Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method and a substrate processing apparatus capable of appropriately processing a substrate.SOLUTION: The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method for processing a substrate includes a placing step, a first supply step, a condensation step, and a melting step. In the placing step, the substrate is placed in a substantially horizontal posture within a housing. In the first supply step, first processing gas is supplied to the housing. In the condensation step, the first process gas is condensed to form a first solid film covering the top surface of the substrate. In the melting step, the first solid film is melted to form a liquid film covering the upper surface of the substrate.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method and a substrate processing apparatus for processing substrates, such as semiconductor wafers, liquid crystal display substrates, organic electroluminescence (EL) substrates, flat panel display (FPD) substrates, optical display substrates, magnetic disk substrates, optical disk substrates, magneto-optical disk substrates, photomask substrates, and solar cell substrates. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method and a substrate processing apparatus. The substrate processing apparatus includes a spin base, an electric motor, and a nozzle. The spin base holds a substrate in a substantially horizontal position. The electric motor rotates the spin base. The nozzle discharges a processing liquid onto the substrate held on the spin base. The processing liquid is, for example, SC1. SC1 is a mixture of ammonia water, hydrogen peroxide water, and deionized water.

[0003] The substrate processing method includes a step of supplying SC1. In the step of supplying SC1, an electric motor rotates the substrate held by a spin base, and a nozzle discharges SC1 onto the substrate. Thus, SC1 is supplied onto the substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2002-329696 A Summary of the Invention [Problem to be solved by the invention]

[0005] Even with conventional substrate processing methods and substrate processing apparatuses, there are cases where a substrate cannot be processed properly. For example, when a substrate has a pattern formed on its upper surface, even with conventional substrate processing methods and substrate processing apparatuses, the pattern may collapse. For example, when the pattern is fine, even with conventional substrate processing methods and substrate processing apparatuses, there are cases where the collapse of the pattern cannot be sufficiently suppressed.

[0006] Furthermore, in conventional substrate processing methods and substrate processing apparatuses, the substrate is rotated and a processing liquid is ejected onto the substrate from a nozzle. At this time, some of the processing liquid ejected onto the substrate overflows onto the substrate. Therefore, a large amount of processing liquid must be supplied to the substrate to process the substrate. As a result, conventional methods and apparatuses use a relatively large amount of processing liquid.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can process a substrate appropriately. [Means for solving the problem]

[0008] The present invention was achieved through further intensive research based on these findings and has the following configuration: That is, the present invention is a substrate processing method for processing a substrate, comprising: a loading step of loading the substrate in a substantially horizontal position within a housing, a first supply step of supplying a first process gas to the housing, a sublimation step of sublimating the first process gas to form a first solid film covering an upper surface of the substrate, and a melting step of melting the first solid film to form a liquid film covering the upper surface of the substrate.

[0009] The substrate processing method includes a placing step and a first supplying step. In the placing step, the substrate is placed in a substantially horizontal position within a housing. In the first supplying step, a first processing gas is supplied to the housing. Therefore, in the placing step and the first supplying step, the upper surface of the substrate does not come into contact with the interface formed between the gas and the liquid. Hereinafter, the interface formed between the gas and the liquid will be referred to as the "gas-liquid interface" as appropriate.

[0010] The substrate processing method includes a sublimation process. In the sublimation process, a first process gas is sublimated in a housing. In the sublimation process, the first process gas is transformed into a first solid film without passing through a liquid state. The first solid film covers the upper surface of the substrate. Therefore, in the sublimation process, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0011] The substrate processing method includes a melting step. In the melting step, the first solid film melts. In the melting step, the first solid film is transformed into a liquid film. The liquid film covers the upper surface of the substrate. As described above, the first solid film covers the upper surface of the substrate. Therefore, in the melting step, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0012] In summary, in the placing step, the first supplying step, the sublimation step, and the melting step, the upper surface of the substrate does not come into contact with the gas-liquid interface. Therefore, the substrate processing method can form a liquid film on the upper surface of the substrate while protecting the upper surface of the substrate. Therefore, the substrate processing method can process the substrate appropriately.

[0013] Furthermore, the substrate processing method sublimates the first processing gas to form a first solid film covering the upper surface of the substrate, and then melts the first solid film to form a liquid film covering the upper surface of the substrate. This effectively prevents the processing liquid from overflowing from the substrate. That is, it effectively reduces loss of processing liquid. Therefore, the substrate processing method can efficiently form a liquid film using less processing liquid. That is, the substrate processing method can process the substrate with a small amount of processing liquid. As a result, the substrate processing method uses a relatively small amount of processing liquid. For example, the amount of processing liquid used in the substrate processing method is less than the amount of processing liquid used in conventional methods.

[0014] In the above-described substrate processing method, it is preferable that the sublimation step cools the first process gas while maintaining the gas pressure within the housing at a pressure at which the first process gas can sublimate, and the melting step heats the first solid film while maintaining the gas pressure within the housing at a pressure at which the first solid film can melt. The sublimation step maintains the gas pressure within the housing at a pressure at which the first process gas can sublimate. Therefore, the sublimation step can effectively suppress condensation of the first process gas. The sublimation step cools the first process gas. Therefore, the first process gas effectively sublimates in the sublimation step. The melting step maintains the gas pressure within the housing at a pressure at which the first solid film can melt. Therefore, the melting step can effectively suppress sublimation of the first solid film. The melting step heats the first solid film. Therefore, the first solid film effectively melts in the melting step.

[0015] In the above-described substrate processing method, it is preferable that the sublimation step cools the substrate to a temperature at which the first process gas sublimes on the upper surface of the substrate, and the melting step heats the substrate to a temperature at which the first solid film melts. The sublimation step cools the first process gas via the substrate. In the sublimation step, the upper surface of the substrate comes into contact with the first process gas. Therefore, the sublimation step can efficiently form the first solid film on the upper surface of the substrate. The sublimation step cools the substrate to a temperature at which the first process gas sublimes on the upper surface of the substrate. Therefore, the sublimation step can efficiently sublimate the first process gas into the first solid film. The melting step heats the first solid film via the substrate. In the melting step, the upper surface of the substrate comes into contact with the first solid film. Therefore, the melting step can efficiently form a liquid film. The melting step heats the substrate to a temperature at which the first solid film melts. Therefore, the melting step can suitably melt the first solid film into a liquid film.

[0016] In the above-described substrate processing method, the first processing gas preferably contains at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas. As described above, the liquid film is derived from the first processing gas. Therefore, the liquid film contains at least one of water, ammonia, methylamine, dimethylamine, trimethylamine, and hydrogen peroxide. Therefore, the liquid film can properly process the substrate.

[0017] In the above-described substrate processing method, it is preferable that the first processing gas is water vapor, and that in the sublimation process, the gas pressure in the housing is lower than the pressure of the triple point of water, and in the melting process, the gas pressure in the housing is higher than the pressure of the triple point of water. In the sublimation process, the gas pressure in the housing is lower than the pressure of the triple point of water. Therefore, in the sublimation process, condensation of water vapor can be suitably suppressed. In the melting process, the gas pressure in the housing is higher than the pressure of the triple point of water. Therefore, in the melting process, sublimation of the first solid film can be suitably suppressed.

[0018] The above-described substrate processing method preferably includes a solidification step of solidifying the liquid film to form a second solid film on the upper surface of the substrate, and a sublimation step of sublimating the second solid film.

[0019] The substrate processing method includes a solidification process. In the solidification process, the liquid film solidifies. In the solidification process, the liquid film is transformed into a second solid film. The second solid film is formed on the upper surface of the substrate. As described above, the liquid film formed in the melting process covers the upper surface of the substrate. Therefore, in the solidification process, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0020] The substrate processing method includes a sublimation process. In the sublimation process, the second solid film sublimes. In the sublimation process, the second solid film leaves the substrate without passing through a liquid. Therefore, in the sublimation process, the upper surface of the substrate does not come into contact with the gas-liquid interface. As the second solid film sublimes, the substrate W is dried.

[0021] In summary, in the solidification and sublimation processes, the upper surface of the substrate does not come into contact with the gas-liquid interface. Therefore, the substrate processing method can dry the substrate while suitably protecting the upper surface of the substrate. Therefore, the substrate processing method can process the substrate more appropriately.

[0022] In the above-described substrate processing method, it is preferable that the solidification step cools the liquid film while maintaining the gas pressure within the housing at a pressure at which the liquid film can be solidified, and the sublimation step heats the second solid film while maintaining the gas pressure within the housing at a pressure at which the second solid film can be sublimated. The solidification step maintains the gas pressure within the housing at a pressure at which the liquid film can be solidified. Therefore, the solidification step can suitably suppress evaporation of the liquid film. The solidification step cools the liquid film. Therefore, the liquid film is suitably solidified in the solidification step. The sublimation step maintains the gas pressure within the housing at a pressure at which the second solid film can be sublimated. Therefore, the sublimation step can suitably suppress melting of the second solid film. The sublimation step heats the second solid film. Therefore, the second solid film is suitably sublimated in the sublimation step.

[0023] In the above-described substrate processing method, it is preferable that the solidification step cools the substrate to a temperature at which the liquid film solidifies, and the sublimation step heats the substrate to a temperature at which the second solid film sublimes. The solidification step cools the liquid film via the substrate. In the solidification step, the upper surface of the substrate comes into contact with the liquid film. Therefore, the solidification step can efficiently form the second solid film. The solidification step cools the substrate to a temperature at which the liquid film solidifies. Therefore, the solidification step can suitably solidify the liquid film. The sublimation step heats the second solid film via the substrate. In the sublimation step, the upper surface of the substrate comes into contact with the second solid film. Therefore, the sublimation step can efficiently sublimate the second solid film. The sublimation step heats the substrate to a temperature at which the second solid film sublimes. Therefore, the sublimation step can suitably sublimate the second solid film.

[0024] In the above-described substrate processing method, the sublimation step preferably includes discharging the gas inside the housing to the outside of the housing, so that the second solid film is more suitably sublimated in the sublimation step.

[0025] In the above-described substrate processing method, it is preferable that the first processing gas is water vapor, and that in the solidification step, the gas pressure in the housing is greater than the pressure of the triple point of water, and in the sublimation step, the gas pressure in the housing is less than the pressure of the triple point of water. In the solidification step, the gas pressure in the housing is greater than the pressure of the triple point of water. Therefore, in the solidification step, evaporation of the liquid film can be suitably suppressed. In the sublimation step, the gas pressure in the housing is less than the pressure of the triple point of water. Therefore, in the sublimation step, melting of the second solid film can be suitably suppressed.

[0026] The substrate processing method preferably further comprises a second supply step of supplying a second process gas into the housing, wherein the liquid film dissolves the second process gas. In the second supply step, the second process gas is supplied. Therefore, in the second supply step, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0027] The liquid film dissolves the second process gas, so that the liquid film can process the substrate more effectively.

[0028] In the above-described substrate processing method, the second processing gas preferably contains at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas. After the second processing gas is dissolved in the liquid film, the liquid film contains at least one of water, ammonia, methylamine, dimethylamine, trimethylamine, and hydrogen peroxide. Therefore, the liquid film can process the substrate more appropriately.

[0029] The above-described substrate processing method preferably further comprises a charging step of charging the second solid film. By charging the second solid film, particles contained in the second solid film can also be easily charged. Therefore, particles contained in the second solid film can be suitably removed.

[0030] The above-described substrate processing method preferably further comprises a collecting step of collecting the charged particles, which can suitably remove the charged particles from the substrate.

[0031] In the above-described substrate processing method, the substrate preferably has a pattern formed on the upper surface of the substrate, and the substrate processing method can appropriately process the substrate while protecting the pattern.

[0032] The present invention is a substrate processing apparatus comprising: a sealable housing; a substrate mounting section installed within the housing and on which a substrate is mounted in a substantially horizontal position; a first supply section that supplies a first process gas into the housing; a pressure adjustment section that adjusts the pressure of the gas within the housing; a temperature adjustment section that adjusts the temperature of a substrate mounted on the substrate mounting section; and a control section that controls the first supply section, the pressure adjustment section, and the temperature adjustment section, wherein the control section causes the first process gas to be supplied to the housing from the first supply section, controls the pressure adjustment section and the temperature adjustment section to sublimate the first process gas and form a first solid film that covers an upper surface of the substrate mounted on the substrate mounting section, and controls the pressure adjustment section and the temperature adjustment section to melt the first solid film and form a liquid film that covers the upper surface of the substrate mounted on the substrate mounting section.

[0033] The housing is hermetically sealable, so that the pressure adjusting unit can suitably adjust the pressure of the gas inside the housing.

