WO2022230669A1

WO2022230669A1 - Substrate processing method and substrate processing device

Info

Publication number: WO2022230669A1
Application number: PCT/JP2022/017689
Authority: WO
Inventors: 昭平中村; 敦谷出
Original assignee: 株式会社Ｓｃｒｅｅｎホールディングス
Priority date: 2021-04-28
Filing date: 2022-04-13
Publication date: 2022-11-03
Also published as: JP2022170013A

Abstract

The present invention pertains to a substrate processing method and a substrate processing device. The substrate processing method for processing a substrate comprises a placement step, a first supply step, a deposition step, and a melting step. In the placement step, the substrate is placed in a substantially horizontal orientation inside a casing. In the first supply step, a first processing gas is supplied into the casing. In the deposition step, the first processing gas is deposited to form a first solid film covering the upper 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.

Description

Substrate processing method and substrate processing apparatus

The present invention relates to a substrate processing method and a substrate processing apparatus for processing substrates. Substrates include, for example, semiconductor wafers, liquid crystal display substrates, organic EL (Electroluminescence) substrates, FPD (Flat Panel Display) substrates, optical display substrates, magnetic disk substrates, optical disk substrates, magneto-optical disk substrates, They are substrates for photomasks and substrates for solar cells.

Patent Document 1 discloses a substrate processing method and a substrate processing apparatus. A substrate processing apparatus includes a spin base, an electric motor, and a nozzle. The spin base holds the substrate in a substantially horizontal posture. An electric motor rotates the spin base. The nozzle ejects the processing liquid onto the substrate held by the spin base. The processing liquid is SC1, for example. SC1 is a mixture of aqueous ammonia, hydrogen peroxide, and deionized water.

The substrate processing method includes an SC1 supply step. In the SC1 supply step, the electric motor rotates the substrate held by the spin base, and the nozzle ejects SC1 onto the substrate. SC1 is thereby supplied to the substrate.

Japanese Patent Application Laid-Open No. 2002-329696

Even with conventional substrate processing methods and substrate processing apparatuses, substrates could not be processed properly in some cases. For example, when a substrate has a pattern formed on the upper surface of the substrate, the pattern may collapse even with the conventional substrate processing method and substrate processing apparatus. For example, when the pattern is fine, even the conventional substrate processing method and substrate processing apparatus may not be able to sufficiently suppress the collapse of the pattern. Incidentally, the conventional substrate processing method is, for example, the substrate processing method disclosed in Japanese Unexamined Patent Application Publication No. 2002-200012. A conventional substrate processing apparatus is, for example, the substrate processing apparatus disclosed in Patent Document 1. As used herein, conventional substrate processing methods are arbitrarily abbreviated as "conventional methods." Conventional substrate processing equipment is appropriately abbreviated as "conventional equipment". Where no distinction is made between conventional methods and conventional devices, conventional methods and conventional devices are abbreviated as "prior art" as appropriate.

Further, the conventional substrate processing method and substrate processing apparatus rotate the substrate and discharge the processing liquid from the nozzle onto the substrate. At this time, part of the treatment liquid discharged onto the substrate overflows the substrate. Therefore, it has been necessary to supply a large amount of processing liquid to the substrate in order to process the substrate. As a result, the conventional method and apparatus used a relatively large amount of processing liquid.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of appropriately processing substrates.

The present invention was obtained through further intensive study 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 placing step of placing the substrate in a substantially horizontal posture in a housing; and a first supplying step of supplying a first processing gas to the housing. a condensation step of condensing the first process gas to form a first solid film covering the top surface of the substrate; and melting the first solid film to form a liquid film covering the top surface of the substrate. and a melting step.

The substrate processing method includes a placement step and a first supply step. In the mounting step, the substrate is mounted in a substantially horizontal posture within the housing. The first supply step supplies the first processing gas 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. In the following, the interface formed between the gas and the liquid is appropriately referred to as the "gas-liquid interface".

The substrate processing method includes a sublimation process. In the condensing step, the first process gas condenses within the housing. In the condensation process, the first process gas is transformed into a first solid film without going through a liquid. A first solid film covers the top surface of the substrate. Therefore, in the condensation process, the top surface of the substrate does not contact the gas-liquid interface.

The substrate processing method includes a melting step. In the melting step, the first solid film is melted. In the melting step, the first solid film transforms into a liquid film. A liquid film covers the top surface of the substrate. As mentioned above, the first solid film covers the top surface of the substrate. Therefore, the upper surface of the substrate does not contact the gas-liquid interface during the melting process.

In summary, the upper surface of the substrate does not come into contact with the gas-liquid interface in the mounting process, the first supply process, the condensation process, and the melting process. 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 properly process the substrate.

Further, the substrate processing method condenses 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. Therefore, it is possible to suitably prevent the processing liquid from overflowing from the substrate. That is, it is possible to suitably suppress the loss of the treatment liquid. Therefore, the substrate processing method can efficiently form a liquid film with a smaller amount of 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 relatively little 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 the conventional method.

