Substrate Processing Method and Substrate Processing Apparatus

Abstract

The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method of the present invention processes a substrate having a pattern on its front surface, and comprises: a mixed drying auxiliary substance supplying step, wherein a mixed drying auxiliary substance is supplied to the front surface of the substrate to form a liquid film of the mixed drying auxiliary substance on the front surface of the substrate, wherein the mixed drying auxiliary substance is obtained by mixing a drying auxiliary substance as a non-polar substance with an amphiphilic solvent and has a freezing point lower than that of the drying auxiliary substance; a solidified film forming step, wherein the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance solidifies to form a solidified film containing the drying auxiliary substance; and a removal step, wherein the drying auxiliary substance contained in the solidified film is converted into a gas without passing through a liquid state and is removed from the front surface of the substrate. The solidification film forming step includes a supply liquid contacting step, wherein the supply liquid contacting step is to contact a supply liquid of a polar substance different from the drying auxiliary substance and the solvent with a liquid film of the mixed drying auxiliary substance. As the solvent dissolved in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid, the concentration of the drying auxiliary substance in the liquid film increases, thereby causing the drying auxiliary substance to precipitate, thereby forming the solidification film.

Description

Technical Field

[0001] 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 (LCDs), substrates for FPDs (flat panel displays) such as organic EL (electroluminescence) displays, substrates for optical disks, magnetic disks, magneto-optical disks, photomask substrates, ceramic substrates, and solar cell substrates. Background Art

[0002] In the manufacturing process of semiconductor devices, wet substrate processing is performed.

[0003] For example, there is a case where etching residues, metal impurities, or organic contaminants, which are reaction byproducts, adhere to the front side (pattern-forming surface) of a substrate formed with a fine pattern having uneven surfaces through a dry etching step or the like. In order to remove these substances from the front side of the substrate, a liquid treatment using a chemical solution (etching solution, cleaning solution, etc.) is implemented. In addition, after the liquid treatment, a rinse treatment is performed to remove the chemical solution using a rinse solution. A typical rinse solution is deionized water, etc. Then, a drying treatment is performed to dry the substrate by removing the rinse solution from the front side of the substrate.

[0004] In recent years, as the concave-convex patterns formed on the front surface of the substrate have become increasingly miniaturized, the aspect ratio (the ratio of the height to the width of the convex portion) of the pattern has tended to increase. Consequently, during the drying process, adjacent convex portions may collapse due to the surface tension of the rinse liquid (the interface between the rinse liquid and the gas above it) acting on the concave portions between the convex portions of the pattern.

[0005] Patent Document 1 discloses that a rinse liquid on the front surface of a substrate is replaced with a liquid of tert-butanol, a sublimable substance, within a chamber to form a film-like solidified film of tert-butanol. Patent Document 1 also discloses that the front surface of the substrate is dried by subsequently converting the tert-butanol contained in the solidified film from a solid phase to a gas phase without passing through a liquid phase.

[0006] Background Art Literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2015-142069 Summary of the Invention

[0009] [Problems to be solved by the invention]

[0010] However, the freezing point of tert-butyl alcohol is slightly higher (about 25.6°C) than the room temperature (within the range of 22°C to 25°C, for example, about 23°C) used for general substrate processing. Therefore, when using a sublimation substance with a freezing point above room temperature, such as tert-butyl alcohol, in order to prevent solidification in the pipe, the sublimation substance in the pipe must be given heat. Specifically, it is considered to set a temperature regulating mechanism in the pipe. In this case, it is hoped that a temperature regulating mechanism will be set in the entire area of the pipe for the sublimation substance to circulate. Therefore, there is a concern that the cost will increase significantly. In addition, if the sublimation substance solidifies in the pipe due to the stoppage of the temperature regulating mechanism caused by a device failure, it will take a very long time to recover. In other words, when a sublimation substance with a freezing point above room temperature, such as tert-butyl alcohol, is directly used for substrate drying, there is still a concern about the solidification of the drying auxiliary substance (sublimation substance) in the pipe.

[0011] In order to eliminate this worry, it is considered to use a sublimation material with a freezing point lower than room temperature for substrate drying. However, sublimation materials with a freezing point lower than normal temperature are generally very expensive. Therefore, if such sublimation materials are used for substrate drying, there is a concern that the cost will increase significantly. Sublimation materials with a freezing point lower than normal temperature will not solidify naturally at room temperature. Therefore, a cooling device or the like must be used inside the chamber to solidify the sublimation material. In this case, there is also a concern that the cost will increase significantly.

[0012] Furthermore, it is also required that the drying auxiliary substance (sublimable substance) supplied to the front surface of the substrate be solidified satisfactorily without significantly increasing the cost.

[0013] Therefore, one of the objects of the present invention is to provide a substrate processing method and a substrate processing apparatus, which can avoid accidental solidification of drying auxiliary substances without significantly increasing costs and can well process the front surface of the substrate.

[0014] In addition, another object of the present invention is to provide a substrate processing method and a substrate processing apparatus, which can effectively solidify the drying auxiliary substance on the front surface of the substrate without significantly increasing the cost.

[0015] [Technical means to solve the problem]

[0016] A first aspect of the present invention provides a substrate processing method for processing a substrate having a pattern on its front surface, and includes: a mixed drying auxiliary substance supplying step of supplying a mixed drying auxiliary substance to the front surface of the substrate to form a liquid film of the mixed drying auxiliary substance on the front surface of the substrate, wherein the mixed drying auxiliary substance is obtained by mixing a drying auxiliary substance as a non-polar substance with an amphiphilic solvent and has a freezing point lower than that of the drying auxiliary substance; and a solidified film forming step of forming a solidified film containing the drying auxiliary substance by solidifying the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance. film; and a removal step, which changes the drying auxiliary substance contained in the solidified film into a gas without passing through a liquid state and removes it from the front surface of the substrate; the solidified film forming step includes a supply liquid contacting step, wherein the supply liquid contacting step is to make a supply liquid of a polar substance different from the drying auxiliary substance and the solvent contact with the liquid film of the mixed drying auxiliary substance, and as the solvent dissolved in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid, the concentration of the drying auxiliary substance in the liquid film increases, thereby causing the drying auxiliary substance to precipitate, thereby forming the solidified film.

[0017] In this specification, "room temperature" refers to the temperature in an air-conditioned environment where a substrate processing apparatus is installed, both in Japan and abroad, and is generally within the range of 22°C to 25°C, for example, approximately 23°C.

[0018] In this specification, the term "polar substance" refers to a substance containing polar molecules.

[0019] In this specification, "non-polar substances" refer to substances containing non-polar molecules. "Non-polar substances" include not only substances that are completely insoluble in polar substances (polar solvents) but also substances that are slightly soluble in polar substances (polar solvents).

[0020] Furthermore, in this specification, "having amphiphilicity" means containing amphiphilic molecules.

[0021] According to this method, a mixed drying auxiliary substance obtained by mixing a drying auxiliary substance with a solvent is supplied to the front surface of the substrate. For example, when the drying auxiliary substance has a freezing point above room temperature, a portion or the entire substance may be solid 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 reduction caused by the mixing of the drying auxiliary substance and the solvent. In other words, even when the freezing point of the mixed drying auxiliary substance is, for example, above room temperature, the freezing point of the mixed drying auxiliary substance is relatively low. Therefore, it is possible to reduce the thermal energy used to maintain the mixed drying auxiliary substance in a liquid state. As a result, it is possible to avoid accidental solidification of the drying auxiliary substance without significantly increasing costs, and to properly process the front surface of the substrate.

[0022] In addition, a liquid film of a mixed drying auxiliary substance, formed by mixing a non-polar drying auxiliary substance with an amphiphilic solvent, is formed on the front surface of the substrate. Furthermore, a supply liquid, a polar substance, is supplied to this liquid film of the mixed drying auxiliary substance. The supply liquid, a polar substance, is (almost) insoluble in the non-polar drying auxiliary substance. Therefore, even if the supply liquid comes into contact with the mixed drying auxiliary substance, the drying auxiliary substance and the supply liquid will not mix with each other.

[0023] When the supply liquid and the liquid film of the mixed drying auxiliary substance are in contact (a system in which the phase of the mixed drying auxiliary substance is in contact with the phase of the supply liquid), a state of equilibrium is reached, and the ratio of the solvent dissolving into the drying auxiliary substance and the supply liquid becomes a fixed value (a value determined by the distribution coefficient). Therefore, for example, if the distribution coefficient of the solvent relative to the drying auxiliary substance and the supply liquid is small, when the supply liquid contacts the liquid film of the mixed drying auxiliary substance, the solvent contained in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid. As the solvent moves, the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance increases. Furthermore, as the concentration of the drying auxiliary substance increases, the freezing point of the mixed drying auxiliary substance increases. When this freezing point reaches room temperature, the drying auxiliary substance contained in the mixed drying auxiliary substance on the front surface of the substrate begins to precipitate, thereby forming a solidified film. Since the drying auxiliary substance contained in the mixed drying auxiliary substance solidifies due to the increase in its freezing point, the mixed drying auxiliary substance does not necessarily need to be cooled for solidification. Therefore, the drying auxiliary substance supplied to the front side of the substrate can be solidified well without significantly increasing the cost.

[0024] As in one embodiment of the present invention, the auxiliary drying substance may include a sublimable substance having sublimability. In this case, the mixed auxiliary drying substance includes a mixed sublimator.

[0025] According to this method, since the drying auxiliary substance has sublimation properties, the drying auxiliary substance contained in the solidified film can be removed satisfactorily from the substrate front surface by sublimating the drying auxiliary substance.

[0026] In one embodiment of the present invention, the supply liquid contacting step includes a step of supplying the supply liquid to the front surface of the substrate while maintaining a liquid film of the mixed drying auxiliary substance in a film shape.

[0027] According to this method, the supply liquid is supplied to the substrate surface while the liquid film of the mixed drying auxiliary substance is maintained in a film shape. Therefore, the solidified film obtained by solidifying the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance can be made into a good film shape.

[0028] As a method of supplying the supply liquid to the front surface of the substrate while maintaining the liquid film of the mixed drying auxiliary material in a film shape, there is a method of ejecting the supply liquid in a burst shape at a weak ejection pressure from multiple tiny ejection outlets, or a method of supplying the supply liquid to the front surface of the substrate at a small flow rate.

[0029] In one embodiment of the present invention, the substrate processing method further includes, before the removing step, a supply liquid removing step of removing the supply liquid present on the front surface of the substrate.

[0030] According to this method, the supply liquid present on the front surface of the substrate is removed from the front surface of the substrate before the removal step. The removed supply liquid also contains the solvent that has migrated from the mixed drying auxiliary substance. Therefore, the mixed drying auxiliary substance and the solvent can be effectively removed from the front surface of the substrate.

[0031] In one embodiment of the present invention, the supply liquid removal step includes at least one of a shaking-off step of rotating the substrate around a specified rotation axis to shake off the supply liquid present on the front surface of the substrate, and a gas blowing step of blowing gas to the front surface of the substrate.

[0032] According to this method, the supply liquid can be flung off the front surface of the substrate by rotating the substrate about the rotation axis. This allows for efficient removal of the supply liquid from the front surface of the substrate. By blowing gas onto the front surface of the substrate instead of or in addition to the substrate's rotation, the supply liquid adhering to the front surface of the substrate can be blown away. This allows for efficient removal of the supply liquid from the front surface of the substrate.

[0033] In one embodiment of the present invention, in the substrate processing method, the supply liquid supplied to the front surface of the substrate in the supply liquid contacting step has a liquid temperature lower than room temperature.

[0034] According to this method, the temperature of the supply liquid is lower than room temperature. Therefore, the front surface of the substrate can be cooled by supplying the supply liquid to the front surface of the substrate. This reduces the temperature of the mixed drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance on the front surface of the substrate. Furthermore, when the temperature of the mixed drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance on the front surface of the substrate falls below its freezing point, the mixed drying auxiliary substance begins to solidify, thereby forming a solidified film.

[0035] Since the mixed drying auxiliary substance solidifies simultaneously by two mechanisms, solidification utilizing the rise in the solidification point of the mixed drying auxiliary substance and solidification accompanying the temperature drop of the mixed drying auxiliary substance, the mixed drying auxiliary substance can be solidified in a short period of time.

[0036] In one embodiment of the present invention, the solvent has a vapor pressure higher than that of the drying auxiliary substance. Furthermore, the supply liquid supplied to the front surface of the substrate in the supply liquid contacting step has a liquid temperature higher than room temperature.

[0037] According to this method, because the solvent has a higher vapor pressure than the drying auxiliary substance, the solvent can be preferentially evaporated from the mixed drying auxiliary substance present on the front surface of the substrate during the liquid supply contact step. 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. This also increases the freezing point of the mixed drying auxiliary substance. When this freezing point reaches room temperature, the drying auxiliary substance contained in the mixed drying auxiliary substance present on the front surface of the substrate begins to solidify. This further promotes the formation of a solidified film during the liquid supply contact step.

[0038] In one embodiment of the present invention, the solvent has a vapor pressure higher than that of the drying auxiliary substance. Furthermore, the solidified film forming step further includes a solvent evaporation step prior to the solidified film forming step, wherein the solvent evaporation step evaporates the solvent from the mixed drying auxiliary substance present on the front surface of the substrate.

[0039] According to this method, because the solvent has a higher vapor pressure than the drying auxiliary substance, the solvent can be preferentially evaporated from the mixed drying auxiliary substance present on the front 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. This also increases the freezing point of the mixed drying auxiliary substance. When this freezing point reaches room temperature, the drying auxiliary substance contained in the mixed drying auxiliary substance present on the front surface of the substrate begins to solidify. This further promotes the formation of a solidified film.

[0040] In one embodiment of the present invention, the solvent evaporation step includes at least one of a heating step of heating the mixed drying auxiliary substance, a gas blowing step of blowing gas to the mixed drying auxiliary substance, a decompression step of decompressing the space around the solidified film, and a substrate high-speed rotation step of rotating the substrate at high speed around a specified rotation axis without supplying liquid to the front surface of the substrate.

[0041] As in one embodiment of the present invention, the heating step may include a step of supplying a heating fluid to the back surface of the substrate.

[0042] As in one embodiment of the present invention, the solvent may have a vapor pressure that is the same as or lower than the vapor pressure of the drying auxiliary substance.