[0034] The control unit controls the first supply unit. The first supply unit supplies a first process gas to the housing. When the first supply unit supplies the first process gas to the housing, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0035] The control unit controls the pressure adjustment unit and the temperature adjustment unit. Specifically, the pressure adjustment unit adjusts the pressure of the gas inside the housing, and the temperature adjustment unit adjusts the temperature of the substrate placed on the substrate placement unit. This causes the first process gas to sublimate and form a first solid film. That is, the first process gas turns into the first solid film without passing through a liquid state. The first solid film covers the upper surface of the substrate placed on the substrate placement unit. Therefore, when the first process gas turns into the first solid film, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0036] The control unit controls the pressure adjustment unit and the temperature adjustment unit. As a result, the first solid film melts and a liquid film is formed. That is, the first solid film changes into a liquid film. The liquid film covers the upper surface of the substrate placed on the substrate placement unit. Therefore, when the first solid film changes into a liquid film, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0037] In summary, the control unit controls the first supply unit, the pressure adjustment unit, and the temperature adjustment unit to supply the first process gas to the housing, sublimate the first process gas, and melt the first solid film. Therefore, the substrate processing apparatus can form a liquid film on the upper surface of the substrate without the upper surface of the substrate coming into contact with the gas-liquid interface. Therefore, the substrate processing apparatus can supply the process liquid to the upper surface of the substrate while protecting the upper surface of the substrate. Therefore, the substrate processing apparatus can process the substrate appropriately.

[0038] Furthermore, the substrate processing apparatus sublimates the first processing gas to form a first solid film covering the upper surface of the substrate, and melts the first solid film to form a liquid film covering the upper surface of the substrate. This effectively prevents the processing liquid from overflowing from the substrate. That is, loss of processing liquid can be effectively reduced. Therefore, the substrate processing apparatus can efficiently form a liquid film using less processing liquid. That is, the substrate processing apparatus can process substrates with a small amount of processing liquid. As a result, the substrate processing apparatus uses a relatively small amount of processing liquid. For example, the amount of processing liquid used in the substrate processing apparatus is less than that used in conventional apparatuses.

[0039] In the above-described substrate processing apparatus, it is preferable that the control unit solidifies the liquid film by controlling the pressure adjustment unit and the temperature adjustment unit to form a second solid film on the upper surface of the substrate placed on the substrate placement unit, and sublimates the second solid film by controlling the pressure adjustment unit and the temperature adjustment unit.

[0040] The control unit controls the pressure adjustment unit and the temperature adjustment unit. This causes the liquid film to solidify and form a second solid film. That is, the liquid film changes into the second solid film. The second solid film is formed on the upper surface of the substrate placed on the substrate placement unit. As described above, the liquid film covers the upper surface of the substrate placed on the substrate placement unit. Therefore, when the liquid film changes into the second solid film, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0041] The control unit controls the pressure adjustment unit and the temperature adjustment unit. This causes the second solid film to sublimate. That is, the second solid film turns into a gas without passing through a liquid state. Therefore, when the second solid film sublimates, the upper surface of the substrate does not come into contact with the gas-liquid interface.

[0042] In summary, the control unit controls the pressure adjustment unit and the temperature adjustment unit to solidify the liquid film and sublimate the second solid film. Therefore, the substrate processing apparatus can remove the second solid film from the upper surface of the substrate without the upper surface of the substrate coming into contact with the gas-liquid interface. Therefore, the substrate processing apparatus can dry the substrate while protecting the upper surface of the substrate. Therefore, the substrate processing apparatus can process the substrate more appropriately.

[0043] The substrate processing apparatus described above preferably further comprises a second supply unit that supplies a second process gas to the housing, and the control unit controls the second supply unit to supply the second process gas into the housing and dissolve the second process gas in the liquid film. The control unit controls the second supply unit. The second supply unit supplies the second process gas to the housing. The second process gas is dissolved in the liquid film. In this way, the substrate processing apparatus can adjust the composition of the liquid film without the upper surface of the substrate coming into contact with the gas-liquid interface. Therefore, the substrate processing apparatus can process the substrate more appropriately while protecting the upper surface of the substrate.

[0044] The substrate processing apparatus described above preferably further comprises an electron emitting section that emits electrons into the housing, The electron emitting section can suitably charge the second solid film.

[0045] The substrate processing apparatus preferably further comprises an electrode installed in the housing and applied with a positive voltage, the electrode being capable of suitably collecting negatively charged particles. [Effects of the Invention]

[0046] According to the substrate processing method and substrate processing apparatus of the present invention, the substrate can be processed appropriately. [Brief explanation of the drawings]

[0047] [Figure 1] FIG. 2 is a plan view showing the inside of the substrate processing apparatus according to the first embodiment. [Figure 2] FIG. 2 is a control block diagram of the substrate processing apparatus. [Figure 3] FIG. 2 is a diagram illustrating a configuration of a processing unit according to the embodiment. [Figure 4] 3 is a flowchart showing a procedure of a substrate processing method according to an embodiment. [Figure 5] 5A and 5B are diagrams schematically showing the upper surface of the substrate in a placing step and a first supplying step. [Figure 6] FIG. 2 is a diagram schematically illustrating the upper surface of the substrate during the sublimation process. [Figure 7] FIG. 2 is a diagram schematically illustrating the upper surface of the substrate during the sublimation process. [Figure 8] FIG. 10 is a diagram schematically illustrating the upper surface of the substrate in a melting step. [Figure 9] FIG. 10 is a diagram schematically illustrating the upper surface of the substrate in a melting step. [Figure 10] FIG. 10 is a diagram schematically illustrating the upper surface of the substrate in a second supplying step. [Figure 11] FIG. 2 is a diagram schematically illustrating the upper surface of the substrate during a solidification step. [Figure 12] FIG. 2 is a diagram schematically illustrating the upper surface of the substrate during a solidification step. [Figure 13] FIG. 2 is a diagram schematically illustrating the upper surface of the substrate in a charging step. [Figure 14] FIG. 2 is a diagram schematically illustrating the upper surface of the substrate in a sublimation process. [Figure 15]FIG. 2 is a diagram schematically illustrating the upper surface of the substrate in a sublimation process. [Figure 16] 10 is a flowchart showing the procedure of a substrate processing method according to a modified embodiment. [Figure 17] 10 is a flowchart showing the procedure of a substrate processing method according to a modified embodiment. [Figure 18] 10 is a diagram schematically showing the upper surface of the substrate W in a solidification step. FIG. [Figure 19] 10 is a diagram schematically showing the upper surface of the substrate W in a solidification step. FIG. [Figure 20] FIG. 10 is a diagram showing the configuration of a processing unit according to a modified embodiment. [Figure 21] 10 is a flowchart showing the procedure of a substrate processing method according to a modified embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0048] A substrate processing method and a substrate processing apparatus according to the present invention will be described below with reference to the drawings.

[0049] <1. Overview of substrate processing equipment> 1 is a plan view showing the inside of a substrate processing apparatus according to an embodiment. The substrate processing apparatus 1 performs processing on a substrate W. The processing performed on the substrate by the substrate processing apparatus 1 is, for example, liquid processing. In the liquid processing, a processing liquid is supplied to the substrate W.

[0050] The substrate W is, for example, a semiconductor wafer, a liquid crystal display substrate, an organic EL (Electroluminescence) substrate, an FPD (Flat Panel Display) substrate, an optical display substrate, a magnetic disk substrate, an optical disk substrate, a magneto-optical disk substrate, a photomask substrate, or a solar cell substrate. The substrate W has a thin, flat plate shape. The substrate W has a substantially circular shape in a plan view.

[0051] The substrate processing apparatus 1 includes an indexer unit 3 and a processing block 7. The processing block 7 is connected to the indexer unit 3. The indexer unit 3 supplies substrates W to the processing block 7. The processing block 7 processes the substrates W. The indexer unit 3 retrieves the substrates W from the processing block 7.

[0052] For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is referred to as the "front-rear direction X." The front-rear direction X is horizontal. Within the front-rear direction X, the direction from the processing block 7 toward the indexer unit 3 is referred to as the "front." The direction opposite to the front is referred to as the "rear." The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y." One direction in the "width direction Y" is referred to as the "right" as appropriate. The direction opposite to the right is referred to as the "left." The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z." For reference, in each figure, front, rear, right, left, top, and bottom are indicated as appropriate.

[0053] The indexer unit 3 includes a plurality of (for example, four) carrier placement units 4. Each carrier placement unit 4 places one carrier C thereon. The carrier C accommodates a plurality of substrates W. The carrier C is, for example, a FOUP (Front Opening Unified Pod), a SMIF (Standard Mechanical Interface), or an OC (Open Cassette).

[0054] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is disposed behind the carrier platform 4. The transport mechanism 5 transports a substrate W. The transport mechanism 5 is accessible to a carrier C placed on the carrier platform 4. The transport mechanism 5 includes a hand 5a and a hand driver 5b. The hand 5a supports the substrate W. The hand driver 5b is connected to the hand 5a. The hand driver 5b moves the hand 5a. The hand driver 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 5b rotates the hand 5a, for example, in a horizontal plane.

[0055] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 and the transport mechanism 5 can exchange substrates W with each other. The transport mechanism 8 includes a hand 8a and a hand driver 8b. The hand 8a supports the substrate W. The hand driver 8b is connected to the hand 8a. The hand driver 8b moves the hand 8a. The hand driver 8b moves the hand 8a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 8b rotates the hand 8a, for example, in a horizontal plane.

[0056] The processing block 7 includes a plurality of processing units 11. The processing units 11 are arranged on the sides of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

[0057] The processing unit 11 includes a housing 12 and a stage 15. The stage 15 is installed inside the housing 12. The stage 15 places a substrate W thereon. The substrate W is processed inside the housing 12.

[0058] The housing 12 has a substrate transfer opening 12a. The substrate transfer opening 12a is provided, for example, on the side of the housing 12. The substrate W can pass through the substrate transfer opening 12a.

[0059] The processing unit 11 is equipped with a shutter 14. The shutter 14 opens and closes the substrate transfer opening 12a. The shutter 14 is attached to the housing 12. The shutter 14 is movable relative to the housing 12. When the shutter 14 opens the substrate transfer opening 12a, the transfer mechanism 8 can move the substrate W between the inside and outside of the housing 12 through the substrate transfer opening 12a.

[0060] 2 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11. The control unit 10 is electrically connected to the transport mechanisms 5 and 8 and the processing unit 11 so as to be able to communicate with them.

[0061] The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a random-access memory (RAM) that serves as a work area for the processes, a storage medium such as a fixed disk, etc. The control unit 10 has various types of information pre-stored in the storage medium. The information held by the control unit 10 is, for example, transport information for controlling the transport mechanisms 5 and 8. The information held by the control unit 10 is, for example, processing information for controlling the processing unit 11. The processing information is also called a processing recipe.

[0062] An example of the operation of the substrate processing apparatus 1 will now be briefly described.

[0063] The indexer unit 3 supplies the substrate W to the processing block 7. Specifically, the transport mechanism 5 transfers the substrate W from the carrier C to the transport mechanism 8 of the processing block 7.

[0064] The processing block 7 distributes the substrates W from the indexer section 3 to the processing units 11. Specifically, the shutter 14 opens the substrate transfer opening 12a. The transport mechanism 8 transports the substrates W from the transport mechanism 5 to the stages 15 of each processing unit 11.

[0065] The shutter 14 closes the substrate transfer opening 12a. The processing unit 11 processes the substrate W placed on the stage 15. The processing unit 11 performs liquid processing on the substrate W, for example.

[0066] After the processing unit 11 processes the substrate W, the processing block 7 returns the substrate W from the processing unit 11 to the indexer section 3. Specifically, the shutter 14 opens the substrate transfer opening 12a. The transfer mechanism 8 transfers the substrate W from the stage 15 to the transfer mechanism 5.

[0067] The indexer unit 3 retrieves the substrate W from the processing block 7. Specifically, the transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C.

[0068] 2. Configuration of processing unit 11 FIG. 3 is a diagram showing the configuration of a processing unit 11. In FIG. 3, the substrate transfer port 12a and the shutter 14 are not shown. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer processing units. That is, each processing unit 11 processes only one substrate W at a time.

[0069] The housing 12 can be sealed. Specifically, the housing 12 has a processing space 13 therein. The housing 12 defines the processing space 13. The stage 15 is placed in the processing space 13. The substrate W is processed in the processing space 13. The housing 12 can substantially seal the processing space 13. For example, when the shutter 14 closes the substrate transfer opening 12a, the processing space 13 is substantially sealed.

[0070] The stage 15 carries one substrate W. The stage 15 carries the substrate W in a substantially horizontal position. The stage 15 supports the substrate W. When the substrate W is placed on the stage 15, the substrate W is stationary.

[0071] The stage 15 has a substantially horizontal plate shape. The stage 15 has an upper surface 15a. The upper surface 15a comes into contact with the lower surface of the substrate W. The stage 15 is disposed in the lower part of the processing space 13, for example.