In the substrate processing method described above, the condensation step includes cooling the first processing gas while maintaining the pressure of the gas in the housing at a pressure at which the first processing gas can condense, and the melting step. Preferably, the first solid film is heated while the pressure of the gas in the housing is maintained at a pressure at which the first solid film can be melted. The condensation step maintains the pressure of the gas within the housing at a pressure at which the first process gas can be condensed. For this reason, the condensation process can suitably suppress the first process gas from condensing. The condensation process cools the first process gas. Therefore, in the sublimation process, the first process gas is suitably sublimated. The melting step maintains the pressure of the gas within the housing at a pressure at which the first solid film can be melted. Therefore, the melting step can suitably suppress the sublimation of the first solid film. The melting step heats the first solid film. Therefore, in the melting step, the first solid film is preferably melted.

In the substrate processing method described above, the condensation step cools the substrate to a temperature at which the first process gas condenses onto the top surface of the substrate, and the melting step cools the substrate to a temperature at which the first solid film melts. Preferably, the substrate is heated up to . The condensation step cools the first process gas through the substrate. In the condensation process, the top surface of the substrate is in contact with the first process gas. Therefore, the condensation process can efficiently form the first solid film on the upper surface of the substrate. The condensation step cools the substrate to a temperature at which the first process gas condenses onto the top surface of the substrate. Therefore, the condensation process can favorably condense the first process gas into the first solid film. In the condensing step, the first process gas preferably condenses into the first solid film. The melting step heats the first solid film through the substrate. In the melting step, the top surface of the substrate is in contact with the first solid film. Therefore, the melting process 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 the liquid film.

In the substrate processing method described above, 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 noted above, the liquid film originates from the first process gas. Therefore, the liquid film contains at least one of water, ammonia, methylamine, dimethylamine, trimethylamine, and hydrogen peroxide. Therefore, the liquid film can properly treat the substrate.

In the substrate processing method described above, the first processing gas is water vapor, in the condensation step, the pressure of the gas in the housing is lower than the pressure at the triple point of water, and in the melting step, is preferably greater than the pressure at the triple point of water. In the condensation process, the pressure of the gas within the enclosure is less than the triple point pressure of water. Therefore, in the condensation process, condensation of water vapor can be suitably suppressed. During the melting process, the pressure of the gas within the enclosure is greater than the pressure at the triple point of water. Therefore, in the melting step, sublimation of the first solid film can be suppressed favorably.

The substrate processing method described above 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.

The substrate processing method includes a solidification step. In the solidification step, the liquid film solidifies. In the solidification step, the liquid film transforms into a second solid film. A second solid film is formed on the top surface of the substrate. As mentioned above, the liquid film formed in the melting process covers the top surface of the substrate. Therefore, in the solidification process, the upper surface of the substrate does not contact the gas-liquid interface.

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

In summary, the upper surface of the substrate does not come into contact with the gas-liquid interface during the solidification process and the sublimation process. Therefore, according to the substrate processing method, the substrate can be dried while suitably protecting the upper surface of the substrate. Therefore, the substrate processing method can process the substrate more appropriately.

In the above-described substrate processing method, the solidification step cools the liquid film while maintaining the pressure of the gas in the housing at a pressure that allows the liquid film to solidify, and the sublimation step cools the gas in the housing. It is preferable to heat the second solid film while maintaining the pressure of the gas at a pressure at which the second solid film can be sublimated. The solidification step maintains the pressure of the gas inside the housing at a pressure that allows the liquid film to solidify. For this reason, the solidification process can suitably suppress the evaporation of the liquid film. The solidification step cools the liquid film. For this reason, in the solidification step, the liquid film is suitably solidified. The sublimation process maintains the pressure of the gas inside the housing at a pressure at which the second solid film can be sublimated. Therefore, the sublimation process can suitably suppress the melting of the second solid film. The sublimation process heats the second solid film. Therefore, in the sublimation step, the second solid film sublimates favorably.

In the substrate processing method described above, 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 sublimates. The solidification step cools the liquid film through the substrate. In the solidification process, the upper surface of the substrate is in 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 process heats the second solid film through the substrate. In the sublimation process, the upper surface of the substrate is in contact with the second solid film. Therefore, the sublimation process efficiently sublimes the second solid film. The sublimation step heats the substrate to a temperature at which the second solid film sublimates. Therefore, the sublimation step can favorably sublimate the second solid film.

In the substrate processing method described above, the sublimation step preferably discharges the gas inside the housing to the outside of the housing. In the sublimation step, the second solid film sublimates more favorably.

In the substrate processing method described above, the first processing gas is water vapor, the pressure of the gas in the housing is higher than the triple point pressure of water in the solidification step, and the pressure of the gas in the housing is higher than the triple point of water in the sublimation step The pressure of the gas is preferably lower than the triple point pressure of water. In the solidification process, the pressure of the gas inside the enclosure is greater than the pressure at the triple point of water. Therefore, in the solidification step, evaporation of the liquid film can be suitably suppressed. In the sublimation process, the pressure of the gas inside the enclosure is less than the triple point pressure of water. Therefore, in the sublimation process, the melting of the second solid film can be suitably suppressed.