[0043] In one embodiment of the present invention, the supply liquid contact step includes the following steps, namely, in parallel with supplying the supply liquid to the front surface of the substrate, the supply position of the supply liquid in the front surface of the substrate is moved from the central part of the substrate to the peripheral part of the substrate, thereby expanding the formation position of the solidified film in the front surface of the substrate from the central part of the substrate to the peripheral part of the substrate.

[0044] According to this method, a solidified film can be formed over the entire surface area of the substrate in a short period of time.

[0045] In one embodiment of the present invention, the removal step includes at least one of a sublimation step of causing the drying auxiliary substance contained in the solidified film to sublime from a solid to a gas, a decomposition step of causing the drying auxiliary substance contained in the solidified film to change into a gas without passing through a liquid state by decomposing the solidified film, and a reaction step of causing the drying auxiliary substance contained in the solidified film to change into a gas without passing through a liquid state by reacting the solidified film.

[0046] The sublimation step may also include at least one of a gas blowing step of blowing gas onto the solidified film, a heating step of heating the solidified film, a decompressing step of decompressing the space around the solidified film, a light irradiating step of irradiating light onto the solidified body, and an ultrasonic vibration imparting step of imparting ultrasonic vibration to the solidified body.

[0047] In one embodiment of the present invention, the mixed drying auxiliary substance supplying step includes immersing the substrate in a first tank storing the mixed drying auxiliary substance, and the supply liquid contacting step includes immersing the substrate in a second tank storing the supply liquid.

[0048] According to this method, a solidified film can be formed satisfactorily even in a batch method.

[0049] As in one embodiment of the present invention, the supply liquid may contain water.

[0050] A second aspect of the present invention provides a substrate processing method for processing a substrate having a pattern on the front side, and includes: a mixed drying auxiliary substance supplying step of supplying the mixed drying auxiliary substance to the front side of the substrate to form a liquid film of the mixed drying auxiliary substance on the front side of the substrate, wherein the mixed drying auxiliary substance is obtained by mixing a drying auxiliary substance as a non-polar substance with an amphiphilic solvent and has a freezing point lower than the freezing point of the drying auxiliary substance; a solidification film forming step of forming a solidification film containing the drying auxiliary substance by solidifying the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance; and a removal step of removing the drying auxiliary substance contained in the solidification film from the front side of the substrate by changing it into a gas without passing through a liquid state; the solidification film forming step includes a liquid-contacting step of supplying a liquid, wherein the liquid-contacting step is to precipitate the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance, thereby forming the solidification film.

[0051] According to this method, a mixed drying auxiliary substance obtained by mixing a drying auxiliary substance with a solvent is supplied to the front surface of the substrate. For example, when the drying auxiliary substance has a freezing point above room temperature, sometimes a part or the whole of it is solid under room temperature conditions. The freezing point is lowered by the mixing of the drying auxiliary substance and the solvent, and the freezing point of the mixed drying auxiliary substance is lower than the freezing point of the drying auxiliary substance. In other words, even when the freezing point of the mixed drying auxiliary substance is, for example, above room temperature, the freezing point of the mixed drying auxiliary substance is relatively low. Therefore, it is possible to seek to reduce the thermal energy used to maintain the mixed drying auxiliary substance in a liquid state. In this way, it is possible to avoid accidental solidification of the drying auxiliary substance without significantly increasing costs, and to properly process the front surface of the substrate.

[0052] Furthermore, the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance is increased. Furthermore, as the concentration of the drying auxiliary substance increases, the freezing point of the mixed drying auxiliary substance rises. When this freezing point reaches room temperature, the drying auxiliary substance contained in the mixed drying auxiliary substance on the front surface of the substrate begins to precipitate. This forms a solidified film. Since the drying auxiliary substance contained in the mixed drying auxiliary substance solidifies by utilizing the increase in its freezing point, the mixed drying auxiliary substance does not necessarily need to be cooled in order to solidify. Therefore, the drying auxiliary substance supplied to the front surface of the substrate can be effectively solidified without significantly increasing costs.

[0053] In one embodiment of the present invention, the solidified film forming step includes a supply liquid contacting step, wherein the supply liquid contacting step is to contact a supply liquid of a polar substance different from the drying auxiliary substance and the solvent with a liquid film of the mixed drying auxiliary substance, thereby causing the drying auxiliary substance to precipitate due to an increase in the concentration of the drying auxiliary substance in the liquid film, thereby forming the solidified film.

[0054] The third form of the present invention provides a substrate processing device, comprising: a substrate holding unit for holding a substrate having a pattern on the front side; a mixed drying auxiliary substance supply unit for supplying a mixed drying auxiliary substance to the front side of the substrate held by the substrate holding unit, the mixed drying auxiliary substance being obtained by mixing a drying auxiliary substance as a non-polar substance with an amphiphilic solvent and having a freezing point lower than that of the drying auxiliary substance; a supply liquid supply unit for supplying a supply liquid which is a polar substance and is different from the drying auxiliary substance and the solvent to the front side of the substrate held by the substrate holding unit; a removal unit for removing the drying auxiliary substance from the front side of the substrate held by the substrate holding unit by changing it into a gas without passing through a liquid state; and a control device for controlling the mixed drying auxiliary substance supply unit, the supply liquid supply unit and the removal unit. In addition, the control device performs: a mixed drying auxiliary substance supplying step, in which the mixed drying auxiliary substance is supplied to the front surface of the substrate by the mixed drying auxiliary substance supplying unit, thereby forming a liquid film of the mixed drying auxiliary substance on the front surface of the substrate; a solidified film forming step, in which the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance is solidified to form a solidified film containing the drying auxiliary substance; and a removal step, in which the drying auxiliary substance contained in the solidified film is changed into a gas without passing through a liquid state by the removal unit and is removed from the front surface of the substrate; the control device performs a supply liquid contacting step in the solidified film forming step, in which the supply liquid contacting step is performed by the supply liquid supplying unit to supply the supply liquid to the liquid film of the mixed drying auxiliary substance, and as the solvent dissolved in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid, the concentration of the drying auxiliary substance in the liquid film increases, thereby causing the drying auxiliary substance to precipitate, thereby forming the solidified film.

[0055] According to this configuration, a mixed drying auxiliary substance obtained by mixing a drying auxiliary substance with a solvent is supplied to the front surface of the substrate. For example, when the drying auxiliary substance has a freezing point above room temperature, sometimes a part or the whole of the drying auxiliary substance is solid under room temperature conditions. The freezing point is lowered by mixing the drying auxiliary substance with the solvent, and the freezing point of the mixed drying auxiliary substance is lower than the freezing point of the drying auxiliary substance. In other words, even when the freezing point of the mixed drying auxiliary substance is, for example, above room temperature, the freezing point of the mixed drying auxiliary substance is relatively low. Therefore, it is possible to seek to reduce the thermal energy used to maintain the mixed drying auxiliary substance in a liquid state. In this way, it is possible to avoid accidental solidification of the drying auxiliary substance without significantly increasing costs, and to properly process the front surface of the substrate.

[0056] In addition, a liquid film of a mixed drying auxiliary substance, formed by mixing a non-polar drying auxiliary substance with an amphiphilic solvent, is formed on the front surface of the substrate. Furthermore, a supply liquid, a polar substance, is supplied to this liquid film of the mixed drying auxiliary substance. The supply liquid, a polar substance, is (almost) insoluble in the non-polar drying auxiliary substance. Therefore, even if the supply liquid comes into contact with the mixed drying auxiliary substance, the drying auxiliary substance and the supply liquid will not mix with each other.

[0057] When the supply liquid and the liquid film of the mixed drying auxiliary substance are in contact (a system in which the phase of the mixed drying auxiliary substance is in contact with the phase of the supply liquid), a state of equilibrium is reached, and the ratio of the solvent dissolving into the drying auxiliary substance and the supply liquid becomes a fixed value (a value determined by the distribution coefficient). Therefore, for example, if the distribution coefficient of the solvent relative to the drying auxiliary substance and the supply liquid is small, when the supply liquid contacts the liquid film of the mixed drying auxiliary substance, the solvent contained in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid. As the solvent moves, the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance increases. Furthermore, as the concentration of the drying auxiliary substance increases, the freezing point of the mixed drying auxiliary substance increases. When this freezing point reaches room temperature, the drying auxiliary substance contained in the mixed drying auxiliary substance on the front surface of the substrate begins to precipitate, thereby forming a solidified film. Since the drying auxiliary substance contained in the mixed drying auxiliary substance solidifies due to the increase in its freezing point, the mixed drying auxiliary substance does not necessarily need to be cooled for solidification. Therefore, the drying auxiliary substance supplied to the front side of the substrate can be solidified well without significantly increasing the cost.

[0058] The above and other objects, features, and effects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1This is a schematic diagram showing the substrate processing apparatus according to the first embodiment of the present invention as viewed from above.

[0060] Figure 2 It is a schematic cross-sectional view for explaining a configuration example of a processing unit included in the substrate processing apparatus.

[0061] Figure 3 It is a state equilibrium diagram of a mixed sublimator containing a sublimable substance and a solvent.

[0062] Figure 4 This is a block diagram for explaining the electrical configuration of the main parts of the substrate processing apparatus.

[0063] Figure 5 This is a cross-sectional view showing an enlarged front view of a substrate to be processed by the substrate processing apparatus.

[0064] Figure 6 This is a flowchart for explaining the content of a substrate processing example executed in the processing unit.

[0065] 7A to 7C are schematic diagrams showing the state of the periphery of the substrate when the above-described substrate processing example is performed.

[0066] 7D and 7E are schematic diagrams showing steps subsequent to FIG. 7C .

[0067] 7F and 7G are schematic diagrams showing steps subsequent to FIG. 7E .

[0068] Figure 8A It is a schematic cross-sectional view for explaining a configuration example of a processing unit according to a second embodiment of the present invention.

[0069] Figure 8B is a schematic diagram showing the removing step (S10) performed in the processing unit.

[0070] 9A and 9B are schematic diagrams showing variations of the supply liquid contact step ( S8 ).

[0071] Figure 10 It is a schematic diagram showing a modified example of the liquid supply nozzle.

[0072] Figure 11 It is a schematic diagram showing an example of a cooling unit.

[0073] Figure 12 It is a schematic diagram showing an example of a cooling unit.

[0074] Figure 13 It is a schematic diagram showing an example of a heating unit.

[0075] Figure 14 It is a schematic diagram showing an example of a heating unit.

[0076] Figure 15 This is a schematic diagram used to illustrate a wet processing unit and a dry processing unit.

[0077] Figure 16 It is a schematic diagram for explaining the structure of a substrate processing apparatus according to a third embodiment of the present invention.

[0078] Figure 17 It is a schematic diagram showing a lifting state in the substrate processing apparatus. DETAILED DESCRIPTION

[0079] Figure 1 This is a schematic diagram 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 apparatus that processes substrates W such as silicon wafers one by one. In this embodiment, the substrate W is a disc-shaped substrate. The substrate processing apparatus 1 includes: a plurality of processing units 2 that process the substrate W using a processing liquid containing a chemical solution and a rinse liquid; a loading port LP for loading a substrate container that holds a plurality of substrates W processed by the processing unit 2; an indexing robot IR and a substrate transport robot CR that transport the substrates W between the loading port LP and the processing unit 2; and a control device 3 that controls the substrate processing apparatus 1. The indexing robot IR transports the substrate W between the substrate container and the substrate transport robot CR. The substrate transport robot CR transports the substrate W between the indexing robot IR and the processing unit 2. For example, a plurality of processing units 2 have the same structure. The substrate processing apparatus 1 is set up under normal pressure (atmospheric pressure) and room temperature (for example, about 23°C).

[0080] Figure 2 It is a schematic cross-sectional view for explaining a configuration example of the processing unit 2.

[0081] The processing unit 2 includes a box-shaped chamber 4; a spin chuck (substrate holding unit) 5 that holds a substrate W in a horizontal position in the chamber 4 and rotates the substrate W around a vertical rotation axis A1 passing through the center of the substrate W; and a chemical liquid supply unit 6 that applies a chemical liquid to the upper surface (front surface Wa of the substrate W (see FIG. 1 )) of the substrate W held by the spin chuck 5. Figure 5 rinsing liquid supply unit 7, the upper surface of the substrate W held by the spin chuck 5 (the front side of the substrate W Wa (reference Figure 5 replacement solvent supply unit 8, the upper surface of the substrate W held by the spin chuck 5 (the front surface of the substrate W Wa (reference Figure 5 )) supplies a solvent for replacement (hereinafter referred to as "replacement solvent"); a mixed sublimation agent supply unit (mixed drying auxiliary material supply unit) 9, to the upper surface of the substrate W held by the spin chuck 5 (the front surface Wa of the substrate W (refer to Figure 5)) supplying a mixed sublimation agent (mixed drying auxiliary substance); supplying a liquid supply unit 10, to the upper surface of the substrate W held by the spin chuck 5 (the front surface Wa of the substrate W (refer to Figure 5 gas blowing unit (removal unit) 11, the upper surface of the substrate W held by the spin chuck 5 (the front surface of the substrate W Wa (reference Figure 5 )) blows gas; a lower surface nozzle 12 sprays a heating fluid toward the center of the lower surface (the back side Wb of the substrate W (refer to Figure 7A, etc.)) of the substrate W held by the rotating chuck 5; and a cylindrical processing cup 13 surrounds the side of the rotating chuck 5.

[0082] In this embodiment, no shielding member is provided to isolate the space above the substrate W from the surrounding atmosphere. This is because supplying cooling fluid to the back surface Wb of the substrate W is not necessary during the solidified film formation step (the liquid supply and connection step S8 described below). Because cooling fluid rebounding from peripheral components (such as the processing cup 13) does not contaminate the front surface Wa of the substrate W, no shielding member is provided.