[0072] The substrate processing apparatus 1 does not include a mechanism for rotating the substrate W placed on the stage 15. When the substrate W is placed on the stage 15, the substrate W does not rotate.

[0073] The processing unit 11 includes one or more (e.g., three) supply parts 17a, 17b, and 17c. Each of the supply parts 17a-17c is connected to the housing 12. Each of the supply parts 17a-17c supplies a gas to the housing 12. Each of the supply parts 17a-17c supplies a gas to the processing space 13.

[0074] The gas supplied by supply unit 17a is water vapor. The gas supplied by supply unit 17b is ammonia gas. The gas supplied by supply unit 17c is dry gas. The water vapor, ammonia gas, and dry gas are each in a gas phase.

[0075] Water vapor and ammonia gas are used to treat the substrate W. The water vapor is, for example, deionized water vapor.

[0076] The dry gas is used to adjust the pressure of the gas inside the housing 12. The supply unit 17c can adjust the pressure of the gas inside the housing 12. The supply unit 17c can increase the pressure of the gas inside the housing 12.

[0077] The dry gas has a dew point lower than room temperature. For example, the dew point is about -76°C. For example, the dry gas is air. For example, the dry gas is compressed air. For example, the dry gas is an inert gas. For example, the dry gas is nitrogen gas.

[0078] It should be noted that supply unit 17a does not supply liquid to housing 12. Supply unit 17b also does not supply liquid to housing 12. Supply unit 17c also does not supply liquid to housing 12.

[0079] Supply unit 17a is connected in communication with supply source 21a. Supply source 21a delivers water vapor to supply unit 17a. Supply unit 17b is connected in communication with supply source 21b. Supply source 21b delivers ammonia gas to supply unit 17b. Supply unit 17c is connected in communication with supply source 21c. Supply source 21c delivers dry gas to supply unit 17c.

[0080] The supply source 21a may be a component of the substrate processing apparatus 1. Alternatively, the supply source 21a may not be a component of the substrate processing apparatus 1. For example, the supply source 21a may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the supply sources 21b and 21c may each be a component of the substrate processing apparatus 1, or may not be a component of the substrate processing apparatus 1.

[0081] The processing unit 11 includes one blowing section 23. The blowing section 23 is connected in communication with the supplying sections 17a-17c. The supplying sections 17a-17c each supply gas to the housing 12 through the blowing section 23.

[0082] The blowing unit 23 is disposed, for example, at a position higher than the stage 15. The blowing unit 23 is attached, for example, to the side of the housing 12. Alternatively, the blowing unit 23 may be attached to the top of the housing 12. Alternatively, the blowing unit 23 may be installed inside the housing 12. The blowing unit 23 may be disposed, for example, above the stage 15.

[0083] The blowing unit 23 blows gas, for example, in a direction away from the substrate W supported by the stage 15. The blowing unit 23 blows gas, for example, in a substantially horizontal direction.

[0084] The arrangement and configuration of supply unit 17a will be described. At least a part of supply unit 17a is arranged outside housing 12. Supply units 17b and 17c are arranged in the same manner as supply unit 17a.

[0085] Supply unit 17a includes pipe 18a and valve 19a. Valve 19a is provided on pipe 18a. Pipe 18a has a first end that is connected to supply source 21a. Pipe 18a has a second end that is connected to blowout unit 23. When valve 19a is open, supply unit 17a supplies steam to housing 12 through blowout unit 23. When valve 19a is closed, supply unit 17a does not supply steam to housing 12.

[0086] Similarly, supply unit 17b includes pipe 18b and valve 19b. Valve 19b is provided on pipe 18b. Pipe 18b has a first end that is connected to supply source 21b. Pipe 18b has a second end that is connected to blowout unit 23. When valve 19b is open, supply unit 17b supplies ammonia gas to housing 12 through blowout unit 23. When valve 19b is closed, supply unit 17b does not supply ammonia gas to housing 12.

[0087] The supply unit 17c includes a pipe 18c and a valve 19c. The valve 19c is provided on the pipe 18c. The pipe 18c has a first end that is connected to the supply source 21c. The pipe 18c has a second end that is connected to the blowing unit 23. When the valve 19c is open, the supply unit 17c supplies the dry gas to the housing 12 through the blowing unit 23. When the valve 19c is closed, the supply unit 17c does not supply the dry gas to the housing 12.

[0088] The processing unit 11 includes an exhaust unit 25. The exhaust unit 25 is connected in communication with the housing 12. The exhaust unit 25 exhausts gas inside the housing 12 to the outside of the housing 12. The exhaust unit 25 exhausts gas inside the processing space 13 to the outside of the housing 12.

[0089] The exhaust unit 25 is capable of adjusting the pressure of the gas inside the housing 12. The exhaust unit 25 is capable of reducing the pressure of the gas inside the housing 12.

[0090] The processing unit 11 includes one suction section 28. The suction section 28 is connected in communication with the exhaust section 25. The exhaust section 25 sucks gas from inside the housing 12 through the suction section 28.

[0091] For example, the suction unit 28 is disposed at a lower position than the blowout unit 23. For example, the suction unit 28 is attached to the side of the housing 12. Alternatively, the suction unit 28 may be attached to the bottom of the housing 12.

[0092] The exhaust unit 25 is connected to a gas processing facility (not shown). The processing facility processes the gas. For example, the processing facility decomposes ammonia gas contained in the gas and removes the ammonia gas from the gas. The processing facility is not an element of the substrate processing apparatus 1. For example, the processing facility is a utility facility installed outside the substrate processing apparatus 1.

[0093] The following describes the arrangement and configuration of the exhaust unit 25. At least a part of the exhaust unit 25 is arranged outside the housing 12.

[0094] The exhaust unit 25 includes a pipe 26 and a vacuum pump 27. The vacuum pump 27 is provided on the pipe 26. The pipe 26 has a first end that is connected to the housing 12. The pipe 26 has a second end that is connected to the processing equipment. When the vacuum pump 27 operates, the exhaust unit 25 exhausts gas from the housing 21.

[0095] The processing unit 11 includes a temperature adjustment section 31. The temperature adjustment section 31 adjusts the temperature of the substrate W placed on the stage 15. The temperature adjustment section 31 cools and heats the substrate W supported by the stage 15.

[0096] At least a part of the temperature adjusting unit 31 is preferably disposed inside the housing 12 .

[0097] The temperature adjustment unit 31 includes a cooling unit 32. The cooling unit 32 cools the substrate W placed on the stage 15.

[0098] An example configuration of the cooling unit 32 will be described. The cooling unit 32 includes a cooling pipe 33. At least a portion of the cooling pipe 33 is installed inside the housing 12. The cooling pipe 33 is attached to the stage 15. The cooling pipe 33 is attached to the stage 15. The cooling pipe 33 is, for example, arranged inside the stage 15. The cooling pipe 33 further extends to the outside of the housing 12. The cooling pipe 33 is connected in communication with a refrigerant supply unit 34. The refrigerant supply unit 34 is provided outside the housing 12. The refrigerant supply unit 34 sends a refrigerant to the cooling pipe 33. The refrigerant supply unit 34 includes, for example, a pump (not shown). The refrigerant flows through the cooling pipe 33. Furthermore, the refrigerant supply unit 34 may receive the refrigerant from the cooling pipe 33. In other words, the refrigerant may circulate between the refrigerant supply unit 34 and the cooling pipe 33. When the coolant flows through the cooling pipe 33, the coolant removes heat from the substrate W supported on the stage 15. When the coolant flows through the cooling pipe 33, the cooling unit 32 cools the substrate W placed on the stage 15. The coolant is, for example, liquid nitrogen.

[0099] The temperature adjustment unit 31 includes a heating unit 36. The heating unit 36 ​​heats the substrate W placed on the stage 15.

[0100] An example configuration of the heating unit 36 ​​will be described. The heating unit 36 ​​includes an electric heater 37 and a power supply 38. The electric heater 37 is installed inside the housing 12. The electric heater 37 is attached to the stage 15. The electric heater 37 is disposed, for example, inside the stage 15. The electric heater 37 includes, for example, an electric heating wire. The power supply 38 is electrically connected to the electric heater 37. The power supply 38 is provided outside the housing 12. The power supply 38 supplies power to the electric heater 37. When the power supply 38 supplies power to the electric heater 37, the electric heater 37 applies heat to the substrate W supported on the stage 15. When the power supply 38 supplies power to the electric heater 37, the heating unit 36 ​​heats the substrate W supported on the stage 15.

[0101] The processing unit 11 includes an electron emitter 41. The electron emitter 41 emits electrons into the housing 12. The electron emitter 41 emits electrons to the substrate W placed on the stage 15.

[0102] At least a part of the electron-emitting portion 41 may be disposed, for example, inside the housing 12. Alternatively, the entire electron-emitting portion 41 may be disposed outside the housing 12.

[0103] An example configuration of the electron emitter 41 will be described. The electron emitter 41 includes an electron beam source 42 and a power supply 43. The electron beam source 42 is, for example, an electron gun. The electron beam source 42 includes, for example, a filament (not shown). The filament is made of, for example, tungsten. At least a portion of the electron beam source 42 may be installed inside the housing 12. The electron beam source 42 may be installed so as to penetrate the housing 12. Alternatively, the entire electron beam source 42 may be installed outside the housing 12. The electron beam source 42 is, for example, located at a higher position than the stage 15. The power supply 43 is electrically connected to the electron beam source 42. The power supply 43 is installed outside the housing 12. The power supply 43 supplies power to the electron beam source 42. When the power supply 43 supplies power to the electron beam source 42, the electron beam source 42 emits electrons into the processing space 13.

[0104] The processing unit 11 includes a collector 45. The collector 45 collects negatively charged particles within the housing 12.

[0105] At least a portion of the collection portion 45 is preferably disposed within the housing 12 .

[0106] An example configuration of the collection unit 45 will be described. The collection unit 45 includes an electrode 46 and a power supply 47. The electrode 46 is preferably installed inside the housing 12, for example. The electrode 46 is disposed above the stage 15, for example. The electrode 46 is made of metal coated with an insulator, for example. The power supply 47 is electrically connected to the electrode 46. The power supply 47 is provided outside the housing 12. The power supply 47 applies a voltage to the electrode 46. The power supply 47 applies a positive voltage to the electrode 46. When the power supply 47 applies a positive voltage to the electrode 46, the electrode 46 attracts negatively charged particles.

[0107] The processing unit 11 includes a pressure sensor 51. The pressure sensor 51 detects the pressure of the gas inside the housing 12. The pressure sensor 51 is installed inside the housing 12.

[0108] The processing unit 11 includes a temperature sensor 52. The temperature sensor 52 detects the temperature of the substrate W. The temperature sensor 52 is installed inside the housing 12. The temperature sensor 52 is attached to, for example, the stage 15. The temperature sensor 52 may indirectly detect the temperature of the substrate W on the stage 15, for example, by directly detecting the stage 15.

[0109] The stage 15 is an example of a substrate placement portion of the present invention.

[0110] Supply unit 17a is an example of a first supply unit in the present invention. Water vapor is an example of a first processing gas in the present invention. Supply unit 17b is an example of a second supply unit in the present invention. Ammonia gas is an example of a second processing gas in the present invention.

[0111] The supply unit 17c and the exhaust unit 25 are examples of the pressure adjusting unit of the present invention.

[0112] Hereinafter, when there is no need to distinguish between the supply unit 17c and the exhaust unit 25, they will be referred to as the "pressure adjustment unit 20" as appropriate.

[0113] See Figure 2. The control unit 10 controls the supply units 17a and 17b. The control unit 10 controls the valves 19a and 19b.

[0114] The control unit 10 controls the pressure adjustment unit 20. The control unit 10 controls the supply unit 17c and the exhaust unit 25. The control unit 10 controls the valve 19c and the vacuum pump 27.

[0115] The control unit 10 controls the temperature adjustment unit 31. The control unit 10 controls the cooling unit 32 and the heating unit 36. The control unit 10 controls the refrigerant supply unit 34 and the power source 38.

[0116] The control unit 10 controls the electron emitting unit 41. The control unit 10 controls the power supply 43.

[0117] The control unit 10 controls the collecting unit 45. The control unit 10 controls the power supply 47.

[0118] The control unit 10 acquires the detection result of the pressure sensor 51. The control unit 10 acquires the detection result of the temperature sensor 52.

[0119] <3. Example of operation of processing unit 11> 4 is a flowchart showing the procedure of the substrate processing method. The substrate processing method for processing a substrate includes steps S1 to S11. Steps S1 to S11 are substantially performed by the processing unit 11. The processing unit 11 operates under the control of the control unit 10.