The above-described substrate processing method preferably includes a second supply step of supplying a second processing gas to the housing, and the liquid film dissolves the second processing gas. In the second supply step, a second processing 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.

The liquid film dissolves the second process gas. Thus, the liquid film can better treat the substrate.

In the substrate processing method described above, 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 liquid film dissolves the second process gas, the liquid film contains at least one of water, ammonia, methylamine, dimethylamine, trimethylamine, and hydrogen peroxide. Thus, the liquid film can better treat the substrate.

The substrate processing method described above preferably includes a charging step of charging the second solid film. By charging the second solid film, the particles contained in the second solid film can also be easily charged. Therefore, particles contained in the second solid film can be preferably removed.

The substrate processing method described above preferably includes a collecting step of collecting the charged particles. The collecting step can advantageously remove charged particles from the substrate.

In the substrate processing method described above, the substrate preferably has a pattern formed on the upper surface of the substrate. The substrate processing method can properly process the substrate while protecting the pattern.

The present invention relates to a substrate processing apparatus comprising a hermetically sealable housing, a substrate placement unit installed in the housing for placing a substrate in a substantially horizontal posture, and supplying a first processing gas into the housing. a pressure adjusting unit for adjusting the pressure of the gas in the housing; a temperature adjusting unit for adjusting the temperature of the substrate placed on the substrate placing unit; the first supplying unit and the a control unit configured to control the pressure adjustment unit and the temperature adjustment unit, the control unit supplying the first processing gas from the first supply unit to the housing, and controlling the pressure adjustment unit and the temperature adjustment unit; forming a first solid film covering the upper surface of the substrate placed on the substrate platform by condensing the first processing gas by controlling the pressure adjusting part and the temperature adjusting part; In the substrate processing apparatus, the control melts the first solid film to form a liquid film covering the upper surface of the substrate placed on the substrate placement part.

The housing can be sealed. Therefore, the pressure adjustment section can preferably adjust the pressure of the gas inside the housing.

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

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. The temperature adjuster adjusts the temperature of the substrate placed on the substrate platform. This causes the first process gas to condense. A first solid film is formed. That is, the first process gas is transformed into the first solid film without passing through the liquid. The first solid film covers the upper surface of the substrate placed on the substrate platform. Therefore, when the first process gas transforms into the first solid film, the top surface of the substrate does not contact the gas-liquid interface.

The control unit controls the pressure adjustment unit and the temperature adjustment unit. This causes the first solid film to melt. A liquid film is formed. That is, the first solid film turns into a liquid film. The liquid film covers the upper surface of the substrate placed on the substrate platform. Therefore, when the first solid film turns into a liquid film, the upper surface of the substrate does not contact the gas-liquid interface.

In summary, the control unit comprises a first supply unit, a pressure adjustment unit, and a temperature adjustment unit to supply a first process gas to the housing, cause the first process gas to condense, and melt the first solid film. to control. Therefore, the substrate processing apparatus can form a liquid film on the upper surface of the substrate without contacting the upper surface of the substrate with the gas-liquid interface. Therefore, the substrate processing apparatus can supply the processing liquid to the upper surface of the substrate while protecting the upper surface of the substrate. Therefore, the substrate processing apparatus can appropriately process the substrate.

Further, the substrate processing apparatus condenses the first processing gas to form a first solid film covering the upper surface of the substrate. The substrate processing apparatus melts the first solid film to form a liquid film covering the upper surface of the substrate. Therefore, it is possible to suitably prevent the processing liquid from overflowing from the substrate. That is, it is possible to suitably suppress the loss of the treatment liquid. Therefore, the substrate processing apparatus can efficiently form a liquid film with a smaller amount of processing liquid. That is, the substrate processing apparatus can process the substrate 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 a substrate processing apparatus is less than the amount of processing liquid used in a conventional apparatus.

In the above-described substrate processing apparatus, the control unit controls the pressure adjustment unit and the temperature adjustment unit to solidify the liquid film on the upper surface of the substrate placed on the substrate placement unit. and sublimating the second solid film by controlling the pressure control unit and the temperature control unit.

The control unit controls the pressure adjustment unit and the temperature adjustment unit. This causes the liquid film to solidify. A second solid film is formed. That is, the liquid film turns into a second solid film. The second solid film is formed on the upper surface of the substrate placed on the substrate platform. As described above, the liquid film covers the upper surface of the substrate placed on the substrate platform. Therefore, when the liquid film turns into the second solid film, the upper surface of the substrate does not contact the gas-liquid interface.

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 changes to gas without passing through liquid. Therefore, when the second solid film sublimates, the upper surface of the substrate does not come into contact with the gas-liquid interface.

In summary, the controller controls the pressure regulator and the temperature regulator so that the liquid film is solidified and the second solid film is sublimated. Therefore, the substrate processing apparatus can remove the second solid film from the upper surface of the substrate without contacting the upper surface of the substrate 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 substrates more appropriately.

The substrate processing apparatus described above includes a second supply unit that supplies a second processing gas to the housing, and the control unit controls the second supply unit to cause the second gas to be supplied to the housing. It is preferable to supply a processing gas to dissolve the second processing gas in the liquid film. The control section controls the second supply section. The second supply unit supplies the second processing gas to the housing. A second process gas is dissolved in the liquid film. Thus, the substrate processing apparatus can adjust the components 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.