[0083] The chamber 4 includes: a box-shaped partition wall 14 that accommodates the spin chuck 5 or the nozzle; an FFU (fan filter unit) 15 as an air supply unit that delivers clean air (filtered air) from the top of the partition wall 14 into the partition wall 14; an exhaust pipe 16 that exhausts the gas in the chamber 4 from the bottom of the partition wall 14; and an exhaust device 17 connected to the other end of the exhaust pipe 16. The FFU 15 is arranged above the partition wall 14 and mounted on the top plate of the partition wall 14. The FFU 15 delivers clean air downward from the top plate of the partition wall 14 into the chamber 4. The exhaust device 17 sucks the interior of the process cup 13 through the exhaust pipe 16 connected to the bottom of the process cup 13. A downflow (downflow) is formed in the chamber 4 by the FFU 15 and the exhaust device 17. The processing of the substrate W is performed in a state where a downflow is formed in the chamber 4.

[0084] A clamping chuck is used as the spin chuck 5 to horizontally clamp and hold the substrate W. Specifically, the spin chuck 5 includes a rotation motor (removal unit) 18, a rotation shaft 19 integrated with the drive shaft of the rotation motor 18, and a disk-shaped spin base 20 mounted substantially horizontally on the upper end of the rotation shaft 19.

[0085] The spin base 20 includes a horizontal, circular upper surface 20a having an outer diameter larger than that of the substrate W. A plurality (three or more, for example, six) of clamping members 21 are arranged on the periphery of the upper surface 20a. The plurality of clamping members 21 are arranged on the periphery of the upper surface 20a at appropriate intervals, for example, at equal intervals, on a circumference corresponding to the outer circumference of the substrate W.

[0086] like Figure 2 As shown, the liquid medicine supply unit 6 includes: a liquid medicine nozzle 31; a nozzle arm 32, the liquid medicine nozzle 31 being mounted at the front end thereof; and a nozzle moving unit 33 (see Figure 4 ), the chemical nozzle 31 is moved by moving the nozzle arm 32. The nozzle moving unit 33 moves the chemical nozzle 31 horizontally by moving the nozzle arm 32 horizontally around the swing axis. The nozzle moving unit 33 includes a motor and the like. The nozzle moving unit 33 moves the chemical nozzle 31 horizontally between a processing position where the chemical liquid ejected from the chemical nozzle 31 impinges on the front surface Wa of the substrate W, and a retreat position set around the spin chuck 5 in a plan view. In other words, the processing position is a position where the chemical liquid ejected from the chemical nozzle 31 is supplied to the front surface Wa of the substrate W. Furthermore, the nozzle moving unit 33 moves the chemical nozzle 31 horizontally between a central position where the chemical liquid ejected from the chemical nozzle 31 impinges on the central portion of the front surface Wa of the substrate W, and a peripheral position where the chemical liquid ejected from the chemical nozzle 31 impinges on the peripheral portion of the front surface Wa of the substrate W. Both the central position and the peripheral position are processing positions.

[0087] The chemical supply unit 6 includes a chemical pipe 34 that guides the chemical to the chemical nozzle 31, and a chemical valve 35 that opens and closes the chemical pipe 34. When the chemical valve 35 is opened, the chemical from the chemical supply source is supplied through the chemical pipe 34 to the chemical nozzle 31. As a result, the chemical is ejected from the chemical nozzle 31.

[0088] The chemical liquid supplied to the chemical liquid piping 34 includes a cleaning liquid and an etching liquid. More specifically, the chemical liquid includes at least one of sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, aqueous ammonia, aqueous hydrogen peroxide, an organic acid (e.g., citric acid, oxalic acid), an organic base (e.g., TMAH: tetramethylammonium hydroxide), a surfactant, and an anti-corrosive agent.

[0089] like Figure 2As shown, the rinsing liquid supply unit 7 includes a rinsing liquid nozzle 36. The rinsing liquid nozzle 36 is, for example, a linear nozzle that ejects liquid in a continuous flow state, and is fixedly arranged above the spin chuck 5 with its ejection port directed toward the center of the upper surface of the substrate W. A rinsing liquid pipe 37 that supplies rinsing liquid from a rinsing liquid supply source is connected to the rinsing liquid nozzle 36. A rinsing liquid valve 38 for switching the supply / supply stop of the rinsing liquid from the rinsing liquid nozzle 36 is installed in the middle 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 ejected from the ejection port set at the lower end of the rinsing liquid nozzle 36. In addition, when the rinsing liquid valve 38 is closed, the supply of rinsing liquid from the rinsing liquid pipe 37 to the rinsing liquid nozzle 36 is stopped. The rinsing liquid is water. The water is, for example, deionized water (DIW), but is not limited to DIW. It can be any of carbonated water, electrolyzed ionized water, hydrogen water, ozone water, ammonia water, and hydrochloric acid water with a diluted concentration (for example, about 10 ppm to 100 ppm).

[0090] Furthermore, the rinse liquid supply unit 7 may include a rinse liquid nozzle moving device that moves the rinse liquid nozzle 36 to scan the landing position of the rinse liquid on the upper surface of the substrate W within the surface of the substrate W.

[0091] like Figure 2 As shown, the replacement solvent supply unit 8 includes: a replacement solvent nozzle 41; a nozzle arm 42, at the front end of which the replacement solvent nozzle 41 is mounted; and a nozzle moving unit 43 (see Figure 4 ), the replacement solvent nozzle 41 is moved by moving the nozzle arm 42. The nozzle moving unit 43 moves the replacement solvent nozzle 41 horizontally by moving the nozzle arm 42 horizontally around the swing axis. The nozzle moving unit 43 includes a motor and the like. The nozzle moving unit 43 moves the replacement solvent nozzle 41 horizontally between a processing position where the replacement solvent ejected from the replacement solvent nozzle 41 lands on the front surface Wa of the substrate W and a retreat position set around the spin chuck 5 in a plan view. In other words, the processing position is a position where the replacement solvent ejected from the replacement solvent nozzle 41 is supplied to the front surface Wa of the substrate W (for example, the center portion).

[0092] like Figure 2 As shown, the replacement solvent supply unit 8 includes a replacement solvent pipe 44 that guides the replacement solvent to the replacement solvent nozzle 41, and a replacement solvent valve 45 that opens and closes the replacement solvent pipe 44. When the replacement solvent valve 45 is opened, the replacement solvent from the replacement solvent supply source is supplied from the replacement solvent pipe 44 to the replacement solvent nozzle 41. As a result, the replacement solvent is ejected from the replacement solvent nozzle 41.

[0093] The replacement solvent supplied to the replacement solvent pipe 44 is soluble in (miscible with) the mixed sublimation agent supplied by the mixed sublimation agent supply unit 9. In other words, the replacement solvent is soluble in (miscible with) the sublimation substance contained in the mixed sublimation agent and the mixed solvent. The replacement solvent serves as a pre-supply liquid supplied to the front surface Wa of the substrate W before the mixed sublimation agent is supplied to the front surface Wa.

[0094] In the following substrate processing example, the replacement solvent is supplied to the front surface Wa of the substrate W after the rinsing liquid is supplied to the front surface Wa and before the mixed sublimation agent is supplied to the front surface Wa of the substrate W. Therefore, the replacement solvent is preferably soluble (miscible) in the rinsing liquid (water).

[0095] Specific examples of the replacement solvent supplied to the replacement solvent pipe 44 include organic solvents such as IPA (isopropyl alcohol). Examples of such organic solvents, in addition to IPA, include methanol, ethanol, acetone, EG (ethylene glycol), HFE (hydrofluoroether), n-butanol, t-butanol, isobutyl alcohol, and 2-butanol. Furthermore, organic solvents may not only consist solely of a single component but may also be liquids mixed with other components. Furthermore, solvents other than organic solvents may also be used as replacement solvents.

[0096] like Figure 2 As shown, the mixed sublimation agent supply unit 9 includes: a mixed sublimation agent nozzle 46; a nozzle arm 47, at the front end of which the mixed sublimation agent nozzle 46 is mounted; and a nozzle moving unit 48 (see Figure 4 ), the mixed sublimate nozzle 46 is moved by moving the nozzle arm 47. The nozzle moving unit 48 moves the mixed sublimate nozzle 46 horizontally by moving the nozzle arm 47 horizontally about the swing axis. The nozzle moving unit 48 includes a motor and other components. The nozzle moving unit 48 moves the mixed sublimate nozzle 46 horizontally between a processing position where the mixed sublimate ejected from the mixed sublimate nozzle 46 lands on the front surface Wa of the substrate W and a retreat position set around the spin chuck 5 in a plan view. In other words, the processing position is a position where the mixed sublimate ejected from the mixed sublimate nozzle 46 is supplied to the front surface Wa of the substrate W (e.g., the center).

[0097] like Figure 2 As shown, the mixed sublimate supply unit 9 further includes a mixed sublimate pipe 49 for guiding the mixed sublimate to the mixed sublimate nozzle 46, and a mixed sublimate valve 50 for opening and closing the mixed sublimate pipe 49. When the mixed sublimate valve 50 is opened, the mixed sublimate from the mixed sublimate supply source is supplied from the mixed sublimate pipe 49 to the mixed sublimate nozzle 46. As a result, the mixed sublimate is ejected from the mixed sublimate nozzle 46.

[0098] The mixed sublimation agent supplied to the mixed sublimation agent pipe 49 is a mixed substance obtained by mixing a sublimation substance (drying auxiliary substance) with a mixing solvent (solvent). The sublimation substance has a freezing point T above room temperature (RT). F1 (Refer to Figure 3 Room temperature (RT) is also affected by the outside air temperature and is not necessarily fixed, but is generally set at 23°C. The mixed sublimation agent is in a form in which the sublimable substance and the mixing solvent are mutually dissolved. Therefore, in the mixed sublimation agent, the sublimable substance and the mixing solvent are uniformly mixed without any deviation.

[0099] The sublimable substance that preferentially sublimates among the substances contained in the mixed sublimation agent is a non-polar substance. The so-called "non-polar substance" refers to a substance containing non-polar molecules. Examples of sublimable substances include camphor (freezing point at atmospheric pressure: approximately 175° C. to 180° C., vapor pressure at room temperature and atmospheric pressure: 120 Pa), cyclohexanol (freezing point at atmospheric pressure: approximately 24° C., vapor pressure at room temperature and atmospheric pressure: 0.13 kPa), tert-butyl alcohol (freezing point at atmospheric pressure: approximately 25.6° C., vapor pressure at room temperature and atmospheric pressure: 5.4 kPa), 1,3,5-trioxane (freezing point at atmospheric pressure: approximately 60° C. to 62° C., vapor pressure at room temperature and atmospheric pressure: 0.75 kPa), naphthalene (freezing point at atmospheric pressure: approximately 80° C., vapor pressure at room temperature and atmospheric pressure: 7.9 Pa), iodine (freezing point at atmospheric pressure: approximately 113° C., vapor pressure at room temperature and atmospheric pressure: 0.04 kPa), methanol, and n-butanol.

[0100] The mixing solvent contained in the mixed sublimation agent is amphiphilic. "Amphiphilic" means containing amphiphilic molecules. The mixing solvent is an organic solvent, for example, represented by IPA (isopropyl alcohol). Examples of organic solvents used as the mixing solvent include, in addition to IPA, ethanol and acetone. Furthermore, the organic solvent used as the mixing solvent may not only consist solely of a single component but may also be a liquid mixed with other components. Furthermore, solvents other than organic solvents may also be used as the mixing solvent.

[0101] In the present embodiment, preferred examples of the combination of the sublimable substance and the mixing solvent include camphor and IPA, cyclohexanol and IPA, and 1,3,5-trioxane and IPA.

[0102] 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 significantly lower vapor pressures than IPA. In other words, when camphor, cyclohexanol, 1,3,5-trioxane, etc. are used as sublimable substances and IPA is used as the mixing solvent, the mixing solvent contained in the mixed sublimation agent has a higher vapor pressure than the sublimable substance.

[0103] In addition, when a combination of camphor and IPA is used as a combination of a sublimable substance and a mixing solvent, the freezing point T of the sublimable substance (camphor) is F1 At atmospheric pressure, the freezing point is, for example, about 175°C to about 180°C. F2 It is about -80°C or lower under atmospheric pressure.

[0104] In the combination example of the sublimable substance and the mixed solvent, the mixed solvent is listed as having a freezing point T below room temperature. F2 For example, the freezing point T of the mixed solvent is F2 It can also be above room temperature.

[0105] Figure 3 This is a state equilibrium diagram of a mixed sublimation agent containing a sublimable substance and a mixing solvent. Due to the freezing point depression caused by the mixing of the sublimable substance and the mixing solvent, the freezing point of the mixed sublimation agent T FM Compared with the freezing point T of sublimable substances F1 Lower the freezing point T of the mixed sublimation agent FM Depends on the concentration of sublimable substances in the mixed sublimation agent. Figure 3 The freezing point curve FPC of the mixed sublimation agent is described in the . The concentration of the sublimation substance in the mixed sublimation agent is reduced to the freezing point T of the mixed sublimation agent. FM The temperature is lower than room temperature (RT), at which the mixed sublimation agent is in liquid form.

[0106] The concentration of the sublimable substance in the mixed sublimation agent is at the freezing point T of the mixed sublimation agent. FM The temperature of the mixed sublimation agent is set appropriately within the range of a temperature lower than room temperature (RT). However, the original purpose of using the mixed sublimation agent is to sublime the sublimable substance ( Figure 6 S10: Removal step), therefore, the concentration of the mixing solvent in the mixed sublimation agent must not be too high, that is, the concentration of the sublimable substance in the mixed sublimation agent must not be too low.

[0107] A chemical liquid supply device is provided outside the chamber 4, either integrally with the substrate processing device 1 or separately from the substrate processing device 1. This chemical liquid supply device is also provided in an environment of room temperature and normal pressure (atmospheric pressure). A storage tank for storing the mixed sublimation agent is provided in the chemical liquid supply device. At room temperature, the mixed sublimation agent is in liquid form. Therefore, there is no need for a heating device, etc., for maintaining the sublimation substance in liquid form. Furthermore, even if such a heating device is provided, it is not necessary to heat the mixed sublimation agent at all times. Therefore, the amount of heat required can be reduced, and as a result, costs can be reduced.