[0120] Step S1: Placement process As described above, the substrate W is placed on the stage 15 by the transport mechanism 8. The substrate W is placed in the housing 12 in a substantially horizontal position.

[0121] 5 is a diagram schematically showing the upper surface of the substrate W in the placing step. The substrate W has a pattern R. The pattern R is formed on the upper surface W1 of the substrate W. When the substrate W is placed on the stage 15, the pattern R is located on the upper surface W1 of the substrate W. When the substrate W is placed on the stage 15, the pattern R faces upward.

[0122] The pattern R has a protrusion W2 and a recess A. The protrusion W2 is a part of the substrate W. The protrusion W2 is a structure. The protrusion W2 is made of, for example, a silicon oxide film (SiO2), a silicon nitride film (SiN), or a polysilicon film. The protrusion W2 protrudes upward. The recess A is a space. The recess A is open upward. The recess A is arranged on the side of the protrusion W2. The recess A contacts the protrusion W2. The protrusion W2 corresponds to a wall that defines the recess A.

[0123] 5 further shows a particle (foreign matter) B. The particle B adheres to the upper surface W1 of the substrate W.

[0124] The upper surface W1 of the substrate W comes into contact with the gas G within the housing 12.

[0125] In the placing step, the substrate W does not come into contact with the liquid. In the placing step, the substrate W is not wet.

[0126] Here, the interface between the gas G and the liquid is appropriately called the gas-liquid interface. In the placing step, the substrate W does not come into contact with the gas-liquid interface. In fact, no gas-liquid interface is generated in the placing step.

[0127] The pressure sensor 51 detects the pressure of the gas G inside the housing 12. The control unit 10 monitors the detection result of the pressure sensor 51.

[0128] In the placing step, the pressure of the gas G inside the housing 12 is atmospheric pressure. Here, atmospheric pressure includes standard atmospheric pressure (1 atmosphere, 1013 hPa). Normal pressure is, for example, an atmospheric pressure in the range of 0.7 atmospheres or more and 1.3 atmospheres or less. In this specification, pressure is indicated as absolute pressure based on absolute vacuum.

[0129] The temperature sensor 52 detects the temperature of the substrate W placed on the stage 15. The control unit 10 monitors the detection result of the temperature sensor 52.

[0130] In the placing step, the substrate W on the stage 15 is at, for example, room temperature. Here, room temperature includes room temperature. Room temperature is, for example, a temperature in the range of 5°C or higher and 35°C or lower. Room temperature is, for example, a temperature in the range of 10°C or higher and 30°C or lower.

[0131] The substrate W is stationary on the stage 15. The substrate W does not rotate. Steps S2 to S9 are performed while the substrate W is stationary.

[0132] Step S2: Sealing process The housing 12 is sealed when the housing 12 contains the substrate W. For example, the shutter 14 closes the substrate transfer opening 12a.

[0133] For convenience, reference will be made to Figure 5. Even in the sealing step, the substrate W does not come into contact with the gas-liquid interface.

[0134] Step S3: Adjustment process The pressure of the gas G in the housing 12 is adjusted to a first pressure P1, which is a pressure at which water vapor can sublimate.

[0135] Here, "sublimation" and "to sublimate" refer to the change from a gas to a solid without passing through a liquid state. On the other hand, "condensation" and "to condense" refer to the change from a gas to a liquid. When the pressure of the gas G in the housing 12 is the first pressure P1, water vapor is unlikely to condense.

[0136] For example, the first pressure P1 is lower than the pressure of the triple point of water, which is approximately 611 Pa. When the pressure of the gas G in the housing 12 is lower than the pressure of the triple point of water, water vapor (water in the gas phase) is unlikely to condense.

[0137] The first pressure P1 is lower than the normal pressure. Therefore, the adjustment step reduces the pressure of the gas G in the housing 12. The adjustment step reduces the pressure of the gas G in the housing 12 from the normal pressure to the first pressure P1.

[0138] Specifically, the control unit 10 adjusts the pressure of the gas G in the housing 12 by controlling the pressure adjustment unit 20. For example, the exhaust unit 25 exhausts the gas inside the housing 12, thereby reducing the pressure of the gas G in the housing 12. When the control unit 10 adjusts the pressure of the gas G in the housing 12, the control unit 10 may refer to the detection result of the pressure sensor 51.

[0139] The first pressure P1 may be a single value or may be a range between two values. The first pressure P1 is set in advance in the processing information held by the control unit 10.

[0140] Furthermore, in the adjusting step, the substrate W placed on the stage 15 is adjusted to a first temperature T1. The first temperature T1 is the temperature at which water vapor sublimes under the first pressure P1. In other words, the first temperature T1 is the temperature at which water exists in a solid phase under the first pressure P1.

[0141] For example, the first temperature T1 is lower than the temperature of the triple point of water, which is 0.01 degrees.

[0142] The first temperature T1 is lower than room temperature. Therefore, the adjustment step cools the substrate W placed on the stage 15. The adjustment step cools the substrate W placed on the stage 15 from room temperature to the first temperature T1.

[0143] Specifically, the control unit 10 controls the temperature adjustment unit 31 to adjust the temperature of the substrate W placed on the stage 15. For example, the cooling unit 32 cools the substrate W placed on the stage 15. When the control unit 10 adjusts the temperature of the substrate W, the control unit 10 may refer to the detection result of the temperature sensor 52.

[0144] The first temperature T1 may be a single value or may be in a range between two values. The first temperature T1 is set in advance in the processing information held by the control unit 10.

[0145] Steps S4 and S5 are performed in a state where the pressure of the gas G in the housing 12 is maintained at a first pressure P1 and the temperature of the substrate W placed on the stage 15 is maintained at a first temperature T1.

[0146] Step S4: First supply process Water vapor is supplied to the enclosure 12 .

[0147] Specifically, the control unit 10 controls the supply unit 17a, which then supplies water vapor to the housing 12.

[0148] For convenience, reference will be made to Figure 5. The upper surface W1 of the substrate W comes into contact with the gas G in the housing 12. The gas G contains water vapor. Therefore, the upper surface W1 of the substrate W comes into contact with the water vapor.

[0149] The water vapor is in a gas phase. That is, the water vapor is not in a liquid phase. Therefore, the gas G is also in a gas phase in the first supplying step.

[0150] In the first supply step, no liquid is supplied to the substrate W.

[0151] In the first supply step, the upper surface W1 of the substrate W does not come into contact with the liquid. Therefore, in the first supply step, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface. In fact, in the first supply step, the gas-liquid interface does not occur.

[0152] Step S5: Sublimation process The water vapor sublimes within the enclosure 12 .

[0153] The water vapor begins to sublimate immediately after it is supplied to the housing 12. Therefore, the period during which the sublimation step is performed may overlap at least partly with the period during which the first supply step is performed.

[0154] 6 is a diagram schematically showing the upper surface W1 of the substrate W in the sublimation process. With the pressure of the gas G in the housing 12 maintained at a first pressure P1, the water vapor is cooled in the housing 12. The water vapor is cooled by the substrate W. The water vapor near the substrate W is cooled to a first temperature T1.

[0155] The water vapor is transformed into a first solid film H without passing through a liquid state. The first solid film H is formed on the upper surface W1 of the substrate W. The upper surface W1 of the substrate W contacts the first solid film H.

[0156] The first solid film H is in a solid phase. The first solid film H is ice. The first solid film H is not in a liquid phase.

[0157] 6, the first solid film H is thinner than the height of the convex portion W2. Therefore, the upper surface W1 (convex portion W2) comes into contact with both the first solid film H and the gas G.

[0158] 6 illustrates a case where the thickness of the first solid film H is not uniform across the upper surface W1 of the substrate W. That is, FIG. 6 illustrates a case where the rate at which the first solidified film H is formed varies across the upper surface W1 of the substrate W. The variation in the rate at which the first solidified film H is formed is caused, for example, by the temperature of the substrate W varying across the upper surface W1 of the substrate W. Note that the rate at which the first solidified film H is formed may also be uniform across the upper surface W1 of the substrate W.

[0159] The first solid film H gradually becomes thicker.

[0160] 7 is a diagram schematically illustrating the upper surface W1 of the substrate W in the sublimation step. In FIG. 7, the first solid film H is thicker than the height of the convex portions W2.

[0161] The first solid film H covers the upper surface W1 of the substrate W. The first solid film H covers the entire upper surface W1 of the substrate W. The upper surface W1 of the substrate W is in contact with the first solid film H. However, the upper surface W1 of the substrate W does not come into contact with the gas G.

[0162] 6 and 7, when the water vapor turns into the first solid film H, the upper surface W1 of the substrate W does not come into contact with the liquid. The water vapor turns into the first solid film H without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface. Therefore, in the sublimation process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface. To begin with, no gas-liquid interface occurs in the sublimation process.

[0163] Even if the formation rate of the first solidified film H varies on the upper surface W1 of the substrate W, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface in the sublimation step.

[0164] Step S6: Melting process The first solid film H melts.

[0165] In the melting step, the pressure of the gas G inside the housing 12 is adjusted to a second pressure P2. The second pressure P2 is a pressure at which the first solid film H can melt.

[0166] Here, "melting" and "to melt" refer to a change from a solid to a liquid. On the other hand, "sublimation" and "to sublimate" refer to a change from a solid to a gas without passing through a liquid state. When the pressure of the gas G inside the housing 12 is the second pressure P2, the first solid film H is unlikely to sublimate.

[0167] For example, the second pressure P2 is greater than the pressure of the triple point of water. When the pressure of the gas G in the housing 12 is greater than the pressure of the triple point of water, ice (solid water) is unlikely to sublimate.

[0168] For example, the second pressure P2 is lower than atmospheric pressure. For example, the second pressure P2 is lower than standard atmospheric pressure.

[0169] The second pressure P2 is greater than the first pressure P1. Therefore, the melting process increases the pressure of the gas G in the housing 12. The melting process increases the pressure of the gas G in the housing 12 from the first pressure P1 to the second pressure P2.

[0170] Specifically, the control unit 10 adjusts the pressure of the gas G in the housing 12 by controlling the pressure adjustment unit 20. For example, the supply unit 17c supplies dry gas to the housing 12, thereby increasing the pressure of the gas G in the housing 12.

[0171] The second pressure P2 may be a single value or may be a range between two values. The second pressure P2 is set in advance in the processing information held by the control unit 10.

[0172] Furthermore, the substrate W placed on the stage 15 is adjusted to a second temperature T2. Here, it is preferable that the substrate W placed on the stage 15 is adjusted to the second temperature T2 after the pressure of the gas G in the housing 12 is adjusted to the second pressure P2. The second temperature T2 is the temperature at which the first solid film H melts under the second pressure P2. In other words, the second temperature T2 is the temperature at which the first solid film H exists in a liquid phase under the second pressure P2.

[0173] For example, the second temperature T2 is higher than the triple point temperature of water, and is approximately equal to room temperature.

[0174] The second temperature T2 is higher than the first temperature T1. Therefore, the melting process heats the substrate W placed on the stage 15. The melting process heats the substrate W placed on the stage 15 from the first temperature T1 to the second temperature T2.

[0175] Specifically, the control unit 10 controls the temperature adjustment unit 31 to adjust the temperature of the substrate W placed on the stage 15. For example, the heating unit 36 ​​heats the substrate W placed on the stage 15.

[0176] The second temperature T2 may be a single value or may be in a range between two values. The second temperature T2 is set in advance in the processing information held by the control unit 10.

[0177] 8 is a diagram schematically showing the upper surface W1 of the substrate W in the melting step. The first solid film H is heated while the pressure of the gas G in the housing 12 is maintained at the second pressure P2. The first solid film H is heated by the substrate W. The first solid film H is heated to a second temperature T2.

[0178] The first solid film H changes into a liquid film J. The liquid film J is formed on the upper surface W1 of the substrate W. The upper surface W1 of the substrate W comes into contact with the liquid film J.

[0179] The liquid film J is in a liquid phase. The liquid film J is formed by a treatment liquid. The treatment liquid that forms the liquid film J is water.

[0180] 8, a portion of the first solid film H changes into a liquid film J. The upper surface W1 of the substrate W contacts both the liquid film J and the first solid film H. However, the upper surface W1 of the substrate W does not contact the gas G because the upper surface W1 of the substrate W is covered by the liquid film J and the first solid film H.

[0181] 8 illustrates a case where the thickness of the liquid film J is not uniform across the upper surface W1 of the substrate W. That is, Fig. 8 illustrates a case where the rate at which the liquid film J is formed varies across the upper surface W1 of the substrate W. The variation in the rate at which the liquid film J is formed is caused, for example, by the temperature of the substrate W varying across the upper surface W1 of the substrate W. Note that the rate at which the liquid film J is formed may also be uniform across the upper surface W1 of the substrate W.