The substrate processing apparatus described above preferably includes an electron emitting section that emits electrons into the housing. The electron emission section can suitably charge the second solid film.

The substrate processing apparatus described above preferably includes an electrode installed in the housing and to which a positive voltage is applied. Electrodes can preferably collect negatively charged particles.

According to the substrate processing method and substrate processing apparatus of the present invention, substrates can be processed appropriately.

It is a top view which shows the inside of the substrate processing apparatus of embodiment. It is a control block diagram of a substrate processing apparatus. It is a figure which shows the structure of the processing unit of embodiment. It is a flow chart which shows the procedure of the substrate processing method of an embodiment. It is a figure which shows typically the upper surface of the board|substrate in a mounting process and a 1st supply process. It is a figure which shows typically the upper surface of the board|substrate in a sublimation process. It is a figure which shows typically the upper surface of the board|substrate in a sublimation process. It is a figure which shows typically the upper surface of the board|substrate in a melting|dissolving process. It is a figure which shows typically the upper surface of the board|substrate in a melting|dissolving process. It is a figure which shows typically the upper surface of the board|substrate in a 2nd supply process. It is a figure which shows typically the upper surface of the board|substrate in a solidification process. It is a figure which shows typically the upper surface of the board|substrate in a solidification process. FIG. 10 is a diagram schematically showing the upper surface of the substrate in the charging process; It is a figure which shows typically the upper surface of the board|substrate in a sublimation process. It is a figure which shows typically the upper surface of the board|substrate in a sublimation process. It is a flowchart which shows the procedure of the substrate processing method of modification embodiment. It is a flowchart which shows the procedure of the substrate processing method of modification embodiment. It is a figure which shows typically the upper surface of the board|substrate in a solidification process. It is a figure which shows typically the upper surface of the board|substrate in a solidification process. It is a figure which shows the structure of the processing unit concerning deformation|transformation embodiment. It is a flowchart which shows the procedure of the substrate processing method of modification embodiment.

The substrate processing method and substrate processing apparatus of the present invention will be described below with reference to the drawings.

<1. Overview of Substrate Processing Apparatus>
FIG. 1 is a plan view showing the inside of the substrate processing apparatus of the embodiment. The substrate processing apparatus 1 processes a substrate W. As shown in FIG. The processing that the substrate processing apparatus 1 performs on the substrate W is, for example, liquid processing. Liquid processing is to supply the substrate W with a processing liquid.

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, or a magneto-optical disk substrate. , photomask substrates, and solar cell substrates. The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in plan view.

The substrate processing apparatus 1 includes an indexer section 3 and a processing block 7. A processing block 7 is connected to the indexer section 3 . The indexer unit 3 supplies substrates W to the processing block 7 . The processing block 7 performs processing on the substrate W. FIG. The indexer section 3 retrieves the substrates W from the processing block 7 .

In this specification, for the sake of convenience, the direction in which the indexer unit 3 and the processing blocks 7 are arranged is called the "front-back direction X". The front-rear direction X is horizontal. Of the front-back direction X, the direction from the processing block 7 to the indexer unit 3 is called "forward". The direction opposite to forward is called "backward". A horizontal direction orthogonal to the front-rear direction X is called a “width direction Y”. One direction of the "width direction Y" is appropriately called "right side". The direction opposite to right is called "left". A direction perpendicular to the horizontal direction is called a “vertical direction Z”. In each figure, front, rear, right, left, top, and bottom are indicated as appropriate for reference.

The indexer section 3 includes a plurality of (for example, four) carrier placement sections 4 . Each carrier mounting portion 4 mounts one carrier C thereon. A carrier C accommodates a plurality of substrates W. As shown in FIG. Carrier C is, for example, FOUP (Front Opening Unified Pod), SMIF (Standard Mechanical Interface), and OC (Open Cassette).

The indexer section 3 has a transport mechanism 5 . The transport mechanism 5 is arranged behind the carrier placement section 4 . The transport mechanism 5 transports the substrate W. As shown in FIG. The transport mechanism 5 can access the carrier C placed on the carrier placement section 4 . The transport mechanism 5 includes a hand 5a and a hand driving section 5b. The hand 5a supports the substrate W. The hand driving section 5b is connected to the hand 5a. The hand driving section 5b moves the hand 5a. The hand drive unit 5b moves the hand 5a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example. The hand drive unit 5b rotates the hand 5a in a horizontal plane, for example.

The processing block 7 has a transport mechanism 8 . The transport mechanism 8 transports the substrate W. As shown in FIG. The transport mechanism 8 and the transport mechanism 5 can transfer substrates W to each other. The transport mechanism 8 includes a hand 8a and a hand driving section 8b. The hand 8a supports the substrate W. The hand driving section 8b is connected to the hand 8a. The hand driving section 8b moves the hand 8a. The hand drive unit 8b moves the hand 8a in the front-rear direction X, the width direction Y, and the vertical direction Z, for example. The hand driving section 8b rotates the hand 8a in a horizontal plane, for example.