[0108] like Figure 2 As shown, the supply liquid supply unit 10 includes: a supply liquid nozzle 51; a nozzle arm 52, the supply liquid nozzle 51 being mounted at the front end thereof; and a nozzle moving unit 53 (see Figure 4 ), the supply liquid nozzle 51 is moved by moving the nozzle arm 52. The nozzle moving unit 53 moves the supply liquid nozzle 51 horizontally by moving the nozzle arm 52 horizontally about the swing axis. The nozzle moving unit 53 includes a motor and other components. The nozzle moving unit 53 moves the supply liquid nozzle 51 horizontally between a processing position where the mixed sublimate ejected from the supply liquid nozzle 51 lands on the front surface Wa of the substrate W and a retreat position set around the spin chuck 5 in a plan view. In other words, the processing position is the position where the supply liquid ejected from the supply liquid nozzle 51 is supplied to the front surface Wa of the substrate W (for example, the center).

[0109] like Figure 2 As shown, the feed liquid supply unit 10 further includes a feed liquid pipe 54 for guiding the mixed sublimation agent to the feed liquid nozzle 51, and a feed liquid valve 55 for opening and closing the feed liquid pipe 54. When the feed liquid valve 55 is opened, the feed liquid from the feed liquid supply source is supplied from the feed liquid pipe 54 to the feed liquid nozzle 51. As a result, the feed liquid is ejected from the feed liquid nozzle 51.

[0110] The supply liquid supplied to the supply liquid piping 54 is a liquid of a different type than the sublimable substance and the mixing solvent. The supply liquid supplied to the supply liquid piping 54 is a polar substance. "Polar substance" refers to a substance containing polar molecules. Furthermore, the supply liquid supplied to the supply liquid piping 54 has a liquid temperature lower than room temperature. In this embodiment, the liquid temperature of the supply liquid is set to 5°C to 10°C lower than room temperature. In other words, the supply liquid also functions as a coolant.

[0111] A specific example of the supply liquid supplied to the supply liquid pipe 54 is an aqueous liquid containing water. A representative example of the aqueous liquid is water such as deionized water (DIW). Examples of such aqueous liquids are not limited to DIW, and include carbonated water, electrolytic ionized water, hydrogen water, ozone water, ammonia water, and hydrochloric acid water.

[0112] Alternatively, an organic solvent may be used as the feed liquid. Examples of such organic solvents include methanol, ethanol, acetone, methanol, and n-butanol.

[0113] like Figure 2 As shown, the gas blowing unit 11 includes: a gas nozzle 56; a nozzle arm 57, the gas nozzle 56 is mounted at the front end; and a nozzle moving unit 58 (refer to Figure 4 ), the gas nozzle 56 is moved by moving the nozzle arm 57. The nozzle moving unit 58 moves the gas nozzle 56 horizontally by moving the nozzle arm 57 horizontally around the swing axis. The nozzle moving unit 53 is a structure including a motor, etc. The nozzle moving unit 58 moves the gas nozzle 56 horizontally between a processing position where the mixed sublimate sprayed from the gas nozzle 56 impinges on the front surface Wa of the substrate W and a retreat position set around the spin chuck 5 in a top view. In other words, the processing position is a position where the gas blown from the liquid supply nozzle 51 is supplied to the front surface Wa of the substrate W. Specifically, the processing position is a central position where the gas blown from the gas nozzle 56 impinges on the central part of the upper surface of the substrate W.

[0114] like Figure 2 As shown, the gas blowing unit 11 further includes a gas pipe 59 for guiding 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. As a result, gas is blown out from the gas nozzle 56.

[0115] The gas supplied to the gas pipe 59 is a dehumidified gas, particularly an inert gas. The inert gas includes, for example, nitrogen or argon. Alternatively, the gas may be an active gas such as air.

[0116] The gas nozzle 56 includes a cylindrical nozzle body 64 with a flange 63 at its lower end. An upper gas outlet 65 and a lower gas outlet 66 are formed on the outer circumference of the flange 63, each opening outward in an annular pattern. A central gas outlet 67 is located on the lower surface of the nozzle body 64. The radial flow of inert gas ejected from the central gas outlet 67 is combined with the two-layer radial flow ejected from the upper gas outlet 65 and the lower gas outlet 66 to form a triple-layer radial flow above the substrate W.

[0117] like Figure 2As shown, the lower surface nozzle 12 has a single discharge port 12a that faces the center of the lower surface of the substrate W held by the spin chuck 5. The discharge port 12a discharges liquid vertically upward. The discharged liquid is incident approximately 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 interior of the vertically arranged hollow rotating shaft 19.

[0118] like Figure 2 As shown, the heating fluid pipe 72 is connected to the supply pipe 71 on the lower surface. A heating fluid valve 73 is installed on the heating fluid pipe 72 to open and close the heating fluid pipe 72. The heating fluid can be a heating liquid such as warm water or a heating gas. The heating fluid has a freezing point T higher than the mixed sublimation agent. FM High liquid temperature.

[0119] When the heating fluid valve 73 is opened, heating fluid from the heating fluid supply source is supplied to the lower surface nozzle 12 via the heating fluid piping 72 and the lower surface supply piping 71. The heating fluid supplied to the lower surface nozzle 12 is ejected approximately vertically upward from the ejection port 12a. The heating fluid ejected from the lower surface nozzle 12 is incident approximately perpendicularly onto the center portion of the lower surface of the substrate W held by the spin chuck 5. In this embodiment, the lower surface nozzle 12, the lower surface supply piping 71, the heating fluid piping 72, and the heating fluid valve 73 constitute a heating unit.

[0120] like Figure 2 As shown, the process cup 13 is positioned outside (away from the rotation axis A1) the substrate W held by the spin chuck 5. The process cup 13 surrounds the spin base 20. When a process liquid, a rinse liquid, a replacement solvent, a mixed sublimation agent, or other liquid is supplied to the substrate W while the spin chuck 5 rotates the substrate W, the liquid supplied to the substrate W is thrown out around the substrate W. When these liquids are supplied to the substrate W, the upper end 13a of the process cup 13 is positioned above the spin base 20. Therefore, the liquid discharged around the substrate W is received by the process cup 13. Furthermore, the liquid received by the process cup 13 is transported to a recovery device or waste liquid device (not shown).

[0121] Figure 4 This is a block diagram for explaining the electrical configuration of the main parts of the substrate processing apparatus 1 .

[0122] The control device 3 is configured using, for example, a microcomputer. The control device 3 includes a computing unit such as a CPU (Central Processing Unit), a storage unit such as a fixed memory device and a hard disk drive, and an input / output unit. The storage unit stores a program executed by the computing unit.

[0123] The rotary motor 18 and nozzle moving units 33, 43, 48, 53, 58 are connected to the control device 3 as control objects. The control device 3 controls the operation of the rotary motor 18 and nozzle moving units 33, 43, 48, 53, 58 according to a predetermined program.

[0124] Furthermore, the control device 3 opens and closes the gas valve 225 , the chemical solution valve 35 , the rinse solution valve 38 , the replacement solvent valve 45 , the mixed sublimation agent valve 50 , the supply liquid valve 55 , the gas valve 60 , the heating fluid valve 73 , and the like according to a predetermined program.

[0125] Hereinafter, a case where a substrate W having a pattern 100 formed on its front surface Wa as a pattern formation surface is processed will be described.

[0126] Figure 5 1 is a cross-sectional view showing an enlarged front surface Wa of a 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 its pattern forming surface, that is, the front surface Wa. The pattern 100 is, for example, a fine pattern. The pattern 100 may also be as follows: Figure 5 As shown, convex (columnar) structures 101 are arranged in a matrix. In this case, the line width W1 of the structures 101 is, for example, approximately 3 nm to 45 nm, and the gap W2 of the pattern 100 is, for example, approximately 10 nm to several μm. The height T of the pattern 100 is, for example, approximately 0.2 μm to 1.0 μm. Furthermore, the aspect ratio (the ratio of the height T to the line width W1) of the pattern 100 can be, for example, approximately 5 to 500 (typically, approximately 5 to 50).

[0127] Alternatively, the pattern 100 may be formed by repeatedly arranging a linear pattern formed by fine grooves. Alternatively, the pattern 100 may be formed by providing a plurality of fine holes (voids or pores) in a thin film.

[0128] The pattern 100 may include, for example, an insulating film. Alternatively, the pattern 100 may include a conductive film. More specifically, the pattern 100 may be formed from a laminated film formed by laminating multiple films, further including an insulating film and a conductive film. Alternatively, the pattern 100 may be a pattern consisting of a single film. The insulating film may be a silicon oxide film (SiO2 film) or a silicon nitride film (SiN film). Furthermore, the conductive film may be an amorphous silicon film into which impurities for reducing resistance have been introduced, or a metal film (e.g., a TiN film).

[0129] Alternatively, the pattern 100 may be a hydrophilic film. Examples of the hydrophilic film include a TEOS film (a type of silicon oxide film).

[0130] Figure 67A to 7G are schematic diagrams showing states around a substrate W when this substrate processing example is executed.

[0131] When the substrate W is subjected to a substrate processing example by the processing unit 2, an unprocessed substrate W is carried into the interior of the chamber 4 ( Figure 6 Step S1).

[0132] The control device 3 controls the substrate transport robot CR (see FIG. 1 ) holding the substrate W in a state where the nozzle and the like are all retracted from above the spin chuck 5. Figure 1 ) enters the interior of the chamber 4. As a result, the substrate W is transferred to the spin chuck 5 with its front surface Wa facing upward and is held on the spin chuck 5.

[0133] After the substrate W is held on 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 specified liquid processing speed (within a range of about 10 rpm to about 1500 rpm, for example, about 500 rpm) and maintains the liquid processing speed.

[0134] When the rotation speed of the substrate W reaches the liquid processing speed, the control device 3 starts to execute the liquid treatment step ( Figure 6 Specifically, the control device 3 controls the nozzle moving unit 33 to move the chemical liquid nozzle 31 from the retreat position to the processing position. Furthermore, the control device 3 opens the chemical liquid valve 35. This causes chemical liquid to be supplied to the chemical liquid nozzle 31 via the chemical liquid piping 34, and the chemical liquid discharged from the discharge port of the chemical liquid nozzle 31 lands on the front surface Wa of the substrate W.

[0135] Furthermore, in the chemical liquid step ( S2 ), the control device 3 may control the nozzle moving unit 23 to move the chemical liquid nozzle 31 between a peripheral position facing the peripheral portion of the front surface Wa of the substrate W and a central position facing the central portion of the upper surface of the substrate W. In this case, the chemical liquid can land at a position on the upper surface of the substrate W that scans the entire area of the front surface Wa of the substrate W. This allows the entire area of the front surface Wa of the substrate W to be uniformly treated.

[0136] When a predetermined period of time has passed since the start of the chemical liquid discharge, the control device 3 closes the chemical liquid valve 35 to stop the discharge of the chemical liquid from the chemical liquid nozzle 31. This completes the chemical liquid step (S2). The control device 3 also returns the chemical liquid nozzle 31 to the retracted position.

[0137] Next, the control device 3 executes a rinsing step ( ) for replacing the chemical solution on the substrate W with a rinsing liquid to rinse the front surface Wa of the substrate W. Figure 6Specifically, the control device 3 opens the rinse liquid valve 38. As a result, the rinse liquid is ejected from the rinse liquid nozzle 36 toward the center of the rotating front surface Wa. The rinse liquid supplied to the front surface Wa of the substrate W is moved toward the periphery of the substrate W by the centrifugal force generated by the rotation of the substrate W, and is discharged from the periphery toward the side of the substrate W. As a result, the chemical solution adhering to the substrate W is washed away by the rinse liquid.

[0138] When a predetermined period of time has passed since the flushing liquid valve 38 was opened, the control device 3 closes the flushing liquid valve 38. Thus, the flushing step (S3) ends.

[0139] Next, the control device 3 executes the replacement step ( Figure 6 The replacement step (S4) is a step of replacing the rinsing liquid on the substrate W with a replacement solvent (in this example, an organic solvent such as IPA) having affinity for both the rinsing liquid (water) and the mixed sublimation agent.

[0140] Specifically, the control device 3 controls the nozzle moving unit 43 to move the replacement solvent nozzle 41 from a retracted position to the side of the spin chuck 5 to above the center of the front surface Wa of the substrate W. The control device 3 then opens the replacement solvent valve 45, causing the replacement solvent nozzle 41 to eject liquid replacement solvent toward the center of the upper surface (front surface Wa) of the substrate W. The replacement solvent supplied to the front surface Wa of the substrate W is diffused over the entire area of the front surface Wa by the centrifugal force generated by the rotation of the substrate W. As a result, the rinsing liquid adhering to the front surface Wa of the substrate W is replaced with the replacement solvent over the entire area of the front surface Wa of the substrate W. The replacement solvent that has moved along the front surface Wa of the substrate W is discharged from the peripheral edge of the substrate W to the sides of the substrate W.

[0141] The replacement step (S4) may be performed while rotating the substrate W at the liquid processing speed. Alternatively, the replacement step (S4) may be performed while rotating the substrate W at a liquid overflow speed slower than the liquid processing speed or while stopping the substrate W.

[0142] When a predetermined period of time has passed since the start of dispensing of the replacement solvent, the control device 3 closes the replacement solvent valve 45, stopping the dispensing of the replacement solvent from the replacement solvent nozzle 41. This completes the replacement step (S4). Furthermore, the control device 3 returns the replacement solvent nozzle 41 to its retracted position.

[0143] Next, the control device 3 executes the mixed sublimation agent supply step ( Figure 6 Step S5, mixing and drying auxiliary material supply step).

[0144] Specifically, the control device 3 controls the nozzle moving unit 48 to move the mixed sublimation agent nozzle 46 from the retreat position on the side of the spin chuck 5 to the position above the center of the front surface Wa of the substrate W. Then, the control device 3 opens the mixed sublimation agent valve 50, and as shown in FIG7A , the mixed sublimation agent is ejected from the mixed sublimation agent nozzle 46 toward the center of the upper surface (front surface Wa) of the substrate W. As described above, the mixed sublimation agent supplied to the mixed sublimation agent nozzle 46 is at its freezing point T FM The concentration of the sublimable substance in the mixed sublimate is set to be lower than room temperature under atmospheric pressure, so that the mixed sublimate ejected from the mixed sublimate nozzle 46 remains in a liquid state.