[0182] The first solid film H gradually decreases, and the liquid film J gradually increases.

[0183] 9 is a diagram schematically illustrating the upper surface W1 of the substrate W in the melting step. In FIG. 9, the first solid film H is entirely transformed into a liquid film J.

[0184] The liquid film J covers the upper surface W1 of the substrate W. The liquid film J covers the entire upper surface W1 of the substrate W. The upper surface W1 of the substrate W is in contact with the liquid film J. However, the upper surface W1 of the substrate W is not in contact with the gas G.

[0185] As is clear from Figures 8 and 9, when the first solid film H changes into a liquid film J, a gas-liquid interface K is generated. The gas-liquid interface K is located between the liquid film J and the gas G. However, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. The first solid film H changes into the liquid film J without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, in the melting process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K.

[0186] Even if the formation rate of the liquid film J varies on the upper surface W1 of the substrate W, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the melting step.

[0187] Step S7: Second supply process Ammonia gas is supplied to the enclosure 12 .

[0188] Specifically, the control unit 10 controls the supply unit 17b, which then supplies the ammonia gas to the housing 12.

[0189] 10 is a diagram schematically illustrating the upper surface W1 of the substrate W in the second supply step. The gas G contains ammonia gas. The ammonia gas is in a gas phase. That is, the ammonia gas is not in a liquid phase. The gas G is also in a gas phase in the second supply step.

[0190] In the second supplying step, no liquid is supplied to the substrate W.

[0191] The upper surface W1 of the substrate W does not come into contact with the gas G because the upper surface W1 of the substrate W is covered with the liquid film J. In the second supply step, the upper surface W1 of the substrate W also does not come into contact with the gas-liquid interface K between the liquid film J and the gas G.

[0192] The liquid film J comes into contact with the gas G. The liquid film J comes into contact with the ammonia gas contained in the gas G. The liquid film J dissolves the ammonia gas contained in the gas G. As a result, the liquid film J contains ammonia water. Ammonia water is also called ammonium hydroxide.

[0193] After the liquid film J dissolves the ammonia gas, the liquid film J becomes alkaline. The upper surface W1 of the substrate W comes into contact with the alkaline liquid film J. Therefore, the upper surface W1 of the substrate W has a negative zeta potential. Similarly, the particle B comes into contact with the alkaline liquid film J. Therefore, the particle B has a negative zeta potential. The zeta potential of the particle B has the same polarity as the zeta potential of the upper surface W1 of the substrate W. Therefore, the upper surface W1 and the particle B repel each other. The particle B moves away from the upper surface W1. The particle B becomes liberated into the liquid film J. Furthermore, after the particle B moves away from the upper surface W1, it is difficult for the particle B to reattach to the upper surface W1. In this way, the liquid film J detaches the particle B from the upper surface W1.

[0194] Step S8: Solidification process The liquid film J solidifies.

[0195] In the solidification step, the pressure of the gas G in the housing 12 is adjusted to a third pressure P3. The third pressure P3 is a pressure at which the liquid film J can be solidified.

[0196] Here, "freezing" and "to solidify" refer to a change from a liquid to a solid. On the other hand, "vaporization" and "to evaporate" refer to a change from a liquid to a gas. When the pressure of the gas G inside the housing 12 is the third pressure P3, the liquid film J is unlikely to evaporate.

[0197] For example, the third pressure P3 is greater than the pressure of the triple point of water. When the pressure of the gas G in the housing 12 is greater than the pressure of the triple point of water, the water (liquid water) is less likely to evaporate.

[0198] For example, the third pressure P3 is lower than atmospheric pressure. For example, the third pressure P3 is lower than standard atmospheric pressure.

[0199] For example, the third pressure P3 is approximately equal to the second pressure P2.

[0200] In the solidification step, the pressure of the gas G inside the housing 12 is adjusted from the second pressure P2 to a third pressure P3.

[0201] Specifically, the control unit 10 controls the pressure adjustment unit 20 to adjust the pressure of the gas G in the housing 12.

[0202] The third pressure P3 may be a single value or may be a range between two values. The third pressure P3 is set in advance in the processing information held by the control unit 10.

[0203] Furthermore, the substrate W placed on the stage 15 is adjusted to a third temperature T3. The third temperature T3 is the temperature at which the liquid film J solidifies under the third pressure P3. In other words, the third temperature T3 is the temperature at which the liquid film J exists in a solid phase under the third pressure P3.

[0204] For example, the third temperature T3 is lower than the triple point temperature of water, and is approximately equal to the first temperature T1.

[0205] The third temperature T3 is lower than the second temperature T2. Therefore, the solidification process cools the substrate W placed on the stage 15. The solidification process cools the substrate W placed on the stage 15 from the second temperature T2 to the third temperature T3.

[0206] Specifically, the control unit 10 controls the temperature adjustment unit 31 to adjust the temperature of the substrate W placed on the stage 15 to the third temperature T3. For example, the cooling unit 32 cools the substrate W placed on the stage 15.

[0207] The third temperature T3 may be a single value or may be a range between two values. The third temperature T3 is set in advance in the processing information stored in the control unit 10.

[0208] 11 is a diagram schematically showing the upper surface W1 of the substrate W in the solidification step. The liquid film J is cooled while the pressure of the gas G in the housing 12 is maintained at a third pressure P3. The liquid film J is cooled by the substrate W. The liquid film J is cooled to a third temperature T3.

[0209] The liquid film J changes into a second solid film L. The second solid film L is formed on the upper surface W1 of the substrate W. The upper surface W1 of the substrate W comes into contact with the second solid film L.

[0210] The second solid film L is a solid phase.

[0211] 11, a part of the liquid film J changes into the second solid film L. The upper surface W1 of the substrate W contacts both the liquid film J and the second solid film L. However, the upper surface W1 of the substrate W does not contact the gas G because the upper surface W1 of the substrate W is covered by the liquid film J and the second solid film L.

[0212] 11 illustrates a case where the thickness of the second solid film L is not uniform across the upper surface W1 of the substrate W. That is, Fig. 11 illustrates a case where the formation rate of the second solid film L varies across the upper surface W1 of the substrate W. The variation in the formation rate of the second solid film L is caused, for example, by variation in the temperature of the substrate W across the upper surface W1 of the substrate W. Note that the formation rate of the second solid film L may also be uniform across the upper surface W1 of the substrate W.

[0213] The liquid film J gradually decreases. The second solid film L gradually increases.

[0214] 12 is a diagram schematically illustrating the upper surface W1 of the substrate W in the solidification step. In FIG.

[0215] The second solid film L covers the upper surface W1 of the substrate W. The second solid film L covers the entire upper surface W1 of the substrate W. The upper surface W1 of the substrate W is in contact with the second solid film L. However, the upper surface W1 of the substrate W does not come into contact with the gas G.

[0216] The liquid film J disappears. As a result, the zeta potential of the upper surface W1 of the substrate W disappears. The zeta potential of the particle B also disappears.

[0217] 11 and 12, when the liquid film J changes into the second solid film L, a gas-liquid interface K is generated. The gas-liquid interface K is located between the liquid film J and the gas G. However, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. The liquid film J changes into the second solid film L without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, in the solidification process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K.

[0218] Even if the formation rate of the second solid film L varies on the upper surface W1 of the substrate W, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the solidification step.

[0219] Step S9: Charging process The second solid film L is charged.

[0220] Specifically, the control unit 10 controls the electron emitting unit 41. As a result, the electron emitting unit 41 emits electrons toward the second solid film L.

[0221] 13 is a diagram schematically showing the upper surface W1 of the substrate W in the charging step. The electron emitter 41 emits electrons M. The second solid film L receives the electrons M. As a result, the second solid film L becomes negatively charged. The electrons M are distributed on the upper surface L1 of the second solid film L. As a result, the upper surface L1 of the second solid film L becomes negatively charged.

[0222] Step S10: Sublimation process The second solid film L sublimes.

[0223] In the sublimation step, the pressure of the gas G in the housing 12 is adjusted to a fourth pressure P4. The fourth pressure P4 is a pressure at which the second solid film L can be sublimated.

[0224] As described above, "sublimation" and "to sublimate" refer to the change from a solid to a gas without passing through a liquid state. On the other hand, "melting" and "to melt" refer to the change from a solid to a liquid. When the pressure of the gas G in the housing 12 is the fourth pressure P4, the second solid film L is unlikely to melt.

[0225] For example, the fourth pressure P4 is lower than the pressure of the triple point of water. When the pressure of the gas G in the housing 12 is lower than the pressure of the triple point of water, ice (solid water) is difficult to melt.

[0226] For example, the fourth pressure P4 is approximately equal to the first pressure P1.

[0227] The fourth pressure P4 is lower than the third pressure P3. Therefore, the sublimation process reduces the pressure of the gas G in the housing 12. The sublimation process reduces the pressure of the gas G in the housing 12 from the third pressure P3 to the fourth pressure P4.

[0228] Specifically, the control unit 10 adjusts the pressure of the gas G in the housing 12 by controlling the pressure adjustment unit 20. For example, the exhaust unit 25 reduces the pressure of the gas G in the housing 12.

[0229] The fourth pressure P4 may be a single value or may be a range between two values. The fourth pressure P4 is set in advance in the processing information held by the control unit 10.

[0230] In the sublimation process, the gas inside the housing 12 is discharged to the outside of the housing 12.

[0231] Specifically, the exhaust unit 25 reduces the pressure of the gas G in the housing 12 and exhausts the gas inside the housing 12 to the outside of the housing 12 .

[0232] Furthermore, the substrate W placed on the stage 15 is adjusted to a fourth temperature T4. The fourth temperature T4 is the temperature at which the second solid film L sublimes under the fourth pressure P4. In other words, the fourth temperature T4 is the temperature at which the second solid film L exists in a gas phase under the fourth pressure P4.

[0233] For example, the fourth temperature T4 is higher than the triple point temperature of water, and is approximately equal to room temperature.

[0234] For example, the fourth temperature T4 is higher than the third temperature T3. In this case, the sublimation process heats the substrate W placed on the stage 15. The sublimation process heats the substrate W placed on the stage 15 from the third temperature T3 to the fourth temperature T4.

[0235] Specifically, the control unit 10 controls the temperature adjustment unit 31 to adjust the temperature of the substrate W placed on the stage 15 to the fourth temperature T4. For example, the heating unit 36 ​​heats the substrate W placed on the stage 15.

[0236] The fourth temperature T4 may be a single value or may be a range between two values. The fourth temperature T4 is set in advance in the processing information held by the control unit 10.

[0237] 14 is a diagram schematically showing the upper surface W1 of the substrate W in the sublimation process. The second solid film L is heated while the pressure of the gas G in the housing 12 is maintained at a fourth pressure P4. The second solid film L is heated by the substrate W. The second solid film L is heated to a fourth temperature T4.

[0238] The second solid film L changes into gas without passing through a liquid state. The gas that has changed from the second solid film L is in a gas phase. The gas G includes the gas that has changed from the second solid film L. The exhaust unit 25 exhausts the gas G to the outside of the housing 12.

[0239] The upper surface L1 of the second solid film L becomes lower. The upper surface L1 of the second solid film L remains negatively charged, and the upper surface L1 of the second solid film L becomes lower. When the upper surface L1 of the second solid film L becomes lower to the same height as particle B, particle B becomes negatively charged. In other words, when particle B is exposed to the upper surface L1 of the second solid film L, particle B becomes negatively charged. When particle B becomes negatively charged, particle B and the upper surface L1 of the second solid film L repel each other. Therefore, particle B easily separates from the second solid film L. Particle B, for example, flies from the second solid film L into the gas G inside the housing 12.

[0240] 14, a part of the second solid film L sublimates. The upper surface W1 of the substrate W contacts both the second solid film L and the gas G. However, the upper surface W1 of the substrate W does not contact the liquid.

[0241] 14 illustrates a case where the thickness of the second solid film L is not uniform across the upper surface W1 of the substrate W. That is, FIG. 14 illustrates a case where the sublimation rate of the second solid film L varies across the upper surface W1 of the substrate W. The variation in the sublimation rate of the second solid film L is caused, for example, by the temperature of the substrate W varying across the upper surface W1 of the substrate W. Note that the sublimation rate of the second solid film L may also be uniform across the upper surface W1 of the substrate W.

[0242] 15 is a diagram schematically illustrating the upper surface W1 of the substrate W in the sublimation step. In FIG. 15, the entire second solid film L is sublimated.

[0243] The second solid film L does not change into a liquid, and the second solid film L is removed from the substrate W. The substrate W is dried, and the second solid film L does not change into a liquid.

[0244] The upper surface W1 of the substrate W is in contact with the gas G. However, the upper surface W1 of the substrate W is not in contact with the liquid.

