liquid film of the mixed drying auxiliary substance on the surface of the substrate,
A coagulation film forming step of forming a coagulation film containing the drying auxiliary material by coagulating the drying auxiliary material contained in the liquid film of the mixed drying auxiliary material,
Removing the drying auxiliary substance contained in the coagulated film from the surface of the substrate by changing to a gas without passing through a liquid state,
The coagulation film forming step,
The drying auxiliary substance and the solvent are different kinds of liquids, and the supply liquid that is a polar substance is brought into contact with a liquid film of the mixed drying auxiliary substance, and the solvent dissolved in the mixed drying auxiliary substance is the solvent. A feed liquid contacting step of forming the coagulated film by precipitating the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film due to moving from the mixed drying auxiliary substance to the supply liquid, Substrate processing method.
The substrate processing method according to claim 1, wherein the drying auxiliary substance includes a sublimable substance having sublimability.
The substrate processing method according to claim 1, wherein the supply liquid contacting step includes a step of supplying the supply liquid to the surface of the substrate while maintaining a liquid film of the mixed and dried auxiliary substance in a film form. .
The substrate processing method according to claim 1 or 2, further comprising a supply liquid removing step of removing the supply liquid existing on the surface of the substrate before the removing step.
The supply liquid removing step includes rotating the substrate around a predetermined rotation axis to shake off the supply liquid existing on the surface of the substrate, and a gas blowing step of blowing gas to the surface of the substrate. The substrate processing method according to claim 4, comprising at least one.
3. The substrate processing method according to claim 1, wherein the supply liquid supplied to the surface of the substrate in the supply liquid contacting step has a liquid temperature lower than room temperature.
The solvent has a higher vapor pressure than the vapor pressure of the drying aid;
The substrate processing method according to claim 1, wherein the supply liquid supplied to the surface of the substrate in the supply liquid contacting step has a liquid temperature higher than room temperature.
The solvent has a higher vapor pressure than the vapor pressure of the drying aid;
The substrate processing method according to claim 1, wherein the coagulation film forming step further includes a solvent evaporating step of evaporating the solvent from the mixed and dried auxiliary substance present on the surface of the substrate.
A heating step of heating the mixed drying auxiliary substance, a gas blowing step of blowing a gas to the mixed drying auxiliary substance, a depressurizing step of depressurizing a space around the solidified film, and a surface of the substrate. 9. The substrate processing method according to claim 8, comprising at least one of a substrate high rotation step of rotating the substrate at a high speed around a predetermined rotation axis without supplying a liquid to the substrate.
10. The substrate processing method according to claim 9, wherein the heating step includes a step of supplying a heating fluid to a back surface of the substrate.
3. The substrate processing method according to claim 1, wherein the solvent has a vapor pressure equal to or lower than a vapor pressure of the drying auxiliary substance.
The supply liquid contacting step moves a supply position of the supply liquid on the surface of the substrate from a central portion of the substrate to a peripheral portion of the substrate in parallel with the supply of the supply liquid to the surface of the substrate. 3. The substrate processing method according to claim 1, further comprising: expanding a formation position of the solidified film on a surface of the substrate from a central portion of the substrate to a peripheral portion of the substrate.
The removing step is a sublimation step of sublimating the drying auxiliary substance contained in the coagulated film from a solid to a gas, and the decomposition of the coagulated film causes the drying auxiliary substance contained in the coagulated film to pass through a liquid state. At least one of a decomposition step of converting the gas into a gas without reacting, and a reaction of the coagulation film, the drying auxiliary substance contained in the coagulation film, a reaction step of changing the gas into a gas without passing through a liquid state. The substrate processing method according to claim 1, further comprising:
The mixing and drying auxiliary substance supply step includes a step of immersing the substrate in a first tank storing the mixing and drying auxiliary substance,
2. The substrate processing method according to claim 1, wherein the supply liquid contacting step includes a step of immersing the substrate in a second tank storing the supply liquid. 3.
The substrate processing method according to claim 1 or 2, wherein the supply liquid contains water.
A substrate processing method for processing a substrate having a pattern on a surface,
A non-polar drying auxiliary substance and a solvent having amphipathic properties are mixed dry auxiliary substances mixed with each other, wherein the mixed drying auxiliary substance having a freezing point lower than the freezing point of the drying auxiliary substance is mixed with the substrate. Supplying to the surface, a mixed drying auxiliary substance supplying step of forming a liquid film of the mixed drying auxiliary substance on the surface of the substrate,
A coagulation film forming step of forming a coagulation film containing the drying auxiliary material by coagulating the drying auxiliary material contained in the liquid film of the mixed drying auxiliary material,
Removing the drying auxiliary substance contained in the coagulated film from the surface of the substrate by changing to a gas without passing through a liquid state,
The coagulation film forming step,
A method for treating a substrate, comprising: a liquid contacting step for forming the coagulated film by depositing the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film.
A substrate holding unit that holds a substrate having a pattern on its surface,
On a surface of the substrate held by the substrate holding unit, a drying auxiliary substance that is a nonpolar substance and a solvent having amphipathic properties are mixed dry auxiliary substances mixed together, and the freezing point of the drying auxiliary substance is mixed. A mixed drying auxiliary substance supply unit for supplying a mixed drying auxiliary substance having a lower freezing point,
On the surface of the substrate held by the substrate holding unit, a supply liquid supply unit for supplying a supply liquid that is a different liquid from the drying auxiliary substance and the solvent, and a polar substance,
A removal unit for removing the drying auxiliary substance from the surface of the substrate held by the substrate holding unit by changing the gas into a gas without passing through a liquid state,
The mixing and drying auxiliary substance supply unit, and a control device that controls the supply liquid supply unit and the removal unit,
A mixing / drying auxiliary substance supplying step of supplying the mixed / drying auxiliary substance to the surface of the substrate by the mixing / drying auxiliary substance supply unit and forming a liquid film of the mixed / drying auxiliary substance on the surface of the substrate; A coagulation film forming step of forming a coagulation film containing the drying auxiliary material by coagulating the drying auxiliary material contained in the liquid film of the mixed drying auxiliary material; and the drying auxiliary material contained in the coagulation film A removing step of removing the substrate from the surface by changing to a gas without passing through a liquid state by the removing unit,
In the coagulation film forming step, the control device supplies the supply liquid to the liquid film of the mixed drying auxiliary substance by the supply liquid supply unit, and the solvent dissolved in the mixed drying auxiliary substance is used as the mixed drying auxiliary substance. Performing a liquid-contacting liquid supply step of forming the coagulated film by depositing the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film accompanying the transfer from a substance to the supply liquid; apparatus.