[0145] The mixed sublimation agent deposited on the central portion of the front surface Wa of the substrate W receives the centrifugal force generated by the rotation of the substrate W and flows toward the peripheral portion of the front surface Wa of the substrate W. As a result, a liquid film 81 of the mixed sublimation agent covering the entire area of the front surface Wa of the substrate W is formed on the front surface Wa of the substrate W. Since the mixed sublimation agent ejected from the mixed sublimation agent nozzle 46 maintains a liquid state, the liquid film 81 can be well formed. In the mixed sublimation agent supplying step (S5), the height of the film thickness W11 of the liquid film 81 of the mixed sublimation agent formed on the front surface Wa of the substrate W is relatively high with respect to the height T of the pattern 100 (refer to Figure 5 ) is high enough.

[0146] The mixed sublimation agent supplying step (S5) may be performed while rotating the substrate W at the liquid processing speed. Furthermore, the mixed sublimation agent supplying step (S5) may be performed while rotating the substrate W at an overflow speed slower than the liquid processing speed (e.g., a speed at which the centrifugal force of the mixed sublimation agent liquid film 81 acting on the upper surface of the substrate W is smaller than the surface tension acting between the mixed sublimation agent and the upper surface of the substrate W, or the centrifugal force and the surface tension are substantially balanced, for example, about 5 rpm) or while stopping the substrate W.

[0147] When a predetermined period has elapsed since the start of discharge of the mixed sublimate, the control device 3 closes the mixed sublimate valve 50. This stops the supply of the mixed sublimate to the front surface Wa of the substrate W. The control device 3 also returns the mixed sublimate nozzle 46 to the retracted position.

[0148] Next, a film thickness reducing step ( Figure 6 Step S6).

[0149] Specifically, the film thickness reduction step (S6) includes a substrate high-speed rotation step (rapid rotation, substrate rotation step). The control device 3 does not supply the mixed sublimation agent to the front surface Wa of the substrate W, but controls the rotation motor 18 to rotate the rotation base 20 at a specified high-speed rotation speed (for example, a specified speed in the range of about 100 rpm to about 2500 rpm). As a result, the substrate W rotates at this high-speed rotation speed. As a result, a large centrifugal force is applied to the front surface Wa of the substrate W, and the mixed sublimation agent contained in the liquid film 81 is removed from the front surface Wa of the substrate W, and the film thickness of the liquid film 81 is reduced. As a result, as shown in Figure 7B, a thin film 82 of the mixed sublimation agent is formed on the front surface Wa of the substrate W. The film thickness W12 of the thin film 82 is thinner than, that is, lower than, the film thickness W11 of the liquid film 81. The film thickness W12 of the thin film 82 is in the order of hundreds of nanometers to several micrometers. The upper surface of the thin film 82 is located at a lower position than each pattern 100 (refer to Figure 5 The film thickness W12 of the thin film 82 is adjusted by adjusting the rotation speed of the substrate W.

[0150] The thicker the pre-solidification liquid film (thin film 82), the greater the internal stress (strain) remaining in the solidified film 83 formed in the supply liquid contact 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) can be minimized.

[0151] Furthermore, the thinner the solidified film 83 is, the less residue will remain on the front surface Wa of the substrate W after the removal step (S10) described below. By thinning the solidified film 83 before the start of the liquid supply contact step (S8), the thickness of the solidified film 83 can be adjusted to be thin. This can suppress the generation of residue after the removal step (S10).

[0152] Furthermore, 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 front surface Wa of the substrate W (solidified film forming step). The solidified film forming step includes a solvent evaporation step of evaporating the mixed solvent contained in the mixed sublimation agent, and a supply liquid contacting step (S8) described below. When the vapor pressure of the mixed solvent contained in the mixed sublimation agent is higher than the sublimable substance contained in the mixed sublimation agent, the mixed solvent can be preferentially evaporated from the mixed sublimation agent present on the front surface Wa of the substrate W, thereby solidifying the mixed sublimation agent through the following mechanism. Furthermore, the film thickness reduction step (S6) of rotating the substrate W at a relatively high speed is included in the solvent evaporation step.

[0153] Specifically, in the film thickness reducing step ( S6 ), the substrate W is rotated at a high rotational speed, thereby increasing the number of collisions per unit time between the liquid film 81 (thin film 82 ) and the gas contained in the atmosphere around the front surface Wa of the substrate W. This promotes the vaporization of molecules of the sublimable substance contained in the mixed sublimation agent.

[0154] In addition, in this embodiment, a heating step (S7) of heating the front side Wa of the substrate W is performed in parallel with the film thickness reduction 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. Thus, as shown in FIG7B , a heating fluid is supplied from the lower surface nozzle 12 to the central portion of the back side Wb of the rotating substrate W. The heating fluid supplied to the back side Wb of the substrate W receives the centrifugal force generated by the rotation of the substrate W and diffuses toward the outer periphery of the substrate W. Thus, the heating fluid is supplied to the entire area of the back side Wb of the substrate W, and the thin film 82 of the mixed sublimation agent is heated over the entire area of the front side Wa of the substrate W. By heating the thin film 82 of the mixed sublimation agent, the mixed solvent with a higher vapor pressure in the mixed sublimation agent contained in the thin film 82 is preferentially evaporated. As the mixed solvent evaporates from the mixed sublimation agent, the concentration of the sublimable substance in the thin film 82 of the mixed sublimation agent increases. As a result, the freezing point T of the mixed sublimation agent increases. FM When the freezing point T FM When the temperature reaches room temperature, the sublimable substance contained in the mixed sublimation agent present on the front surface Wa of the substrate W starts to solidify. This further promotes the formation of the solidified film 83 .

[0155] As the mixed solvent evaporates from the mixed sublimation agent in the film thickness reducing step (S6) and the heating step (S7), the Figure 3 As shown by the hollow arrow, the concentration of the sublimable substance in the liquid film 81 (thin film 82) of the mixed sublimation agent increases. FM When the freezing point T FM When the temperature reaches room temperature, the mixed sublimation agent present on the front surface Wa of the substrate W begins to solidify.

[0156] When a predetermined period has elapsed since the start of the film thickness reducing step ( S6 ) and the heating step ( S7 ), the supply of the heating fluid to the back surface Wb of the substrate W is stopped.

[0157] Furthermore, the control device 3 decelerates the rotation speed of the spin base 20 to the liquid processing speed or the liquid processing speed, and constantly maintains the rotation speed.

[0158] 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 retreat position on the side of the spin chuck 5 to above the center of the front surface Wa of the substrate W. Then, the control device 3 opens the supply liquid valve 55, and as shown in Figure 7C, the supply liquid is ejected from the supply liquid nozzle 51 toward the center of the upper surface (front surface Wa) of the substrate W. The supply liquid is supplied from the supply liquid nozzle 51 at a low flow rate (e.g., approximately 150 mL / min). Therefore, the mixed sublimation agent thin film 82 can be maintained in a film-like shape regardless of the supply liquid to the front surface Wa of the substrate W. Furthermore, by supplying the supply liquid to the front surface Wa of the substrate W while maintaining the mixed sublimation agent thin film 82 in a film-like shape without causing the mixed sublimation agent thin film 82 to collapse, the solidified film 83 obtained by solidifying the sublimation substance contained in the mixed sublimation agent thin film 82 can be made into a good film-like shape.

[0159] The supply liquid deposited on the center portion of the front surface Wa of the substrate W receives the centrifugal force generated by the rotation of the substrate W and flows toward the peripheral portion of the front surface Wa of the substrate W. As a result, a supply liquid film 84 is formed on the thin film 82 of the mixed sublimation agent on the front surface Wa of the substrate W, covering the entire upper surface of the thin film 82. This allows the mixed sublimation agent and the supply liquid to contact over the entire upper surface of the thin film 82 of the mixed sublimation agent. Consequently, the mixed sublimation agent and the supply liquid can be brought into contact over a larger contact area. This allows for more efficient removal of the mixed solvent from the mixed sublimation agent. Consequently, the sublimable substance can be more effectively solidified.

[0160] Furthermore, the liquid temperature of the supply liquid supplied to the front surface Wa of the substrate W in the supply liquid contacting step ( S8 ) is lower than room temperature. Therefore, the front surface Wa of the substrate W is cooled by supplying the supply liquid to the front surface Wa of the substrate W. This can lower the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 .

[0161] In addition, the supply liquid as a polar substance and the sublimable substance as a non-polar substance are (almost) insoluble in each other (strictly speaking, camphor dissolves only a very small amount in water). Therefore, even if the supply liquid is brought into contact with the mixed sublimation agent, the sublimable substance and the supply liquid will not mix with each other.

[0162] If the supply liquid is in contact with the film 82 of the mixed sublimation agent (in a system in which the phase of the mixed sublimation agent is in contact with the phase of the supply liquid) and an equilibrium state is reached, then the ratio of the mixed solvent dissolved in the sublimation substance and the supply liquid becomes an inherent value (a value determined by the distribution coefficient).

[0163] In the case where the sublimable substance is camphor and the supply liquid is water, the partition coefficient of the mixed solvent relative to camphor and water is small (that is, it is significantly more likely to partition into water). In this case, if the supply liquid comes into contact with the thin film 82 of the mixed sublimation agent, the mixed solvent contained in the mixed sublimation agent moves from the mixed sublimation agent to the supply liquid, and the mixed solvent dissolves in the supply liquid. As the mixed solvent moves, the concentration of the sublimable substance in the thin film 82 of the mixed sublimation agent increases. Furthermore, as the concentration of the sublimable substance increases, the freezing point T of the mixed sublimation agent increases. FM When the freezing point T FM When the temperature reaches room temperature, the mixed sublimation agent present on the front surface Wa of the substrate W starts to precipitate. The precipitation of the mixed sublimation agent forms a solidified film 83 containing a sublimable substance.

[0164] Furthermore, as described above, the temperature of the supply liquid supplied to the front surface Wa of the substrate W is lower than room temperature (for example, the supply liquid is a cooling liquid). Therefore, the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 can be lowered by supplying the supply liquid to the front surface Wa of the substrate W. Furthermore, if the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 is lower than the freezing point T of the mixed sublimation agent, the mixed sublimation agent will be cooled. FM , then the mixed sublimation agent begins to solidify. Thus, a solidified film 83 is formed.

[0165] That is, the solidification of the mixed sublimation agent utilizes the solidification point T FM Since the two mechanisms of solidification due to the rise of the temperature and solidification accompanying the temperature drop of the mixed sublimation agent proceed simultaneously, the mixed sublimation agent can be solidified in a short period of time.

[0166] When a period of time sufficient for the supply liquid to spread over the entire front surface Wa of the substrate W has elapsed since the supply of the supply liquid was started, the control device 3 closes the supply liquid valve 55 to stop supplying the supply liquid to the front surface Wa of the substrate W.

[0167] Then, when a processing time sufficient for the sublimable substances contained in the thin film 82 of the mixed sublimate on the front surface Wa of the substrate W to be completely solidified has elapsed, the supply liquid contacting step (S8) is completed. Next, a supply liquid removing step (S9) is performed to remove the supply liquid from the front surface Wa of the substrate W. Specifically, the control device 3 controls the rotary motor 18 to accelerate the rotation speed of the substrate W to a throwing-off rotation speed capable of throwing off the supply liquid from the front surface Wa of the substrate W. In this way, the supply liquid containing the mixed solvent moved from the mixed sublimate is thrown off from the entire area of the front surface Wa of the substrate W. At this time, the removed supply liquid also contains the mixed solvent moved from the sublimable substances. In this way, the mixed solvent and the supply liquid can be effectively removed from the entire area of the front surface Wa of the substrate W. After the supply liquid removing step (S9), only a solidified film 83 is formed on the front surface Wa of the substrate W, as shown in Figure 7E.

[0168] After the solidified film 83 is formed, the sublimator substance contained in the solidified film 83 sublimates from a solid to a gas. In this embodiment, a removal step (S10) is implemented in which the sublimator substance contained in the solidified film 83 is removed without liquefying by sublimation of the sublimator substance.

[0169] In addition, in order to promote the sublimation of the solidified film 83, a gas blowing step of blowing a gas to the front surface Wa of the substrate W is performed in parallel with the removal step (S10).

[0170] Specifically, before the removal step (S10) begins, 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 processing position (above the center of the front surface Wa of the substrate W) as shown in FIG7F , and then lowers the gas nozzle 56 from the processing position to the approach position close to the substrate W. When the gas nozzle 56 is arranged at the processing position (including the approach position), the central axis of the gas nozzle 56 is aligned with the rotation axis A1.

[0171] Then, the control device 3 opens the gas valve 60 and starts to eject gas from the three gas outlets (upper gas outlet 65, lower gas outlet 66, and center gas outlet 67) of the gas nozzle 56. This three-layer annular airflow blows the dehumidified gas over the entire area of the solidified film 83. This blowing of gas promotes the sublimation of the sublimable substance contained in the solidified film 83.

[0172] Thus, in the removal step (S10), all the sublimable substances contained in the solidified film 83 can be sublimated. Since the sublimable substances are removed from the front surface Wa of the substrate W by vaporizing them without passing through a liquid state, the collapse of the pattern 100 can be effectively suppressed or prevented, and the front surface Wa of the substrate W can be dried.

[0173] Next, as shown in FIG7G , a final spin drying step ( S11 ) is performed to dry the substrate W. Specifically, the control device 3 controls the spin motor 18 to accelerate the substrate W to a drying rotation speed (e.g., several thousand rpm) that is higher than the rotation speed in each step from the chemical liquid step ( S2 ) to the removal step ( S10 ), and rotates the substrate W at this drying rotation speed. This exerts a strong centrifugal force on the substrate W. Liquid adhering to the back surface Wb of the substrate W is thrown off and dropped around the substrate W. In this way, the liquid is removed from the substrate W, and the back surface Wb of the substrate W is dried.

[0174] When a predetermined period of time has passed since the acceleration of the substrate W, the control device 3 stops the rotation of the substrate W by the spin chuck 5 by controlling the spin motor 18. Then, the substrate W is unloaded from the chamber 4 ( Figure 6 Specifically, the control device 3 causes the hand H of the substrate transport robot CR to enter the interior of the chamber 4. The control device 3 then causes the substrate W on the spin chuck 5 to be held by the hand H of the substrate transport robot CR. The control device 3 then causes the hand H of the substrate transport robot CR to retract from the chamber 4. This allows the processed substrate W to be unloaded from the chamber 4.