[0245] 14 and 15, when the second solid film L turns into gas, the upper surface W1 of the substrate W does not come into contact with the liquid. The second solid film L sublimes without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, in the sublimation process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface. In fact, no gas-liquid interface is formed in the sublimation process.

[0246] Even if the sublimation rate of the second solid film L varies on the upper surface W1 of the substrate W, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface during the sublimation step.

[0247] Step S11: Collection process The collecting unit 45 collects the charged particles B.

[0248] The collecting step is preferably carried out in parallel with the sublimation step, and the period during which the collecting step is carried out preferably overlaps with at least a portion of the period during which the sublimation step is carried out, e.g., the collecting step begins simultaneously with the sublimation step.

[0249] Specifically, the control unit 10 controls the collecting unit 45. As a result, the electrode 46 has a positive potential.

[0250] 14, the electrode 46 attracts the charged particle B. The electrode 46 attracts the particle B exposed from the second solid film L. The particle B moves toward the electrode B. The particle B moves, for example, upward.

[0251] 15, all particles B contained in the second solid film L are collected on the electrode 46. All particles B contained in the second solid film L are removed from the substrate W.

[0252] <4. Effects of the embodiment> The substrate processing method includes a placing step in which the substrate W is placed in a substantially horizontal position in the housing 12. In the placing step, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface.

[0253] The substrate processing method includes a first supply step. In the first supply step, water vapor is supplied to the housing 12. In the first supply step, the upper surface W1 of the substrate W comes into contact with the water vapor. The water vapor is in a gas phase. That is, the water vapor is not in a liquid phase. In the first supply step, no liquid is supplied to the substrate W. Therefore, in the first supply step, the upper surface W1 of the substrate W does not come into contact with the liquid. Therefore, in the first supply step, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface.

[0254] The substrate processing method includes a sublimation process. In the sublimation process, water vapor sublimes within the housing 12. As a result, a first solid film H is formed in the sublimation process. The first solid film H covers the upper surface W1 of the substrate W. In the sublimation process, water vapor changes into the first solid film H without first becoming a liquid. In the sublimation process, the upper surface W1 of the substrate W comes into contact with the first solid film H. The first solid film H is in a solid phase. That is, the first solid film H is not in a liquid phase. Therefore, when the water vapor changes into the first solid film H, the upper surface W1 of the substrate W does not come into contact with a liquid. Therefore, the upper surface W1 of the substrate W does not come into contact with a gas-liquid interface, and the water vapor sublimes (changes) into the first solid film H. Therefore, in the sublimation process, the upper surface W1 of the substrate W does not come into contact with a gas-liquid interface.

[0255] The substrate processing method includes a melting process. In the melting process, the first solid film H melts. As a result, the melting process forms a liquid film J. The liquid film J covers the upper surface W1 of the substrate W. In the melting process, the first solid film H changes into the liquid film J. In the melting process, the upper surface W1 of the substrate W comes into contact with the liquid film J. The liquid film J is in a liquid phase. As described above, the first solid film H formed in the sublimation process covers the upper surface W1 of the substrate W. Therefore, when the first solid film H changes into the liquid film J, the upper surface W1 of the substrate W does not come into contact with the gas G. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K, and the first solid film H melts into the liquid film J. Therefore, in the melting process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K.

[0256] In summary, in the placing step, first supply step, sublimation step, and melting step, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. Therefore, the surface tension of the liquid film J does not substantially act on the upper surface W1 of the substrate W. Therefore, the liquid film J can be formed on the upper surface W1 of the substrate W while protecting the upper surface W1 of the substrate W. In other words, the processing liquid can be supplied to the upper surface W1 of the substrate W while protecting the upper surface W1 of the substrate W. Therefore, the substrate processing method can process the substrate W appropriately.

[0257] In the prior art, in which a nozzle ejects a processing liquid onto the upper surface W1 of the substrate W, when the upper surface W1 of the substrate W begins to come into contact with the processing liquid, the substrate W comes into contact with the gas-liquid interface. That is, in the prior art, there is a moment when the substrate W comes into contact with the gas-liquid interface. At this moment, the surface tension of the processing liquid acts on the upper surface W1 of the substrate W. Therefore, in the prior art, the upper surface W1 of the substrate W is subjected to a relatively large force.

[0258] The substrate processing method sublimates water vapor to form a first solid film H covering the upper surface W1 of the substrate W, and then melts the first solid film H to form a liquid film J covering the upper surface W1 of the substrate W. This effectively prevents the processing liquid from overflowing from the substrate W. That is, it effectively reduces loss of processing liquid. Therefore, the substrate processing method can efficiently form the liquid film J with less processing liquid. That is, the substrate processing method can process the substrate W with a small amount of processing liquid. As a result, the substrate processing method uses a relatively small amount of processing liquid. For example, the amount of processing liquid used in the substrate processing method is less than the amount of processing liquid used in conventional methods.

[0259] The sublimation step maintains the pressure of the gas G inside the housing 12 at a first pressure P1 at which water vapor can sublimate. Therefore, the sublimation step can suitably suppress the condensation of water vapor.

[0260] The sublimation step cools the water vapor, so that the water vapor is preferably sublimated in the sublimation step.

[0261] In the melting step, the pressure of the gas G inside the housing 12 is maintained at the second pressure P2 at which the first solid film H can melt. Therefore, the melting step can suitably prevent the first solid film H from sublimating.

[0262] The melting step heats the first solid film H. Therefore, in the melting step, the first solid film H melts suitably.

[0263] The sublimation process cools the substrate W. Therefore, the sublimation process cools the water vapor through the substrate W. In the sublimation process, the upper surface W1 of the substrate W comes into contact with the water vapor. Therefore, the sublimation process can efficiently form the first solid film H.

[0264] The sublimation step cools the substrate W to a first temperature T1 at which the water vapor sublimes onto the upper surface W1 of the substrate W. Thus, the water vapor can be suitably sublimated (transformed) into the first solid film H in the sublimation step.

[0265] The melting step heats the substrate W. Therefore, the melting step heats the first solid film H through the substrate W. In the melting step, the upper surface W1 of the substrate W comes into contact with the first solid film H. Therefore, the melting step can efficiently form the liquid film J.

[0266] In the melting step, the substrate W is heated to the second temperature T2 at which the first solid film H melts. Therefore, in the melting step, the first solid film H can be suitably melted into the liquid film J.

[0267] In the sublimation step, the pressure of the gas G inside the housing 12 is lower than the pressure at the triple point of water, and therefore, in the sublimation step, condensation of water vapor can be suitably suppressed.

[0268] In the melting step, the pressure of the gas G inside the housing 12 is greater than the pressure at the triple point of water, so that in the melting step, the first solid film H can be suitably prevented from sublimating.

[0269] The substrate processing method includes an adjusting step. In the adjusting step, the pressure of the gas G in the housing 12 is adjusted to a first pressure P1. In the adjusting step, the temperature of the substrate W is adjusted to a first temperature T1. The adjusting step is performed before the sublimation step. This allows the sublimation step to be started smoothly. This reduces the time required for the substrate processing method.

[0270] The adjusting step is performed before the first supplying step, so that the sublimation step can be started immediately after the first supplying step is started, thereby further shortening the time required for the substrate processing method.

[0271] The substrate processing method includes a solidification process. In the solidification process, the liquid film J solidifies. As a result, a second solid film L is formed in the solidification process. The second solid film L is formed on the upper surface W1 of the substrate W. In the solidification process, the liquid film J changes into the second solid film L. In the solidification process, the upper surface W1 of the substrate W comes into contact with the second solid film L. The second solid film L is in a solid phase. As described above, the liquid film J formed in the melting process covers the upper surface W1 of the substrate W. Therefore, when the liquid film J changes into the second solid film L, the upper surface W1 of the substrate W does not come into contact with the gas G. Therefore, the liquid film J solidifies without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, in the solidification process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K.

[0272] The substrate processing method includes a sublimation process. In the sublimation process, the second solid film L sublimes. In the sublimation process, the second solid film L changes into a gas phase without passing through a liquid state. Therefore, when the second solid film L sublimes, the upper surface W1 of the substrate W does not come into contact with the liquid. Therefore, the first solid film L sublimes without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface. Therefore, in the sublimation process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface.

[0273] As the second solid film L sublimes, the second solid film leaves the substrate W. As the second solid film L sublimes, the substrate W is dried.

[0274] In summary, in the solidification and sublimation steps, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface. Therefore, according to the substrate processing method, the substrate can be dried while the upper surface W1 of the substrate W is suitably protected. Therefore, the substrate processing method can process the substrate W more appropriately.

[0275] In the solidification step, the pressure of the gas G inside the housing 12 is maintained at a third pressure P3 at which the liquid film J can be solidified. Therefore, in the solidification step, evaporation of the liquid film J can be suitably suppressed.

[0276] The solidification step cools the liquid film J. Therefore, in the solidification step, the liquid film J is solidified suitably.

[0277] In the sublimation step, the pressure of the gas G inside the housing 12 is maintained at a fourth pressure P4 at which the second solid film L can be sublimated. Therefore, in the sublimation step, the second solid film L can be suitably prevented from melting.

[0278] The sublimation step heats the second solid film L. Therefore, in the sublimation step, the second solid film L is suitably sublimated.

[0279] The solidification step cools the substrate W. Therefore, the solidification step cools the liquid film J through the substrate W. In the solidification step, the upper surface W1 of the substrate W comes into contact with the liquid film J. Therefore, the solidification step can efficiently form the second solid film L.

[0280] In the solidification step, the substrate W is cooled to a third temperature T3 at which the liquid film J solidifies. Therefore, in the solidification step, the liquid film J can be solidified suitably.

[0281] The sublimation process heats the substrate W. Therefore, the sublimation process heats the second solid film L through the substrate W. In the sublimation process, the upper surface W1 of the substrate W comes into contact with the second solid film L. Therefore, the sublimation process can efficiently sublimate the second solid film L.

[0282] In the sublimation step, the substrate W is heated to a fourth temperature T4 at which the second solid film L sublimes. Therefore, in the sublimation step, the second solid film L can be suitably sublimated.

[0283] In the sublimation step, the gas G inside the housing 12 is discharged to the outside of the housing 12. Therefore, in the sublimation step, the second solid film L is more effectively sublimated. In the sublimation step, the second solid film L can be more effectively removed from the substrate W.

[0284] In the solidification process, the pressure of the gas G inside the housing 12 is greater than the pressure at the triple point of water, so that evaporation of the liquid film J can be suitably suppressed in the solidification process.

[0285] In the sublimation step, the pressure of the gas G inside the housing 12 is lower than the pressure at the triple point of water, so that the second solid film L can be suitably prevented from melting in the sublimation step.

[0286] The substrate processing method includes a second supply step. The second supply step supplies ammonia gas. The ammonia gas is in a gas phase. Therefore, in the second supply step, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. Therefore, in the second supply step, the ammonia gas can be supplied to the housing 12 while suitably protecting the upper surface W1 of the substrate W.

[0287] The liquid film J dissolves ammonia gas. Therefore, the liquid film J is derived from not only water vapor but also ammonia gas. Therefore, the liquid film J can process the substrate W more appropriately.

[0288] The substrate processing method includes a charging step. The charging step charges the second solid film L. Therefore, particles B contained in the second solid film L can be easily charged. Specifically, when particles B are exposed from the second solid film L in the sublimation step, particles B can be easily charged.

[0289] In the charging step, the second solid film L is negatively charged. Therefore, the particles B are also negatively charged. Therefore, electrostatic repulsion occurs between the negatively charged second solid film L and the negatively charged particles B. Therefore, the particles B can be suitably removed.

[0290] The substrate processing method includes a collecting step in which the charged particles B are collected. Therefore, the collecting step can effectively remove the charged particles B from the substrate W.

[0291] The substrate W has a pattern R. The pattern R is formed on the upper surface W1 of the substrate W. As described above, the substrate processing method processes the substrate W without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, the pattern R does not come into contact with the gas-liquid interface K. Therefore, the substrate processing method can appropriately process the substrate W while protecting the pattern R. For example, the substrate processing method can supply a processing liquid to the pattern R while preferably preventing the pattern R from collapsing. For example, the substrate processing method can supply a processing liquid to the pattern R while preferably preventing the convex portion W2 from collapsing.

[0292] The substrate processing apparatus 1 includes a housing 12 and a pressure adjusting unit 20. The pressure adjusting unit 20 adjusts the pressure of the gas G inside the housing 12. The housing 12 is airtight. Therefore, the pressure adjusting unit 20 can suitably adjust the pressure of the gas G inside the housing 12.