The processing block 7 includes a plurality of processing units 11. The processing unit 11 is arranged on the side of the transport mechanism 8 . Each processing unit 11 processes the substrate W. FIG.

The processing unit 11 includes a housing 12 and a stage 15. The stage 15 is installed inside the housing 12 . A substrate W is placed on the stage 15 . The substrate W is processed within the housing 12 .

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

The processing unit 11 has a shutter 14 . The shutter 14 opens and closes the substrate transfer port 12a. A shutter 14 is attached to the housing 12 . The shutter 14 is movable with respect to the housing 12 . When the shutter 14 opens the substrate transfer port 12a, the transfer mechanism 8 can move the substrate W between the inside and the outside of the housing 12 through the substrate transfer port 12a.

FIG. 2 is a control block diagram of the substrate processing apparatus 1. FIG. The substrate processing apparatus 1 includes a control section 10 . The controller 10 controls the transport mechanisms 5 and 8 and the processing unit 11 . The controller 10 is electrically connected to the transport mechanisms 5 and 8 and the processing unit 11 so as to be communicable.

The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a RAM (Random-Access Memory) that serves as a work area for arithmetic processing, a storage medium such as a fixed disk, and the like. The control unit 10 has various types of information stored in advance in a storage medium. 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 . Processing information is also called a processing recipe.

An operation example of the substrate processing apparatus 1 will be briefly described.

The indexer section 3 supplies substrates 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 .

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 port 12a. The transport mechanism 8 transports the substrate W from the transport mechanism 5 to the stage 15 of each processing unit 11 .

The shutter 14 closes the substrate transfer port 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.

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 port 12a. The transport mechanism 8 transports the substrate W from the stage 15 to the transport mechanism 5 .

The indexer section 3 recovers the substrates W from the processing block 7 . Specifically, the transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C. As shown in FIG.

<2. Configuration of Processing Unit 11>
FIG. 3 is a diagram showing the configuration of the processing unit 11. As shown in FIG. In FIG. 3, illustration of the substrate transfer port 12a and the shutter 14 is omitted. Each processing unit 11 has the same structure. The processing unit 11 is classified as a single wafer type. That is, each processing unit 11 processes only one substrate W at a time.

The housing 12 can be sealed. Specifically, the enclosure 12 has a processing space 13 within the enclosure 12 . The housing 12 defines a processing space 13 . A stage 15 is installed in the processing space 13 . A 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 port 12a, the processing space 13 is substantially sealed.

A single substrate W is placed on the stage 15 . The stage 15 mounts the substrate W in a substantially horizontal posture. The stage 15 supports the substrate W. When the substrate W is placed on the stage 15, the substrate W stands still.

The stage 15 has a substantially horizontal plate shape. The stage 15 has an upper surface 15a. The upper surface 15a contacts the lower surface of the substrate W. As shown in FIG. The bottom surface of the substrate W is also called the backside of the substrate W. As shown in FIG. The stage 15 is arranged below the processing space 13, for example.

The substrate processing apparatus 1 does not have 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.

The processing unit 11 includes one or more (for example, three)

supply units

17a, 17b, 17c. Supply units 17a-17c are connected to housing 12, respectively. Supply portions 17a-17c communicate with housing 12, respectively. The supply units 17a-17c supply gas to the housing 12, respectively. The supply units 17a-17c supply gas to the processing space 13, respectively.

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

Water vapor and ammonia gas are used to process the substrate W. Water vapor is, for example, deionized water vapor.

The dry gas is used to adjust the pressure of the gas inside the housing 12. The supply part 17c can adjust the pressure of the gas inside the housing 12 . The supply part 17c can increase the pressure of the gas inside the housing 12 .

A dry gas has a dew point lower than normal temperature. The dew point is, for example, about -76°C. Dry gas is, for example, air. Dry gas is, for example, compressed air. A dry gas is, for example, an inert gas. Dry gas is, for example, nitrogen gas.

Note that the supply unit 17a does not supply liquid to the housing 12. The supply unit 17b does not supply liquid to the housing 12 either. The supply unit 17c also does not supply liquid to the housing 12 .

The supply unit 17a is connected to the supply source 21a. The supply part 17a communicates with the supply source 21a. The supply source 21a sends water vapor to the supply section 17a. The supply part 17b is connected to the supply source 21b. The supply part 17b communicates with the supply source 21b. Supply source 21b sends ammonia gas to supply unit 17b. The supply part 17c is connected to the supply source 21c. The supply part 17c communicates with the supply source 21c. Supply source 21c delivers dry gas to supply 17c.

The supply source 21 a may be an element of the substrate processing apparatus 1 . Alternatively, source 21 a may not be a component of substrate processing apparatus 1 . For example, the supply source 21a may be utility equipment installed outside the substrate processing apparatus 1 . Similarly, source 21 b and source 21 c may each be elements of substrate processing apparatus 1 . Alternatively, the

supply sources

21b and 21c may not be elements of the substrate processing apparatus 1, respectively.