[0175] As described above, according to this embodiment, a mixed sublimation agent obtained by mixing a sublimable substance with a mixing solvent is supplied to the front surface Wa of the substrate W. Since the sublimable substance has a freezing point T above room temperature, F1 , so sometimes part or the whole of it is solid under room temperature conditions. The freezing point of the mixed sublimator is lowered by the freezing point of the sublimable substance and the mixing solvent. FM Lower than the freezing point T of the sublimable substance F1 That is to say, even at the freezing point T FM For example, when the freezing point T of the mixed sublimation agent is above room temperature, FM The heat energy required to maintain the mixed sublimation agent in a liquid state can be reduced. This prevents unintended solidification of the sublimation material without significantly increasing costs, and allows for good processing of the front surface Wa of the substrate W.

[0176] Furthermore, a liquid film (liquid film 81) of a mixed sublimation agent, formed by mixing a sublimation agent (a nonpolar substance) with an amphiphilic mixed solvent, is formed on the front surface Wa of the substrate W. Furthermore, a supply liquid (a polar substance) is supplied to this mixed sublimation agent liquid film (film 82). The supply liquid (a polar substance) is (almost) insoluble in the sublimation agent (a nonpolar substance). Therefore, even if the supply liquid comes into contact with the mixed sublimation agent, the sublimation agent and the supply liquid will not mix with each other.

[0177] If the supply liquid is in contact with the liquid film of the mixed sublimation agent (film 82) (in a system in which the phase of the mixed sublimation agent is in contact with the phase of the supply liquid), and an equilibrium state is reached, then the ratio of the mixing solvent dissolved in the sublimation substance and the supply liquid becomes an inherent value (a value determined by the distribution coefficient). Therefore, for example, when the distribution coefficient of the mixing solvent relative to the sublimation substance and the supply liquid is small, if the supply liquid contacts 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. As the mixing solvent moves, the concentration of the sublimation substance in the liquid film of the mixed sublimation agent increases. In addition, as the concentration of the sublimation substance increases, the freezing point T of the mixed sublimation agent increases. FM When the freezing point T FMWhen the temperature reaches room temperature, the sublimable substance contained in the mixed sublimation agent present on the front surface Wa of the substrate W begins to precipitate. Thus, a solidified film 83 is formed. FM The rise of the temperature solidifies the sublimable substance contained in the mixed sublimation agent, so the mixed sublimation agent does not necessarily need to be cooled for solidification. Therefore, the sublimable substance supplied to the front surface Wa of the substrate W can be well solidified without significantly increasing the cost.

[0178] In addition, in the supply liquid contact step (S8), the supply liquid is supplied to the front surface Wa of the substrate W while maintaining the mixed sublimation agent film 82 in a film shape without collapsing the mixed sublimation agent film 82. Therefore, the solidified film 83 obtained by solidifying the sublimable substance contained in the mixed sublimation agent film 82 can be made into a good film shape.

[0179] Furthermore, in the supply liquid contacting step (S8), the temperature of the supply liquid supplied to the front surface Wa of the substrate W is lower than room temperature. Therefore, the front surface Wa of the substrate W can be cooled by supplying the supply liquid to the front surface Wa of the substrate W. As a result, the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 can be lowered. Furthermore, when the temperature of the mixed sublimation agent contained in the mixed sublimation agent thin film 82 is lower than the freezing point T of the mixed sublimation agent, the mixed sublimation agent is cooled. FM When the sublimable substance contained in the mixed sublimation agent begins to solidify, a solidified film 83 is formed.

[0180] In addition, since the vapor pressure of the mixed solvent is higher than that of the sublimable substance, the mixed solvent can be preferentially evaporated from the mixed sublimation agent present on the front surface Wa of the substrate W. As the mixed solvent evaporates from the mixed sublimation agent, the concentration of the sublimable substance in the thin film 82 of the mixed sublimation agent increases. As a result, the freezing point T FM When the freezing point T FM When the temperature reaches room temperature, the sublimable substance contained in the mixed sublimation agent present on the front surface Wa of the substrate W starts to solidify. This further promotes the formation of the solidified film 83 .

[0181] Furthermore, cooling water is supplied to the front surface Wa of the substrate W in the liquid supply and contact step (S8), and a heating fluid is supplied to the back surface Wb of the substrate W in the heating step (S7). Therefore, temperature zones can be divided between the front surface Wa side of the substrate W and the back surface Wb side of the substrate W. Consequently, the operating time of each step can be set without considering the influence of the thermal history on each side of the substrate W.

[0182] Figure 8A It is a schematic cross-sectional view for explaining a configuration example of the processing unit 202 according to the second embodiment of the present invention.

[0183] In the second embodiment, the parts common to the first embodiment are marked with Figure 1 The same reference numerals as in FIG. 7 are used and description thereof will be omitted.

[0184] The processing unit 202 of the second embodiment is different from the processing unit 2 of the first embodiment (see Figure 2 ) in that a shielding member 210 is provided. This shielding member 210 faces the upper surface of the substrate W held by the spin chuck 5 and shields the space above the substrate W from the surrounding atmosphere. Furthermore, a gas blowing unit 211 is provided in place of the gas blowing unit 11. In this embodiment, the gas blowing unit 211 is composed of an upper surface nozzle 221, a gas pipe 224, and a gas valve 225.

[0185] The blocking member 210 includes a blocking plate 220 and an upper surface nozzle 221 that vertically penetrates the center portion of the blocking plate 220. A blocking plate rotation unit (not shown) including an electric motor is coupled to the blocking plate 220. This blocking plate rotation unit rotates the blocking plate 220 about a rotation axis (not shown) coaxial with the rotation axis A1.

[0186] The shielding plate 220 has a circular substrate-facing surface 220a on its lower surface, facing the entire upper surface of the substrate W. A cylindrical through-hole 220b is formed in the center of the substrate-facing surface 220a, extending vertically through the shielding plate 220. An upper surface nozzle 221 is inserted through the through-hole 220b. Alternatively, a cylindrical portion protruding downward over the entire outer periphery of the substrate-facing surface 220a may be formed.

[0187] The upper surface nozzle 221 is mounted on the shielding plate 220 so as to be movable upward and downward as a whole. The upper surface nozzle 221 has a discharge port 221 a formed at its lower end portion so as to face the center portion of the upper surface of the substrate W held by the spin chuck 5 .

[0188] A blocking member lifting unit (not shown) including an electric motor, a ball screw, etc. is coupled to the blocking member 210. The blocking member lifting unit (not shown) vertically lifts the blocking plate 220 and the upper surface nozzle 221.

[0189] The blocking member lifting unit moves the blocking plate 220 to a blocking position ( ) where the substrate facing surface 220 a is close to the upper surface of the substrate W held by the spin chuck 5 . Figure 8B The position shown) and the retreat position ( Figure 2The blocking member lifting unit can hold the blocking plate 220 at both the blocking position and the retreat position. The blocking position is, for example, a position where a blocking space 230 is formed between the substrate facing surface 220a and the front surface Wa of the substrate W (see FIG. Figure 8B The shutoff space 230 is not completely isolated from the surrounding space, but gas does not flow from the surrounding space into the shutoff space 230. In other words, the shutoff space 230 is substantially shut off from the surrounding space.

[0190] The upper surface nozzle 221 is connected to a gas pipe 224. A gas valve 225 for opening and closing the gas pipe 224 is installed in the gas pipe 224. The gas supplied to the gas pipe 224 is a dehumidified gas, particularly an inert gas. Inert gases include, for example, nitrogen or argon. Alternatively, the gas may be an active gas such as air. By opening the gas valve 225, an inert gas is supplied to the upper surface nozzle 221. As a result, gas is ejected downward from the ejection port 221a and blown onto the front surface Wa of the substrate W. In this embodiment, the upper surface nozzle 221, the gas pipe 224, and the gas valve 225 constitute a gas blowing unit.

[0191] Furthermore, the rinse liquid supply unit 7 may include the upper surface nozzle 221 as the rinse liquid nozzle. In other words, the rinse liquid from the rinse liquid pipe 37 may be supplied to the upper surface nozzle 221.

[0192] Figure 8B Schematic diagram showing the removal step (S10) performed in the processing unit 202. The control device 3 controls the shielding member lifting unit before the removal step (S10) starts, such as Figure 8B As shown, the blocking member 210 is lowered and arranged at the blocking position.

[0193] In the gas blowing step, the control device 3 opens the gas valve 225. Figure 8B As shown, dehumidified gas is ejected from the nozzle 221a of the upper surface nozzle 221 toward the center of the front surface Wa of the rotating substrate W. The gas from the upper surface nozzle 221 is blown toward the center of the front surface Wa of the substrate W. Furthermore, the gas from the upper surface nozzle 221 moves along the shielded space 230 toward the outer periphery of the substrate W. Thus, the gas is blown across the entire area of the front surface Wa of the substrate W. This blowing of gas promotes the sublimation of the sublimable substance contained in the solidified film 83.

[0194] As mentioned above, although two embodiments of the present invention have been described, the present invention can also be implemented in other aspects.

[0195] For example, in the supply liquid contacting step ( S8 ), the supply position of the supply liquid on the front surface Wa of the substrate W may be moved within the front surface Wa of the substrate W.

[0196] As shown in FIG. 9A and FIG. 9B , the nozzle moving unit 53 (see FIG. Figure 4 ) The supply liquid nozzle 51 is moved horizontally between a central position where the supply liquid ejected from the supply liquid nozzle 51 lands on the central portion of the upper surface of the substrate W and a peripheral position where the supply liquid ejected from the supply liquid nozzle 51 lands on the peripheral portion of the upper surface of the substrate W. Both the central position and the peripheral position are processing positions. A gas nozzle 301 for ejecting gas downward is mounted on the nozzle arm 52. Therefore, when the nozzle arm 52 is moved, the supply liquid nozzle 51 and the gas nozzle 301 move while maintaining a fixed positional relationship between the supply liquid nozzle 51 and the gas nozzle 301. The gas nozzle 301 is mounted on the nozzle arm 52 so that the gas blowing region on the front surface Wa of the substrate W is located radially inward of the supply position of the supply liquid on the front surface Wa of the substrate W.

[0197] A gas pipe 302 that guides gas to the gas nozzle 301 is connected to the gas nozzle 301. A gas valve 303 is installed in the gas pipe 302. 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. As a result, the gas is blown downward from the gas nozzle 301.

[0198] The gas supplied to the gas pipe 302 is a dehumidified gas, particularly an inert gas. Examples of inert gases include nitrogen and argon. Alternatively, the gas may be an active gas such as air.

[0199] Next, in the supply liquid contact step ( S8 ), the control device 3 controls the nozzle moving unit 53 to horizontally move the supply liquid nozzle 51 for discharging the supply liquid and the gas nozzle 301 for discharging the gas from the center of the substrate W toward the periphery of the substrate W.

[0200] At the supply position PS on the front surface Wa of the substrate W, the supplied liquid solidifies immediately after being supplied, forming a solidified body 83A. Furthermore, at the gas blowing position PB on the front surface Wa of the substrate W, the supplied liquid is blown away by the gas. Thus, after the supplied liquid assists in solidification on the front surface Wa of the substrate W, it is quickly removed from the front surface Wa.

[0201] The moving speed of the supply position PS is preferably adjusted so that the solidified body 83A of the supplied liquid can be satisfactorily formed at each supply position PS, and the supply position PS is moved from the center to the peripheral portion of the substrate W. As a result, the formation position of the solidified body 83A is expanded from the center to the peripheral portion of the substrate W. In this way, the solidified film 83 can be formed over the entire front surface Wa of the substrate W.

[0202] Since the solidified film 83 can be formed on the entire front surface Wa of the substrate W by moving the liquid supply nozzle 51 from the central position to the peripheral position, the solidified film 83 covering the entire front surface Wa of the substrate W can be formed in a short time.

[0203] Furthermore, since the supply liquid supplied to the front 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 shortened, thereby improving the throughput.

[0204] In addition, although the supply liquid is supplied from the supply liquid nozzle 51 to the front surface Wa of the substrate W in a continuous flow in the supply liquid contact step (S8), it may be supplied as follows. Figure 10 As shown, the supply liquid nozzle 451, which has a plurality of tiny nozzles on its lower surface 451a, ejects the supply liquid in a jet-like pattern. The supply liquid ejected from the supply liquid nozzle 451 is supplied to the entire front surface Wa of the substrate W in a jet-like pattern. The supply liquid ejected from the supply liquid nozzle 451 is ejected at a relatively low ejection pressure. Because the supply liquid is supplied to the front surface Wa of the substrate W in a jet-like pattern with a relatively low ejection pressure, the supply of the supply liquid does not cause deformation of the film 82 of the mixed sublimation agent during the supply liquid contacting step (S8). Therefore, the supply liquid can be supplied to the front surface Wa of the substrate W while maintaining the film shape of the mixed sublimation agent film 82.

[0205] In addition, Figure 10 In the example shown in FIG, the supply range of the supply liquid from the supply liquid nozzle 451 is the entire front surface Wa of the substrate W. However, the supply range of the supply liquid from the supply liquid nozzle 451 may be a portion of the front surface Wa of the substrate W. 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 front surface Wa of the substrate W.

[0206] In addition, for example, in the liquid supply and contact step (S8), the substrate W may be cooled. As a method for cooling the substrate W in this way, a method of supplying a cooling fluid to the back surface Wb of the substrate W or a method of cooling the substrate W as shown in FIG. Figure 11 The cooling plate 501 shown is arranged close to the back surface Wb of the substrate W.

[0207] A cooling plate 501 serving as a cooling unit is provided in place of the lower surface nozzle 12. The cooling plate 501 is disposed above the spin base 20 and below the substrate W held by the clamping member 21. The cooling plate 501 has an upper surface 501a facing the entire back 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 within the surface. The temperature of the cooling plate 501 is lowered by the control device 3, thereby uniformly cooling the entire front surface Wa of the substrate W. In addition, the cooling plate 501 can also be used to cool a cooling fluid or a heating fluid.

[0208] In addition, as another form of the cooling unit for cooling the front surface Wa of the substrate W, a configuration in which a cooler is built into the interior of the blocking member 210 can be cited.

[0209] like Figure 12 As shown, the internal cooler 601 is disposed within the shielding plate 220 of the shielding member 210. The internal cooler 601 is raised and lowered together with the shielding member 210. The substrate W is disposed below the internal cooler 601. The internal cooler 601 is, for example, a piezoelectric element. The temperature of the internal cooler 601 is controlled by the control device 3. The temperature of the substrate facing surface 220a is uniform across the surface.