[0293] The substrate processing apparatus 1 includes a stage 15, a supply unit 17a, a temperature adjustment unit 31, and a control unit 10. The stage 15 is installed in a housing 12. A substrate W is placed on the stage 15 in a substantially horizontal position. The supply unit 17a supplies water vapor into the housing 12. The temperature adjustment unit 31 adjusts the temperature of the substrate W placed on the stage 15. The control unit 10 controls the supply unit 17a, the supply unit 17c, the exhaust unit 25, and the temperature adjustment unit 31.

[0294] The control unit 10 causes the supply unit 17a to supply water vapor to the housing 12. When the supply unit 17a supplies water vapor to the housing 12, the upper surface W1 of the substrate W is not in contact with the gas-liquid interface.

[0295] The control unit 10 controls the pressure adjustment unit 20 and the temperature adjustment unit 31 to sublimate the water vapor and form a first solid film H that covers the upper surface W1 of the substrate W placed on the stage 15. Therefore, when the water vapor turns into the first solid film H, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface.

[0296] The control unit 10 controls the pressure adjustment unit 20 and the temperature adjustment unit 31 to melt the first solid film and form a liquid film J that covers the upper surface W1 of the substrate W placed on the stage 15. Therefore, when the first solid film H turns into the liquid film J, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K.

[0297] In summary, the control unit 10 controls the supply unit 17a, the pressure adjustment unit 20, and the temperature adjustment unit 31 to supply water vapor to the housing 12, sublimate the water vapor, and melt the first solid film H. Therefore, the substrate processing apparatus 1 can form a liquid film J on the upper surface W1 of the substrate W without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, the substrate processing apparatus 1 can process the substrate W appropriately.

[0298] The substrate processing apparatus 1 sublimes water vapor to form a first solid film H that covers the upper surface W1 of the substrate W, and melts the first solid film H to form a liquid film J that covers the upper surface W1 of the substrate W. This effectively prevents the processing liquid from overflowing from the substrate W. That is, it effectively reduces loss of processing liquid. Therefore, the substrate processing apparatus 1 can efficiently form the liquid film J with less processing liquid. That is, the substrate processing apparatus 1 can process the substrate W with a small amount of processing liquid. As a result, the substrate processing apparatus 1 uses a relatively small amount of processing liquid. For example, the amount of processing liquid used in the substrate processing apparatus 1 is less than that used in conventional apparatuses.

[0299] The control unit 10 controls the pressure adjustment unit 20 and the temperature adjustment unit 31 to solidify the liquid film J and form a second solid film L on the upper surface W1 of the substrate W placed on the stage 15. Therefore, when the liquid film J turns into the second solid film H, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K.

[0300] The control unit 10 sublimates the second solid film L by controlling the pressure adjustment unit 20 and the temperature adjustment unit 31. Therefore, when the second solid film L sublimes, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface.

[0301] In summary, the control unit 10 controls the pressure adjustment unit 20 and the temperature adjustment unit 31 so as to solidify the liquid film J and sublimate the second solid film L. Therefore, the substrate processing apparatus 1 can remove the second solid film L from the upper surface W1 of the substrate W without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, the substrate processing apparatus 1 can dry the substrate W while protecting the upper surface W1 of the substrate W. Therefore, the substrate processing apparatus 1 can process the substrate W more appropriately.

[0302] The substrate processing apparatus 1 includes a supply unit 17b. The supply unit 17b supplies ammonia gas to the housing 12. The control unit 10 controls the supply unit 17b to supply the ammonia gas into the housing 12 and dissolve the ammonia gas in the liquid film J. In this manner, the substrate processing apparatus 1 can adjust the components of the liquid film J without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, the substrate processing apparatus 1 can process the substrate W more appropriately while protecting the upper surface W1 of the substrate W.

[0303] The temperature adjustment unit 31 is attached to the stage 15. Therefore, the temperature adjustment unit 31 can appropriately adjust the temperature of the substrate W placed on the stage 15.

[0304] The substrate processing apparatus 1 includes an electron emitter 41. The electron emitter 41 emits electrons into the housing 12. Therefore, the second solid film H can be suitably charged.

[0305] The substrate processing apparatus 1 includes an electrode 46. The electrode 46 is installed inside the housing 12. A positive voltage is applied to the electrode 46. Therefore, the electrode 46 can suitably collect negatively charged particles B.

[0306] The present invention is not limited to the embodiments, and can be modified as follows.

[0307] (1) In the embodiment, one type of gas (water vapor) is sublimated in the sublimation process. However, this is not limited to this. For example, multiple types of gases may be sublimated in the sublimation process. For example, at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas may be sublimated in the sublimation process. According to this modified embodiment, a liquid film J derived from at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas can be formed.

[0308] For example, the liquid film J derived from water vapor can be used to perform a rinsing process on the substrate W. The liquid film J derived from at least one of ammonia gas, methylamine gas, dimethylamine gas, and trimethylamine gas can be used to perform a cleaning process on the substrate W. For example, the liquid film J can suitably remove particles B from the upper surface W1 of the substrate W. The liquid film J derived from hydrogen peroxide gas can be used to perform an oxidation process on the substrate W. For example, the upper surface W1 of the substrate W can be oxidized by the liquid film J.

[0309] When multiple types of gases are sublimated, the multiple types of gases may or may not be sublimated simultaneously. For example, when multiple types of gases are sublimated, the multiple types of gases may be sublimated in the same sublimation step. Alternatively, the multiple types of gases may be sublimated in different sublimation steps.

[0310] Two alternative embodiments are described.

[0311] (1-1) Figure 16 is a flowchart showing the procedure of a substrate processing method according to a modified embodiment. Note that the same steps as those in the embodiment are denoted by the same reference numerals, and detailed explanations thereof will be omitted. The substrate processing method according to the modified embodiment differs from the substrate processing method according to the embodiment in steps S4-S6.

[0312] In the first supply step (step S4), water vapor and ammonia gas are supplied to the housing 12. For example, water vapor and ammonia gas are simultaneously supplied to the housing 12. Therefore, the gas G in the housing 12 contains water vapor and ammonia gas.

[0313] Specifically, the supply unit 17a and the supply unit 17b may respectively supply water vapor and ammonia gas to the housing 12. Alternatively, the configuration of the supply unit 17a may be modified so that the supply unit 17a supplies a mixed gas of water vapor and ammonia gas to the housing 12.

[0314] In the sublimation step (step S5), the water vapor and ammonia gas are sublimated to form a first solid film H.

[0315] In the sublimation process, the pressure of the gas G in the housing 12 is adjusted to a first pressure P1. In the sublimation process, the substrate W placed on the stage 15 is adjusted to a first temperature T1. Here, the first pressure P1 and the first temperature T1 are appropriately selected and changed depending on the type of gas to be sublimated. For example, the first pressure P1 is a pressure at which water vapor and ammonia gas can sublimate. For example, the first temperature T1 is a temperature at which water vapor and ammonia gas sublimate under the first pressure P1.

[0316] In the melting process (step S6), the first solid film H melts to form a liquid film J. The liquid film J is formed of a processing liquid derived from water vapor and ammonia gas. That is, the liquid film J contains ammonia water. Therefore, the melting process can perform a cleaning process on the substrate W using the liquid film J. For example, the melting process can separate particles B from the upper surface W1 of the substrate W.

[0317] In the melting process, the pressure of the gas G in the housing 12 is adjusted to a second pressure P2. In the melting process, the substrate W placed on the stage 15 is adjusted to a second temperature T2. Here, the second pressure P2 and the second temperature T2 are appropriately selected and changed depending on the components of the first solid film H.

[0318] Similarly, the third pressure P3 and the third temperature T3 in the solidification step are also selected and changed appropriately depending on the components of the liquid film J. The fourth pressure P4 and the fourth temperature T4 in the sublimation step are also selected and changed appropriately depending on the components of the second solid film L.

[0319] In this modified embodiment, the second supplying step (step S7) may be omitted.

[0320] In this modified embodiment, the supply unit 17a and the supply unit 17b are examples of the first supply unit of the present invention. The water vapor and the ammonia gas are examples of the first processing gas of the present invention.

[0321] (1-2) Figure 17 is a flowchart showing the procedure of a substrate processing method according to a modified embodiment. Note that the same steps as those in the embodiment are denoted by the same reference numerals, and detailed explanations thereof will be omitted. The substrate processing method according to the modified embodiment differs from the substrate processing method according to the embodiment in steps S4-S6.

[0322] The substrate processing method of the modified embodiment includes steps S4a and S4b instead of step S4, and includes steps S5a and S5b instead of step S5.

[0323] In the first supplying step of step S4a, water vapor is supplied to the housing 12.

[0324] In the sublimation step of step S5a, the water vapor is sublimated.

[0325] 18 is a diagram schematically illustrating the upper surface W1 of the substrate W in the solidification process of step S5a. The water vapor contained in the gas G within the housing 12 turns into a first solid film Ha without passing through a liquid state.

[0326] In the first supply step of step S4b, ammonia gas is supplied to the housing 12.

[0327] After the sublimation step of step S5a, the sublimation step of step S5b is carried out. In the sublimation step of step S5b, ammonia gas is sublimated.

[0328] 19 is a diagram schematically illustrating the upper surface W1 of the substrate W during the solidification process of step S5b. The ammonia gas contained in the gas G in the housing 12 is transformed into a first solid film Hb without passing through a liquid state. The first solid film Hb is layered on the first solid film Ha. The first solid film Ha and the second solid film Hb entirely cover the upper surface W1 of the substrate W.

[0329] In this way, water vapor is sublimated first. After the water vapor is sublimated, the ammonia gas is sublimated. Alternatively, the ammonia gas may be sublimated first, and then the water vapor may be sublimated.

[0330] In the melting process (step S6), the first solid film Ha and the first solid film Hb are entirely melted to form a liquid film J. The liquid film J is formed of a processing liquid derived from water vapor and ammonia gas. That is, the liquid film J contains ammonia water. Therefore, the melting process can perform a cleaning process on the substrate W using the liquid film J. For example, the melting process can separate particles B from the upper surface W1 of the substrate W.

[0331] In this modified embodiment, the second supplying step (step S7) may be omitted.

[0332] In this modified embodiment, the supply unit 17a and the supply unit 17b are examples of the first supply unit of the present invention. The water vapor and the ammonia gas are examples of the first processing gas of the present invention.

[0333] (2) In the embodiment, one type of gas (ammonia gas) is dissolved in the liquid film J in the second supply step. However, this is not limited to this. For example, multiple types of gases may be sublimated in the second supply step. For example, in the second supply step, at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas may be dissolved in the liquid film J. According to this modified embodiment, a liquid film J derived from at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas can be formed.

[0334] When multiple types of gases are dissolved in the liquid film J, the multiple types of gases may or may not be dissolved in the liquid film J simultaneously. For example, when multiple types of gases are dissolved in the liquid film J, the multiple types of gases may be dissolved in the liquid film J in the same second supply step. Alternatively, the multiple types of gases may each be dissolved in the liquid film J in a different second supply step.

[0335] Two alternative embodiments are described.

[0336] (2-1) Fig. 20 is a diagram showing the configuration of a processing unit 11 according to a modified embodiment. Note that the same components as those in the embodiment are given the same reference numerals and detailed description thereof will be omitted.

[0337] The processing unit 11 includes a supply unit 17d in addition to the supply units 17a-17c. The supply unit 17d is also connected in communication with the housing 12. The supply unit 17d supplies a gas to the housing 12. The gas supplied by the supply unit 17d is hydrogen peroxide gas. The hydrogen peroxide gas is in a gas phase.

[0338] The supply unit 17d is connected in communication with a supply source 21d. The supply source 21d sends hydrogen peroxide gas to the supply unit 17d. The supply source 21d may or may not be a component of the substrate processing apparatus 1.

[0339] The supply unit 17d is connected to the blowout unit .

[0340] Supply unit 17d includes pipe 18d and valve 19d. Valve 19d is provided on pipe 18d. Pipe 18d has a first end that is connected to supply source 21d. Pipe 18d has a second end that is connected to blowout unit 23. When valve 19d is open, supply unit 17d supplies hydrogen peroxide gas to housing 12 through blowout unit 23. When valve 19d is closed, supply unit 17d does not supply hydrogen peroxide gas to housing 12.

[0341] For convenience, reference will be made to Figure 4. Detailed explanations of steps that are the same as those in the embodiment will be omitted. The substrate processing method of this modified embodiment differs from the substrate processing method of the embodiment in step S7.

[0342] In the second supply step (step S7), ammonia gas and hydrogen peroxide gas are supplied to the housing 12. For example, ammonia gas and hydrogen peroxide gas are simultaneously supplied to the housing 12. Therefore, the gas G inside the housing 12 contains ammonia gas and hydrogen peroxide gas.

[0343] Specifically, supply unit 17b and supply unit 17d supply ammonia gas and hydrogen peroxide gas to housing 12, respectively.