The processing unit 11 includes one blowing section 23 . The blowout section 23 is connected to the supply sections 17a-17c. The blowout section 23 communicates with the supply sections 17a-17c. The supply units 17a to 17c supply gas to the housing 12 through the blowout unit 23, respectively.

The blowout part 23 is arranged at a position higher than the stage 15, for example. The blow-out part 23 is attached to the side part of the housing|casing 12, for example. Alternatively, the blowout part 23 may be attached to the top of the housing 12 . Alternatively, the blowout part 23 may be installed inside the housing 12 . The blowout part 23 may be arranged above the stage 15, for example.

The blowout part 23 blows out gas in a direction away from the substrate W supported by the stage 15, for example. The blow-out part 23 blows off gas in a substantially horizontal direction, for example.

The arrangement and configuration of the supply unit 17a will be described. At least part of the supply unit 17 a is arranged outside the housing 12 .

Supply portions

17b and 17c are also arranged in the same manner as supply portion 17a.

The supply unit 17a includes a pipe 18a and a valve 19a. The valve 19a is provided on the pipe 18a. Tubing 18a has a first end connected to source 21a. A first end of the pipe 18a communicates with the supply source 21a. The pipe 18 a has a second end connected to the blowout portion 23 . A second end of the pipe 18 a communicates with the blowout portion 23 . When the valve 19a is opened, the supply section 17a supplies water vapor to the housing 12 through the blowout section 23. As shown in FIG. When the valve 19a is closed, the supply 17a does not supply water vapor to the housing 12;

Similarly, the supply unit 17b includes a pipe 18b and a valve 19b. The valve 19b is provided on the pipe 18b. Tubing 18b has a first end connected to source 21b. A first end of the pipe 18b communicates with the supply source 21b. The pipe 18b has a second end connected to the blowout portion 23 . A second end of the pipe 18 b communicates with the blowout portion 23 . When the valve 19b opens, the supply unit 17b supplies ammonia gas to the housing 12 through the blowout unit 23. As shown in FIG. When the valve 19b is closed, the supply part 17b does not supply the ammonia gas to the housing 12.

The supply unit 17c includes a pipe 18c and a valve 19c. The valve 19c is provided on the pipe 18c. Tubing 18c has a first end connected to source 21c. A first end of the pipe 18c communicates with the supply source 21c. The pipe 18c has a second end connected to the blowout portion 23 . A second end of the pipe 18 c communicates with the blowout portion 23 . When the valve 19c is opened, the supply section 17c supplies dry gas to the housing 12 through the blowout section 23. As shown in FIG. The supply 17c does not supply dry gas to the housing 12 when the valve 19c is closed.

The processing unit 11 has an exhaust section 25 . The exhaust part 25 is connected to the housing 12 . The exhaust part 25 communicates with the housing 12 . The exhaust unit 25 exhausts the gas inside the housing 12 to the outside of the housing 12 . The exhaust unit 25 exhausts the gas in the processing space 13 to the outside of the housing 12 .

The exhaust part 25 can adjust the pressure of the gas inside the housing 12 . The exhaust part 25 can reduce the pressure of the gas inside the housing 12 .

The processing unit 11 has one suction part 28 . The suction section 28 is connected to the exhaust section 25 . The suction portion 28 communicates with the exhaust portion 25 . The exhaust part 25 sucks the gas inside the housing 12 through the suction part 28 .

The suction part 28 is arranged at a position lower than the blowout part 23, for example. The suction part 28 is attached to the side of the housing 12, for example. Alternatively, suction portion 28 may be attached to the bottom of housing 12 .

The exhaust unit 25 is connected to processing equipment (not shown). The exhaust section 25 communicates with the processing equipment. The treatment facility treats the gas. The treatment equipment decomposes ammonia gas contained in the gas, for example. The treatment facility, for example, excludes ammonia gas from the gas. The processing equipment is not an element of substrate processing apparatus 1 . The processing equipment is, for example, utility equipment installed outside the substrate processing apparatus 1 .

The arrangement and configuration of the exhaust section 25 will be explained. At least part of the exhaust unit 25 is arranged outside the housing 12 .

The exhaust section 25 includes a pipe 26 and a vacuum pump 27 . A vacuum pump 27 is provided in the pipe 26 . Tubing 26 has a first end connected to housing 12 . A first end of the pipe 26 communicates with the housing 12 . Piping 26 has a second end connected to a processing facility. A second end of tubing 26 communicates with a processing facility. The exhaust unit 25 exhausts gas from the housing 12 when the vacuum pump 27 operates.

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

At least part of the temperature control unit 31 is preferably arranged inside the housing 12 .