[0210] In the supply liquid contact step ( S8 ), the control device 3 may lower the temperature of the internal cooler 601 to a temperature lower than room temperature to cool the front surface Wa of the substrate W. Thus, the mixed sublimation agent on the front surface Wa of the substrate W can be cooled.

[0211] In addition, in the supply liquid contacting step (S8), the supply liquid supplied to the supply liquid piping 54 may also have a liquid temperature higher than room temperature. In the present embodiment, the liquid temperature of the supply liquid is 50°C to 60°C. In the case where the mixed solvent has a vapor pressure higher than the vapor pressure of the sublimable substance, in the supply liquid contacting step (S8), the mixed solvent can be preferentially evaporated from the mixed sublimator present on the front surface Wa of the substrate W. As the mixed solvent evaporates from the mixed sublimator, the concentration of the sublimable substance in the liquid film of the mixed sublimator increases. As a result, the freezing point T of the mixed sublimator increases. FM When the freezing point T FM When the temperature reaches room temperature, the sublimable substance contained in the mixed sublimation agent present on the front surface Wa of the substrate W begins to solidify. This further promotes the formation of the solidified film 83 in the supply liquid contact step (S8).

[0212] In the above embodiment, the solidified film forming step is described as including the supply liquid contact step (S8) and the solvent evaporation step, and the solvent evaporation step is described as including the film thickness reduction step (S6: substrate rotation step) and the heating step (S7). The heating step (S7) and the film thickness reduction step (S6) may be performed separately rather than in parallel.

[0213] The heating unit for heating the front surface Wa of the substrate W in the heating step (S7) is not limited to the configuration of supplying the heating fluid to the back surface Wb of the substrate W as in the above embodiment. Figure 13 The heating plate 701 shown, which is arranged below and opposite to the back surface Wb of the substrate W, serves as a heating unit. The heating plate 701 is provided in place of the lower surface nozzle 12. The heating plate 701 has a built-in heater 702. The built-in heater 702 is, for example, a heating wire that generates heat when energized. The heating plate 701 is arranged above the spin base 20 and below the substrate W held by the clamping member 21. The heating plate 701 has an upper surface 701a that faces the entire back surface Wb of the substrate W. Even if the spin chuck 5 rotates, the heating plate 701 does not rotate. The temperature of the heating plate 701 is changed by the control device 3. The temperature of the upper surface 701a of the heating plate 701 is uniform across the surface. The temperature of the heating plate 701 is increased by the control device 3, thereby uniformly heating the entire front surface Wa of the substrate W.

[0214] In this case, in the heating step (S7), the heating fluid may not be supplied to the back side Wb of the substrate W, but the controller 3 may raise the temperature of the heating plate 701 to a temperature higher than room temperature, thereby heating the front side Wa of the substrate W. Alternatively, the heating plate 701 may be used to raise the temperature of the fluid at room temperature to a temperature higher than room temperature before supplying it to the substrate W. Furthermore, the heating fluid may be raised to a higher temperature before supplying it to the substrate W. In this manner, the mixed solvent contained in the mixed sublimation agent on the front side Wa of the substrate W can be evaporated effectively.

[0215] In addition, as another form of the heating unit for heating the front surface Wa of the substrate W, there can be mentioned the following: Figure 14 The structure shown is that a heater is built into the interior of the blocking member 210.

[0216] like Figure 14 As shown, the built-in heater 801 is disposed within the shielding plate 220 of the shielding member 210. The built-in heater 801 is raised and lowered together with the shielding 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 controlled by the control device 3. The temperature of the substrate facing surface 220a is uniform across the surface.

[0217] In the heating step (S7), the control device 3 may also be as follows Figure 14 As shown, the blocking member 210 is placed in the blocking position and the temperature of the built-in heater 801 is raised to a temperature higher than room temperature, thereby heating the front surface Wa of the substrate W. This allows the mixed solvent contained in the mixed sublimation agent on the front surface Wa of the substrate W to evaporate satisfactorily.

[0218] The solvent evaporation step may include at least one of the four steps after adding the gas blowing step and the decompression step to the film thickness reduction step (S6) and the heating step (S7). The gas blowing step is equivalent to the gas blowing step performed in parallel with the removal step (S10).

[0219] The decompression step is carried out as follows. Figure 2 ) is set to be able to adjust its exhaust force (suction force). The exhaust device 17 is provided with an exhaust force adjustment unit (decompression unit) 901 ( Figure 2 (illustrated by double-dashed lines). The exhaust force adjustment unit 901 is, for example, a regulator or an opening adjustment valve. By adjusting the exhaust force of the exhaust device 17 using the exhaust force adjustment unit 901, the pressure inside the chamber 4 is changed. In other words, the pressure inside the chamber 4 is changed by the control device 3.

[0220] In the solidified film forming step, the control device 3 can effectively evaporate the second sublimable substance contained in the mixed sublimation agent on the front surface Wa of the substrate W by reducing the pressure inside the chamber 4. Furthermore, it is sufficient to provide a pipe connected to the exhaust force adjustment unit (decompression unit) 901 in the chamber 4, and it is not necessary to provide the exhaust device 17.

[0221] In addition, the solvent evaporation step can also be combined with or replace at least one of the film thickness reduction step (S6), the heating step (S7), the gas blowing step and the decompression step, by naturally drying or imparting ultrasonic vibration to the mixed sublimation agent on the front surface Wa of the substrate W, so that the mixed solvent contained in the mixed sublimation agent on the front surface Wa of the substrate W is evaporated.

[0222] In addition, the solidified film forming step only needs to include the supply liquid contacting step ( S8 ), and does not necessarily need to include the solvent evaporating step.

[0223] In particular, when the vapor pressure of the mixing solvent is the same as or lower than that of the sublimable substance, the mixing solvent contained in the mixed sublimator does not evaporate preferentially, and therefore, there is no point in performing the solvent evaporation step.

[0224] In addition, as the supply liquid removal step (S9), a shaking-off step is described in which the substrate W is rotated about the rotation axis A1 to shake off the supply liquid present on the front surface Wa of the substrate W. Alternatively, a gas blowing step in which gas is blown onto the front surface Wa of the substrate W may be performed as the supply liquid removal step (S9) in place of or in addition to the shaking-off step. The gas blowing step is equivalent to the gas blowing step performed in parallel with the removal step (S10).

[0225] In addition, the description has been given of performing a gas blowing step in parallel with the removal step (S10) to promote sublimation of the mixed sublimation agent. The step for promoting sublimation may simply include at least one of the three steps following the addition of the substrate high-speed rotation step and the heating step to the gas blowing step. The heating step is equivalent to the heating step (S7) or its variations. The substrate high-speed rotation step is equivalent to the substrate high-speed rotation step (rapid rotation) performed in the film thickness reduction step (S6).

[0226] Furthermore, when the substrate is spun at high speed during the removal step (S10), since the back surface Wb of the substrate W is already dry after the removal step (S10), it is not necessary to spin dry the substrate after the removal step (S10). Therefore, the final spin drying step (S11) can be omitted.

[0227] When an aqueous liquid is used as the supply liquid, the supply liquid supply unit 10 may be 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 shared with the substitution solvent supply unit 8.

[0228] In each of the substrate processing examples described above, the replacement step (S4) is performed between the rinsing step (S3) and the mixed sublimation agent supply step (S5). However, if the mixed sublimation agent is miscible with the rinsing liquid (i.e., water), the replacement step (S4) may be omitted. In this case, the replacement solvent supply unit 8 of the processing unit 2 may be eliminated.

[0229] In addition, the freezing point T of the mixed sublimation agent supplied from the mixed sublimation agent supply unit 9 is FM It can also be above room temperature instead of below room temperature. In this case, a device (temperature control device) for maintaining the mixed sublimation agent in a liquid state is required inside the mixed sublimation agent supply unit 9. However, due to the freezing point T FM Lowered to below the freezing point T of the sublimable substance by freezing point depression F1 , so it is possible to seek to reduce the amount of heat used to maintain the mixed sublimation agent in a liquid state.

[0230] In addition, if Figure 15 As shown, the removal step (S10) of converting the sublimable substance contained in the solidified film 83 into a gas without passing through a liquid state may be a plasma irradiation step of irradiating the substrate W with plasma instead of a sublimation step. In other words, in the removal step, the sublimable substance contained in the solidified film 83 may be converted into a gas without passing through a liquid state through decomposition or chemical reaction based on oxygen free radicals or the like. Furthermore, the removal step, such as the plasma irradiation step, may also be performed by other processing units.

[0231] Figure 15 Schematic diagram for explaining the transport 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 gas without passing through the liquid state. Figure 15 Regarding the Figures 1 to 14 The same structure as shown is marked with Figure 1 The same reference symbols are used and their descriptions are omitted.

[0232] The processing unit 2 includes, in addition to a wet processing unit 2W that supplies a processing liquid to the substrate W, a dry processing unit 2D that processes the substrate W without supplying a processing liquid to the substrate W. Figure 15 The dry processing unit 2D includes a processing gas pipe 1001 for introducing processing gas into a chamber (second chamber) 4D, and a plasma generating device 1002 for converting the processing gas in the chamber 4D into plasma. The plasma generating device 1002 includes an upper electrode 1003 disposed above the substrate W and a lower electrode 1004 disposed below the substrate W.

[0233] Figure 15 The steps from the loading of the substrate W (S1) to the supply liquid removal step (S9) are performed in the chamber 4 of the wet processing unit 2W. Figure 15 As shown, the substrate W is carried out of the chamber 4 of the wet processing unit 2W by the substrate transport 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 front surface Wa of the substrate W is converted into gas by chemical and physical reactions caused by the plasma in the chamber 4D without passing through liquid. In this way, the solidified film 83 is removed from the substrate W. Figure 15 In the example, the formation of the solidified film 83 and the removal of the solidified film 83 are performed in the chamber 4 and the chamber 4D, respectively. Therefore, the structures in the chamber 4 and the chamber 4D can be simplified, and the chamber 4 and the chamber 4D can be miniaturized.

[0234] The present invention can also be applied to a batch-type substrate processing apparatus.

[0235] Figure 16It is a schematic diagram for explaining the structure of a substrate processing apparatus 1101 according to a third embodiment of the present invention. Figure 17 Schematic diagram showing a lifting state in the substrate processing apparatus 1101.

[0236] The substrate processing apparatus 1101 is a batch-type substrate processing apparatus that processes multiple substrates W at once. The substrate processing apparatus 1101 includes a chemical solution storage tank 1102 storing chemical solution; a rinse liquid storage tank 1103 storing rinse liquid (e.g., water); a mixed sublimation agent storage tank (first tank) 1104 storing mixed sublimation agent; and a supply liquid storage tank 1105 (second tank) storing supply liquid (e.g., aqueous solution).

[0237] The substrate processing apparatus 1101 further includes: an elevator 1106 for immersing the substrate W in the supply liquid stored in the supply liquid storage tank 1105; and an elevator lifting unit 1107 for lifting the elevator 1106. The elevator 1106 supports a plurality of substrates W in a vertical position. The elevator lifting unit 1107 moves the elevator 1106 to a processing position ( Figure 16 The substrate W held by the lifter 1106 is withdrawn from the supply liquid storage tank 1105 to the upper withdrawal position ( Figure 16 The position indicated by the double-dotted line in the figure is raised or lowered.

[0238] During a series of processes in the substrate processing apparatus 1101, multiple substrates W loaded into a processing unit of the substrate processing apparatus 1101 are immersed in a chemical solution stored in a chemical solution storage tank 1102. Thus, each substrate W undergoes chemical solution processing (cleaning or etching) (chemical solution step). After a predetermined period of time has passed since the start of immersion in the chemical solution, the multiple substrates W are lifted from the chemical solution storage tank 1102 and moved to the rinse solution storage tank 1103. Next, the multiple substrates W are immersed in a rinse solution stored in the rinse solution storage tank 1103. Thus, the substrates W undergo a rinse process (rinsing step). After a predetermined period of time has passed since the start of immersion in the rinse solution, the multiple substrates W are lifted from the rinse solution storage tank 1103 and moved to the mixed sublimation agent storage tank 1104. Next, the multiple substrates W are immersed in the mixed sublimation agent stored in the mixed sublimation agent storage tank 1104. Thus, the mixed sublimation agent treatment (mixed sublimation agent supplying step) is performed on the substrates W. When a predetermined period of time has passed since 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 .

[0239] A liquid film of the mixed sublimation agent is formed over the entire surface Wa of each substrate W that has been moved to the supply liquid reservoir 1105. The elevator raising / lowering unit 1107 is then controlled to move the elevator 1106 from the retreat position to the processing position. This immerses the plurality of substrates W held by the elevator 1106 in the supply liquid. The supply liquid is thus supplied to the front 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 front surface Wa of the substrate W (supply liquid contact step).

[0240] When the feed liquid contacts 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 feed liquid, and the mixing solvent dissolves in the feed liquid. As the mixing solvent moves, the concentration of the sublimable substance in the liquid film of the mixed sublimation agent increases. Furthermore, as the concentration of the sublimable substance increases, the freezing point T of the mixed sublimation agent decreases. FM When the freezing point T FM When the temperature reaches room temperature, the mixed sublimation agent present on the front surface Wa of the substrate W starts to precipitate. The precipitation of the mixed sublimation agent forms a solidified film 83 containing a sublimable substance.

[0241] Furthermore, when the temperature of the supply liquid stored in the supply liquid storage tank 1105 is lower than room temperature, the temperature of the mixed sublimation agent contained in the liquid film of the mixed sublimation agent can be lowered by supplying the supply liquid to the front surface Wa of the substrate W. Furthermore, when the temperature of the mixed sublimation agent contained in the liquid film of the mixed sublimation agent is lower than the freezing point T FM When the mixed sublimation agent starts to solidify, a solidified film 83 is formed.

[0242] That is, the solidification of the mixed sublimation agent is carried out by utilizing the solidification point T of the mixed sublimation agent. FM Since the two mechanisms of solidification due to the rise of the temperature and solidification accompanying the temperature drop of the mixed sublimation agent proceed simultaneously, the solidified film 83 can be formed in a short period of time.