[0344] In the second supply step (step S7), the liquid film J dissolves ammonia gas and hydrogen peroxide gas. As a result, the liquid film J contains ammonia water and hydrogen peroxide water. Because the liquid film J contains ammonia water, the liquid film J can perform a cleaning process on the substrate W. For example, the liquid film J can effectively remove particles B from the upper surface W1 of the substrate W. Because the liquid film J contains hydrogen peroxide water, the liquid film J can perform an oxidation process on the substrate W. For example, the liquid film J can oxidize the upper surface W1 of the substrate W.

[0345] In this modified embodiment, supply unit 17b and supply unit 17d are examples of the second supply unit of the present invention. Ammonia gas and hydrogen peroxide gas are examples of the second process gas of the present invention.

[0346] (2-2) Figure 21 is a flowchart showing the procedure of a substrate processing method according to a modified embodiment. Note that the same steps as those in the embodiment are denoted by the same reference numerals, and detailed explanations thereof will be omitted. The substrate processing method according to the modified embodiment includes steps S7a and S7b instead of step S7.

[0347] In the second supply process of step S7a, hydrogen peroxide gas is supplied to the housing 12. In the second supply process of step S7a, the liquid film J dissolves the hydrogen peroxide gas. As a result, the liquid film J contains aqueous hydrogen peroxide. Because the liquid film J contains aqueous hydrogen peroxide, the liquid film J can perform an oxidation process on the substrate W. For example, the liquid film J can oxidize the upper surface W1 of the substrate W.

[0348] After the second supply process of step S7a, the second supply process of step S7b is performed. In the second supply process of step S7b, ammonia gas is supplied to the housing 12. In the second supply process of step S7b, the liquid film J dissolves the ammonia gas. As a result, the liquid film J contains ammonia water in addition to hydrogen peroxide water. Because the liquid film J contains ammonia water, the liquid film J can further perform a cleaning process on the substrate W. For example, the liquid film J can suitably remove particles B from the upper surface W1 of the substrate W.

[0349] In this way, the hydrogen peroxide gas is first dissolved in the liquid film J. After the hydrogen peroxide gas is dissolved in the liquid film J, the ammonia gas is dissolved in the liquid film J. Alternatively, the ammonia gas may be dissolved in the liquid film J first, and then the hydrogen peroxide gas may be dissolved in the liquid film J.

[0350] In this modified embodiment, supply unit 17b and supply unit 17d are examples of the second supply unit of the present invention. Ammonia gas and hydrogen peroxide gas are examples of the second process gas of the present invention.

[0351] (3) In the embodiment, the second supply step is provided. However, this is not limited to this. The second supply step may be omitted. For example, as in the modified embodiment shown in FIG. 16 or FIG. 17, the second supply step may be omitted.

[0352] (4) In the embodiment, the adjusting step is performed before the first supplying step. However, this is not limited to this. For example, the adjusting step may be performed after the first supplying step. For example, the adjusting step may be performed after the first supplying step and before the sublimation step.

[0353] (5) In the embodiment, the substrate processing method includes an adjusting step. However, this is not limited to this. The adjusting step may be omitted. For example, either the first supplying step or the sublimation step may perform an operation equivalent to the adjusting step. For example, in the first supplying step, the pressure of the gas G in the housing 12 and the temperature of the substrate W placed on the stage 15 may be adjusted. For example, in the sublimation step, the pressure of the gas G in the housing 12 and the temperature of the substrate W placed on the stage 15 may be adjusted.

[0354] (6) In the embodiment, the solidification step solidifies the liquid film J while suppressing evaporation of the liquid film J. However, this is not limited to this. For example, the solidification step may allow only a portion of the liquid film J to evaporate. For example, if the liquid film J contains water and ammonia, the liquid film J may be solidified while allowing the ammonia to evaporate and suppressing the evaporation of the water.

[0355] (7) In the embodiment, the collecting step is included. However, this is not limiting. The collecting step may be omitted. For example, as shown in FIGS. 17 and 21, the substrate processing method does not have to include the collecting step. The charging step alone can generate a repulsive force between the negatively charged second solid film L and the negatively charged particles B. This allows the particles B to fly away from the second solid film L. Therefore, even if the collecting step is omitted, the particles B can be suitably removed from the substrate W.

[0356] (8) In the embodiment, a charging step is provided. However, this is not limited to this. The charging step may be omitted. For example, as shown in FIG. 21, the substrate processing method does not have to include the charging step. For example, the charging step may be omitted as appropriate depending on the processing performed on the substrate W by the substrate processing method. For example, if the substrate processing method performs an oxidation processing on the substrate W, the charging step may be omitted. For example, if the substrate processing method does not perform a cleaning processing on the substrate W, the charging step may be omitted.

[0357] (9) In the embodiment, supply unit 17a supplies water vapor to housing 12. However, this is not limited to this. For example, supply unit 17a may supply at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas to housing 12. Supply unit 17b may also be modified in the same manner as supply unit 17a.

[0358] (10) In the embodiment, supply unit 17a supplies one type of gas to housing 12. However, this is not limited to this. For example, supply unit 17a may supply a mixed gas containing two or more types of gas to housing 12. For example, supply unit 17a may supply a mixed gas containing at least two or more of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas to housing 12. Supply unit 17b may also be modified in the same way as supply unit 17a.

[0359] (11) In the embodiment, the supply units 17a, 17b, and 17c are all connected in communication with the common blowout unit 23. However, this is not limited to this. The supply units 17a, 17b, and 17c may each be connected in communication with a different blowout unit.

[0360] (12) In the embodiment, a specific configuration of the temperature adjustment unit 31 has been exemplified. For example, the temperature adjustment unit 31 includes a cooling pipe 33 and an electric heater 37. However, this is not limited to this. The configuration of the temperature adjustment unit 31 may be changed as appropriate. For example, the temperature adjustment unit 31 may include a Peltier element that generates and absorbs heat. For example, the temperature adjustment unit 31 may include a thermoelectric element that generates and absorbs heat.

[0361] (13) In the embodiment, the substrate W has a pattern R formed on the upper surface W1 of the substrate W. However, this is not limited to this. For example, the substrate W may not have a pattern R. For example, the pattern R may not be formed on the upper surface W1 of the substrate W. For example, the substrate W may have an upper surface W1 on which no pattern R is formed. Even in these modified embodiments, the substrate processing method and substrate processing apparatus 1 described above can form a liquid film J on the upper surface W1 of the substrate W while protecting the upper surface W1 of the substrate W. Therefore, even in these modified embodiments, the substrate W can be appropriately processed by the substrate processing method and substrate processing apparatus 1.

[0362] (14) The embodiment and each of the modified embodiments described above in (1) to (13) may be further modified as appropriate by replacing or combining each configuration with the configuration of another modified embodiment. [Explanation of symbols]

[0363] 1... Substrate processing equipment 10...Control section 11... Processing unit 12 … Housing 13... Processing space 15... Stage (substrate placement area) 17a... Supply section (1st supply section / 2nd supply section) 17b... Supply section (second supply section) 17c ... Supply section (pressure adjustment section) 20... Pressure adjustment section 25...Exhaust section (pressure adjustment section) 31 … Temperature adjustment section 32 … Cooling section 36 … Heating section 41...Electron emission section 43 … Electron beam source 45 … Collection Department 46 … Electrode P1: First pressure (pressure at which the first process gas can be sublimated) P2: Second pressure (pressure at which the first solid film can melt) P3: Third pressure (pressure at which the liquid film can solidify) P4: Fourth pressure (pressure at which the second solid film can sublimate) T1: First temperature (the temperature at which the first process gas condenses under the first pressure) T2: Second temperature (the temperature at which the first solid film H melts under the second pressure) T3: Third temperature (the temperature at which the liquid film solidifies under the third pressure) T4: Fourth temperature (the temperature at which the second solid film sublimes under the fourth pressure) A ... recess B... Particle G: Gas inside the enclosure H…first solid film J…Liquid film K … air-liquid interface L…Second solid membrane R... Pattern W: Substrate W1: Top surface of the board W2: Convex part

Claims

1. A substrate processing method for processing a substrate, comprising: a placing step of placing the substrate in a substantially horizontal position within the housing; a first supply step of supplying a first processing gas to the housing; a sublimation step of sublimating the first process gas to form a first solid film covering an upper surface of the substrate; a melting step of melting the first solid film to form a liquid film covering the top surface of the substrate; solidifying the liquid film to form a second solid film on the upper surface of the substrate; a sublimation step of sublimating the second solid film; A substrate processing method comprising:

2. 2. The substrate processing method according to claim 1, the sublimation step includes cooling the first process gas while maintaining a gas pressure in the housing at a pressure at which the first process gas can be sublimated; The melting step includes heating the first solid film while maintaining the pressure of the gas in the housing at a pressure at which the first solid film can be melted. Substrate processing method.

3. 3. The substrate processing method according to claim 1, the sublimation step includes cooling the substrate to a temperature at which the first process gas sublimes onto the upper surface of the substrate; The melting step includes heating the substrate to a temperature at which the first solid film melts. Substrate processing method.

4. 4. The substrate processing method according to claim 1, further comprising: The first process gas contains at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas. Substrate processing method.

5. 5. The substrate processing method according to claim 1, further comprising: the first process gas is water vapor; In the sublimation step, the gas pressure in the housing is lower than the pressure of the triple point of water, In the melting step, the pressure of the gas in the housing is greater than the pressure of the triple point of water. Substrate processing method.

6. A substrate processing method according to any one of claims 1 to 5, the solidifying step includes cooling the liquid film while maintaining the gas pressure in the housing at a pressure at which the liquid film can be solidified; The sublimation step includes heating the second solid film while maintaining the pressure of the gas in the housing at a pressure at which the second solid film can be sublimated. Substrate processing method.

7. A substrate processing method according to any one of claims 1 to 6, The solidifying step includes cooling the substrate to a temperature at which the liquid film solidifies; The sublimation step includes heating the substrate to a temperature at which the second solid film sublimes. Substrate processing method.

8. A substrate processing method according to claim 1, comprising: The sublimation step includes discharging the gas inside the housing to the outside of the housing. Substrate processing method.

9. A substrate processing method according to claim 1, comprising: the first process gas is water vapor; In the solidification step, the pressure of the gas in the housing is greater than the pressure of the triple point of water, In the sublimation process, the pressure of the gas inside the housing is lower than the pressure of the triple point of water. Substrate processing method.

10. A substrate processing method according to any one of claims 1 to 9, comprising: a second supply step of supplying a second process gas to the housing; Equipped with The liquid film dissolves the second process gas. Substrate processing method.

11. The substrate processing method according to claim 10, The second process gas contains at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas. Substrate processing method.

12. A substrate processing method according to any one of claims 1 to 11, comprising: a charging step of charging the second solid film; Equipped with Substrate processing method.

13. A substrate processing method according to any one of claims 1 to 12, comprising: a collecting step of collecting the charged particles; Equipped with Substrate processing method.

14. A substrate processing method according to any one of claims 1 to 13, comprising: The substrate has a pattern formed on the top surface of the substrate. Substrate processing method.

15. A substrate processing apparatus, a sealable housing; a substrate placement section that is installed within the housing and that places a substrate in a substantially horizontal position; a first supply unit that supplies a first processing gas into the housing; a pressure adjusting unit that adjusts the pressure of the gas inside the housing; a temperature adjusting unit that adjusts the temperature of the substrate placed on the substrate placement unit; a control unit that controls the first supply unit, the pressure adjustment unit, and the temperature adjustment unit; Equipped with The control unit supplying the first processing gas from the first supply unit to the housing; by controlling the pressure adjusting unit and the temperature adjusting unit, the first process gas is sublimated to form a first solid film that covers an upper surface of the substrate placed on the substrate placement unit; by controlling the pressure adjusting unit and the temperature adjusting unit, the first solid film is melted to form a liquid film that covers the upper surface of the substrate placed on the substrate placement unit; solidifying the liquid film by controlling the pressure adjusting unit and the temperature adjusting unit to form a second solid film on the upper surface of the substrate placed on the substrate placement unit; The second solid film is sublimated by controlling the pressure adjusting unit and the temperature adjusting unit. Substrate processing equipment.

16. The substrate processing apparatus according to claim 15, a second supply unit that supplies a second process gas to the housing; Equipped with The control unit The second processing gas is supplied from the second supply unit to the housing, and the second processing gas is dissolved in the liquid film. Substrate processing equipment.

17. The substrate processing apparatus according to claim 15 or 16, an electron emitting unit that emits electrons into the housing; Equipped with The control unit causes the electron emission unit to negatively charge the second solid film. Substrate processing equipment.

18. The substrate processing apparatus according to claim 17, an electrode installed in the housing and to which a positive voltage is applied; Equipped with Substrate processing equipment.

Images