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

A configuration example of the cooling unit 32 will be described. The cooling unit 32 includes cooling pipes 33 . At least part of the cooling pipe 33 is installed inside the housing 12 . A cooling pipe 33 is attached to the stage 15 . The cooling pipe 33 is arranged inside the stage 15, for example. The cooling pipe 33 also extends outside the housing 12 . The cooling pipe 33 is connected to the coolant supply section 34 . The cooling pipe 33 communicates with the coolant supply section 34 . The coolant supply unit 34 is provided outside the housing 12 . A coolant supply unit 34 sends coolant to the cooling pipe 33 . The coolant supply unit 34 includes, for example, a pump (not shown). A coolant flows through the cooling pipe 33 . Furthermore, the coolant supply section 34 may receive coolant from the cooling pipe 33 . In other words, the coolant may circulate between the coolant supply 34 and the cooling pipes 33 . When the coolant flows through the cooling pipe 33 , the coolant takes heat from the substrate W supported by the stage 15 . The cooling unit 32 cools the substrate W placed on the stage 15 when the coolant flows through the cooling pipe 33 . The coolant is liquid nitrogen, for example.

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

A configuration example of the heating unit 36 will be described. The heating section 36 includes an electric heater 37 and a power source 38 . The electric heater 37 is installed inside the housing 12 . An electric heater 37 is attached to the stage 15 . The electric heater 37 is arranged inside the stage 15, for example. The electric heater 37 includes, for example, a heating wire. A power supply 38 is electrically connected to the electric heater 37 . A power supply 38 is provided outside the housing 12 . A 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 heats the substrate W supported by the stage 15 . When the power supply 38 supplies power to the electric heater 37 , the heating section 36 heats the substrate W supported by the stage 15 .

The processing unit 11 includes an electron emitting section 41 . The electron emission section 41 emits electrons into the housing 12 . The electron emitter 41 emits electrons to the substrate W placed on the stage 15 .

At least a part of the electron emitting section 41 may be arranged inside the housing 12, for example. Alternatively, the entire electron emitting section 41 may be arranged outside the housing 12 .

A configuration example of the electron emission unit 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 material of the filament is tungsten, for example. At least part of the electron beam source 42 may be installed within the housing 12 . The electron beam source 42 may be provided, for example, 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 arranged at a position higher than the stage 15, for example. A power supply 43 is electrically connected to the electron beam source 42 . The power supply 43 is provided outside the housing 12 . A power supply 43 supplies power to the electron beam source 42 . When power supply 43 powers electron beam source 42 , electron beam source 42 emits electrons into process space 13 .

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

At least part of the collection unit 45 is preferably arranged inside the housing 12 .

A configuration example of the collection unit 45 will be described. The collection unit 45 includes electrodes 46 and a power source 47 . The electrodes 46 are preferably installed inside the housing 12, for example. The electrode 46 is arranged above the stage 15, for example. Electrode 46 is, for example, metal covered with an insulator. A power supply 47 is electrically connected to the electrode 46 . The power supply 47 is provided outside the housing 12 . A power supply 47 applies a voltage to the electrodes 46 . Power supply 47 applies a positive voltage to electrode 46 . When power supply 47 applies a positive voltage to electrode 46, electrode 46 attracts negatively charged particles.

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

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

The stage 15 is an example of the substrate mounting part of the present invention.

The supply unit 17a is an example of the first supply unit of the present invention. Water vapor is an example of the first process gas in the present invention. The supply section 17b is an example of the second supply section of the present invention. Ammonia gas is an example of the second process gas in the present invention.

The supply section 17c and the exhaust section 25 are examples of the pressure adjustment section of the present invention.

Hereinafter, when the supply section 17c and the exhaust section 25 are not distinguished from each other, they are appropriately referred to as the "pressure adjustment section 20".

See Figure 2. The control unit 10 controls the

supply units

17a and 17b. The control unit 10 controls the valves 19a and 19b.

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

The control unit 10 controls the temperature adjustment unit 31. The control section 10 controls the cooling section 32 and the heating section 36 . The control unit 10 controls the coolant supply unit 34 and the power supply 38 .

The control unit 10 controls the electron emission unit 41 . The control unit 10 controls the power supply 43 .

The control unit 10 controls the collection unit 45. The control unit 10 controls the power supply 47 .

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 .

<3. Example of Operation of Processing Unit 11>
FIG. 4 is a flow chart showing the procedure of the substrate processing method. A substrate processing method for processing a substrate W includes steps S1-S11. Steps S 1 -S 11 are substantially performed by processing unit 11 . The processing unit 11 operates under the control of the control section 10 .

Step S<b>1 : Mounting Process As described above, the substrate W is mounted on the stage 15 by the transport mechanism 8 . The substrate W is placed in a substantially horizontal posture within the housing 12 .

FIG. 5 is a diagram schematically showing the upper surface of the substrate W in the mounting process. The substrate W has a pattern R. The pattern R is formed on the upper surface W1 of the substrate W. As shown in FIG. The pattern R is positioned on the upper surface W1 of the substrate W when the substrate W is placed on the stage 15 . When the substrate W is placed on the stage 15, the pattern R faces upward.

The pattern R has a convex portion W2 and a concave portion A. The protrusion W2 is part of the substrate W. As shown in FIG. The protrusion W2 is a structure. The protrusion W2 is composed 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 concave portion A is arranged on the side of the convex portion W2. The concave portion A contacts the convex portion W2. The convex portion W2 corresponds to a wall that partitions the concave portion A. As shown in FIG.

Furthermore, in FIG. 5, particles (foreign matter) B are shown. The particles B adhere to the upper surface W1 of the substrate W. As shown in FIG.