[0243] When a predetermined period of time has passed since the substrates W were first immersed in the supply liquid, the elevator raising and lowering unit 1107 is controlled to move the elevator 1106 from the processing position to the retreat position.

[0244] When the substrate W is lifted from the supply liquid, lift drying (supply liquid removal step) is performed. Figure 17 As shown, the supply liquid is removed from the entire front surface Wa of the substrate W by blowing gas (e.g., inert gas such as nitrogen) onto the front surface Wa of the substrate W lifted from the supply liquid storage tank 1105 at a relatively slow speed (e.g., several mm / second).

[0245] Then, the sublimator substance contained in the solidified film 83 sublimates from a solid to a gas. Thus, the sublimator substance can be removed from the front surface Wa of the substrate W by vaporizing without passing through a liquid state, thereby effectively suppressing or preventing the collapse of the pattern 100 and drying the front surface Wa of the substrate W.

[0246] In addition, in each of the embodiments, the substrate processing device 1, 1101 is described as a device for processing a substrate W including a semiconductor wafer, but the substrate processing device can also be a device for processing substrates such as liquid crystal display device substrates, organic EL (electroluminescence) display device FPD (Flat Panel Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates, etc.

[0247] Furthermore, various design changes can be made within the scope of the matters described in the claims.

[0248] This application corresponds to Japanese Patent Application No. 2018-177377 filed with the Japan Patent Office on September 21, 2018, the entire disclosure of which is incorporated herein by reference.

[0249] [Explanation of Symbols]

[0250] 1 Substrate processing device

[0251] 2 processing units

[0252] 3 Control device

[0253] 4 chambers

[0254] 5. Rotary chuck (substrate holding unit)

[0255] 9. Mixed sublimation agent supply unit (mixed drying auxiliary material supply unit)

[0256] 10 Supply liquid supply unit

[0257] 11 Gas blowing unit (removal unit)

[0258] 18 Rotation motor (removal unit)

[0259] 81 Liquid Film

[0260] 82 film

[0261] 83 solidified film

[0262] 100 patterns

[0263] 1104 Mixed sublimation agent storage tank (tank 1)

[0264] 1105 Supply liquid storage tank (tank 2)

[0265] A1 rotation axis

[0266] T F1 Freezing point of sublimable substances (freezing point of drying auxiliary substances)

[0267] T FM Freezing point of mixed sublimation agent (freezing point of mixed drying auxiliary substance)

[0268] W substrate

[0269] Wa front.

Claims

1. A substrate processing method, comprising processing a substrate having a pattern on its front surface, and comprising: a mixed drying auxiliary substance supplying step of supplying the mixed drying auxiliary substance to the front surface of the substrate to form a liquid film of the mixed drying auxiliary substance on the front surface of the substrate, wherein the mixed drying auxiliary substance is obtained by mixing a drying auxiliary substance as a non-polar substance and an amphiphilic solvent, and has a freezing point lower than that of the drying auxiliary substance; a solidified film forming step of forming a solidified film containing the drying auxiliary substance by solidifying the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance; and a removing step of removing the drying auxiliary substance contained in the solidified film from the front surface of the substrate by changing the drying auxiliary substance into a gas without changing the liquid state; The solidified film forming step includes a liquid supply and liquid contact step, The supply liquid contact step is to contact a supply liquid of a polar substance different from the drying auxiliary substance and the solvent with the liquid film of the mixed drying auxiliary substance, thereby increasing the concentration of the drying auxiliary substance in the liquid film and causing the drying auxiliary substance to precipitate, thereby forming the solidified film.

2. The substrate processing method according to claim 1 , wherein the concentration increase of the drying auxiliary substance in the supply liquid contact step is caused by the solvent dissolved in the mixed drying auxiliary substance moving from the mixed drying auxiliary substance to the supply liquid. 3 . The substrate processing method according to claim 1 , wherein the drying auxiliary substance contains a sublimable substance having sublimability.

4. The substrate processing method according to claim 1 or 2, wherein the supply liquid contacting step includes the step of supplying the supply liquid to the front surface of the substrate while maintaining a liquid film of the mixed drying auxiliary substance in a film shape. 5 . The substrate processing method according to claim 1 , further comprising a supply liquid removing step of removing the supply liquid present on the front surface of the substrate before the removing step.

6. A substrate processing method according to claim 5, wherein the supply liquid removal step includes at least one of a shaking-off step of rotating the substrate around a specified rotation axis to shake off the supply liquid existing on the front surface of the substrate, and a gas blowing step of blowing gas to the front surface of the substrate. 7 . The substrate processing method according to claim 1 , wherein the supply liquid supplied to the front surface of the substrate in the supply liquid contacting step has a liquid temperature lower than room temperature.

8. The substrate processing method according to claim 1 or 2, wherein the solvent has a vapor pressure higher than the vapor pressure of the drying auxiliary substance, and The supply liquid supplied to the front surface of the substrate in the supply liquid contacting step has a liquid temperature higher than room temperature.

9. The substrate processing method according to claim 1 or 2, wherein the solvent has a vapor pressure higher than the vapor pressure of the drying auxiliary substance, and The solidified film forming step further includes a solvent evaporating step of evaporating the solvent from the mixed drying auxiliary substance present on the front surface of the substrate.

10. The substrate processing method according to claim 9, wherein the solvent evaporation step includes at least one of a heating step of heating the mixed drying auxiliary substance, a gas blowing step of blowing gas to the mixed drying auxiliary substance, a decompression step of decompressing the space around the solidified film, and a substrate high-speed rotation step of rotating the substrate at high speed around a specified rotation axis without supplying liquid to the front surface of the substrate. 11 . The substrate processing method according to claim 10 , wherein the heating step includes the step of supplying a heating fluid to a back surface of the substrate. 12 . The substrate processing method according to claim 1 , wherein the solvent has a vapor pressure that is the same as or lower than a vapor pressure of the drying auxiliary substance.

13. A substrate processing method according to claim 1 or 2, wherein the supply liquid contact step includes the following step, namely, in parallel with supplying the supply liquid to the front surface of the substrate, the supply position of the supply liquid in the front surface of the substrate is moved from the central part of the substrate to the peripheral part of the substrate, thereby expanding the formation position of the solidified film in the front surface of the substrate from the central part of the substrate to the peripheral part of the substrate.

14. The substrate processing method according to claim 1 or 2, wherein the removal step includes at least one of a sublimation step of causing the dry auxiliary substance contained in the solidified film to sublime from a solid to a gas, a decomposition step of causing the dry auxiliary substance contained in the solidified film to change into a gas without passing through a liquid state by decomposing the solidified film, and a reaction step of causing the dry auxiliary substance contained in the solidified film to change into a gas without passing through a liquid state by reacting the solidified film.

15. The substrate processing method according to claim 1 or 2, wherein the mixed dry auxiliary substance supplying step comprises the step of immersing the substrate in a first tank storing the mixed dry auxiliary substance, and The supply liquid contacting step includes immersing the substrate in a second tank storing the supply liquid.

16. The substrate processing method according to claim 1 or 2, wherein the supply liquid contains water.

17. A substrate processing apparatus comprising: a substrate holding unit for holding a substrate having a pattern on its front side; a mixed drying auxiliary substance supplying unit for supplying a mixed drying auxiliary substance to the front surface of the substrate held by the substrate holding unit, wherein the mixed drying auxiliary substance is obtained by mixing a drying auxiliary substance as a non-polar substance with an amphiphilic solvent and has a freezing point lower than that of the drying auxiliary substance; a supply liquid supply unit for supplying a supply liquid of a polar substance different from the drying auxiliary substance and the solvent to the front surface of the substrate held by the substrate holding unit; a removal unit for removing the drying auxiliary substance from the front surface of the substrate held by the substrate holding unit by changing the drying auxiliary substance into a gas without changing the state from a liquid state; and a control device for controlling the mixed drying auxiliary substance supply unit, the supply liquid supply unit, and the removal unit; The control device executes: a mixed drying auxiliary substance supplying step, supplying the mixed drying auxiliary substance to the front surface of the substrate through the mixed drying auxiliary substance supplying unit, and forming a liquid film of the mixed drying auxiliary substance on the front surface of the substrate; a solidified film forming step of forming a solidified film containing the drying auxiliary substance by solidifying the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance; and a removing step of removing the drying auxiliary substance contained in the solidified film from the front surface of the substrate by the removing unit so as to change the drying auxiliary substance into a gas without passing through a liquid state; and The control device executes a supply liquid contacting step during the solidified film forming step, wherein the supply liquid contacting step includes supplying the supply liquid to the liquid film of the mixed drying auxiliary substance through the supply liquid supply unit, and as the solvent dissolved in the mixed drying auxiliary substance moves from the mixed drying auxiliary substance to the supply liquid, the concentration of the drying auxiliary substance in the liquid film increases, thereby causing the drying auxiliary substance to precipitate, thereby forming the solidified film.

18. A substrate processing apparatus comprising: a substrate holding unit for holding a substrate having a pattern on its front side; a mixed drying auxiliary substance supplying unit for supplying a mixed drying auxiliary substance to the front surface of the substrate held by the substrate holding unit, wherein the mixed drying auxiliary substance is obtained by mixing a drying auxiliary substance as a non-polar substance with an amphiphilic solvent and has a freezing point lower than that of the drying auxiliary substance; a supply liquid supply unit for supplying a supply liquid of a polar substance different from the drying auxiliary substance and the solvent to the front surface of the substrate held by the substrate holding unit; a removal unit for removing the drying auxiliary substance from the front surface of the substrate held by the substrate holding unit by changing the drying auxiliary substance into a gas without changing the state from a liquid state; and a control device for controlling the mixed drying auxiliary substance supply unit, the supply liquid supply unit, and the removal unit; The control device executes: a mixed drying auxiliary substance supplying step, supplying the mixed drying auxiliary substance to the front surface of the substrate through the mixed drying auxiliary substance supplying unit, and forming a liquid film of the mixed drying auxiliary substance on the front surface of the substrate; a solidified film forming step of forming a solidified film containing the drying auxiliary substance by solidifying the drying auxiliary substance contained in the liquid film of the mixed drying auxiliary substance; and a removing step of removing the drying auxiliary substance contained in the solidified film from the front surface of the substrate by the removing unit so as to change the drying auxiliary substance into a gas without passing through a liquid state; and The control device executes, in the solidified film forming step, a step of forming the solidified film by precipitating the drying auxiliary substance by increasing the concentration of the drying auxiliary substance in the liquid film of the mixed drying auxiliary substance.

19. A substrate processing device according to claim 18, wherein the control device performs a supply liquid contacting step in the solidified film forming step, and the supply liquid contacting step is to make a supply liquid that is a polar substance different from the drying auxiliary substance and the solvent contact with the liquid film of the mixed drying auxiliary substance, and the concentration of the drying auxiliary substance in the liquid film increases to cause the drying auxiliary substance to precipitate, thereby forming the solidified film. 20 . The substrate processing apparatus according to claim 17 , wherein the drying auxiliary substance contains a sublimable substance having sublimability.

21. The substrate processing apparatus according to claim 17 or 19, wherein the supply liquid contacting step includes the step of supplying the supply liquid to the front surface of the substrate while maintaining a liquid film of the mixed drying auxiliary substance in a film shape.

22. The substrate processing apparatus according to claim 17 or 19, further comprising a supply liquid removing step of removing the supply liquid present on the front surface of the substrate before the removing step.

23. A substrate processing device according to claim 22, wherein the supply liquid removal step includes at least one of a shaking-off step of rotating the substrate around a specified rotation axis to shake off the supply liquid present on the front surface of the substrate, and a gas blowing step of blowing gas to the front surface of the substrate. 24 . The substrate processing apparatus according to claim 17 , wherein the supply liquid supplied to the front surface of the substrate in the supply liquid contacting step has a liquid temperature lower than room temperature.

25. The substrate processing apparatus according to claim 17 or 19, wherein the solvent has a vapor pressure higher than a vapor pressure of the drying auxiliary substance, and The supply liquid supplied to the front surface of the substrate in the supply liquid contacting step has a liquid temperature higher than room temperature.

26. The substrate processing apparatus according to claim 17 or 19, wherein the solvent has a vapor pressure higher than a vapor pressure of the drying auxiliary substance, and The solidified film forming step further includes a solvent evaporating step of evaporating the solvent from the mixed drying auxiliary substance present on the front surface of the substrate.

27. A substrate processing device according to claim 26, wherein the solvent evaporation step includes at least one of a heating step of heating the mixed drying auxiliary substance, a gas blowing step of blowing gas to the mixed drying auxiliary substance, a decompression step of decompressing the space around the solidified film, and a substrate high-speed rotation step of rotating the substrate at high speed around a specified rotation axis without supplying liquid to the front surface of the substrate.

28. The substrate processing apparatus according to claim 27, wherein the heating step includes the step of supplying a heating fluid to a back surface of the substrate. 29 . The substrate processing apparatus according to claim 17 , wherein the solvent has a vapor pressure that is the same as or lower than a vapor pressure of the drying auxiliary substance.

30. A substrate processing device according to claim 17 or 19, wherein the supply liquid contact step includes the following steps, namely, in parallel with supplying the supply liquid to the front surface of the substrate, the supply position of the supply liquid in the front surface of the substrate is moved from the central part of the substrate to the peripheral part of the substrate, thereby expanding the formation position of the solidified film in the front surface of the substrate from the central part of the substrate to the peripheral part of the substrate.

31. A substrate processing device according to claim 17 or 19, wherein the removal step includes at least one of a sublimation step of causing the dry auxiliary substance contained in the solidified film to sublime from a solid to a gas, a decomposition step of causing the dry auxiliary substance contained in the solidified film to change into a gas without passing through a liquid state by decomposing the solidified film, and a reaction step of causing the dry auxiliary substance contained in the solidified film to change into a gas without passing through a liquid state by reacting the solidified film.

32. The substrate processing apparatus according to claim 17 or 19, wherein the mixed dry auxiliary substance supplying step comprises the step of immersing the substrate in a first tank storing the mixed dry auxiliary substance, and The supply liquid contacting step includes immersing the substrate in a second tank storing the supply liquid.

33. The substrate processing apparatus according to claim 17 or 19, wherein the supply liquid contains water.

Images