The upper surface W1 of the substrate W is in contact with the gas G inside the housing 12.

In the mounting process, the substrate W does not come into contact with the liquid. In the mounting step, the substrate W is not wet.

Here, the interface between the gas G and the liquid is appropriately called the gas-liquid interface. In the mounting step, the substrate W does not come into contact with the gas-liquid interface. In the first place, no gas-liquid interface occurs in the mounting process.

The pressure sensor 51 detects the pressure of the gas G inside the housing 12 . The control unit 10 monitors detection results of the pressure sensor 51 .

In the placing process, the pressure of the gas G inside the housing 12 is normal pressure. Here, normal pressure includes standard atmospheric pressure (1 atm, 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. Pressure is indicated herein in terms of absolute pressure relative to absolute vacuum.

A 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 .

In the mounting process, the substrate W on the stage 15 is at room temperature, for example. Here, normal temperature includes room temperature. Normal temperature is, for example, a temperature within the range of 5° C. or higher and 35° C. or lower. Normal temperature is, for example, a temperature within the range of 10° C. or higher and 30° C. or lower.

The substrate W stands still on the stage 15. The substrate W does not rotate. Steps S2-S9 are performed with the substrate W stationary. Steps S2-S11 are performed with the substrate W stationary.

Step S2: Sealing Step With the substrate W housed in the housing 12, the housing 12 is sealed. For example, the shutter 14 closes the substrate transfer port 12a.

For convenience, refer to Figure 5. The substrate W does not come into contact with the gas-liquid interface even in the sealing process.

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

Here, the terms "deposition" and "condensation" refer to the change from gas to solid without passing through liquid. On the other hand, "condensation" and "to condense" refer to a 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 difficult to condense.

For example, the first pressure P1 is less than the triple point pressure of water. The triple point pressure of water is about 611 Pa. When the pressure of the gas G in the housing 12 is lower than the triple point pressure of water, water vapor (gas phase water) is less likely to condense.

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

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 pressure of the gas G in the housing 12 is reduced by discharging the gas in the housing 12 using the exhaust unit 25 . 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 .

The first pressure P1 may be one value. The first pressure P1 may range between two values. The first pressure P1 is set in advance in the processing information held by the control section 10 .

Furthermore, in the adjustment process, the substrate W placed on the stage 15 is adjusted to the first temperature T1. The first temperature T1 is the temperature at which water vapor condenses under the first pressure P1. In other words, the first temperature T1 is the temperature at which water exists in solid phase under the first pressure P1.

For example, the first temperature T1 is lower than the triple point temperature of water. The temperature of the triple point of water is 0.01 degrees.

The first temperature T1 is lower than normal temperature. Therefore, the adjustment process cools the substrate W placed on the stage 15 . In the adjustment process, the substrate W placed on the stage 15 is cooled from room temperature to the first temperature T1.

Specifically, the control unit 10 adjusts the temperature of the substrate W placed on the stage 15 by controlling the temperature adjustment unit 31 . For example, the cooling unit 32 cools the substrate W placed on the stage 15 . When the controller 10 adjusts the temperature of the substrate W, the controller 10 may refer to the detection result of the temperature sensor 52 .

The first temperature T1 may be one value. The first temperature T1 may range between two values. The first temperature T1 is preset in the processing information held by the control unit 10 .

Steps S4 and S5 are executed while the pressure of the gas G in the housing 12 is kept at the first pressure P1 and the temperature of the substrate W placed on the stage 15 is kept at the first temperature T1. be.

Step S<b>4 : First supply step Water vapor is supplied to the housing 12 .

Specifically, the control unit 10 controls the supply unit 17a. Thereby, the supply unit 17 a supplies water vapor to the housing 12 .

For convenience, refer to Figure 5. A top surface W1 of the substrate W is in contact with the gas G inside the housing 12 . The gas G contains water vapor. Therefore, the upper surface W1 of the substrate W is in contact with water vapor.

"Water vapor is in the gas phase." That is, water vapor is not in liquid phase. Therefore, the gas G is in the gas phase also in the first supply step.

The liquid is not supplied to the substrate W in the first supply process.

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 the first place, no gas-liquid interface occurs in the first supply step.

Step S<b>5 : Condensation Process Water vapor condenses within the housing 12 .

Immediately after the water vapor is supplied to the housing 12, the water vapor begins to condense. Therefore, the period during which the sublimation process is performed may overlap at least part of the period during which the first supply process is performed.

FIG. 6 is a diagram schematically showing the upper surface W1 of the substrate W in the sublimation process. The water vapor is cooled in the housing 12 while the pressure of the gas G in the housing 12 is maintained at the first pressure P1. The water vapor is cooled by the substrate W. Through the substrate W, the water vapor is cooled. Water vapor in the vicinity of the substrate W is cooled to the first temperature T1.

The water vapor turns into the first solid film H without going through liquid. The first solid film H is formed on the upper surface W1 of the substrate W. As shown in FIG. A top surface W1 of the substrate W is in contact with the first solid film H. As shown in FIG.

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

In FIG. 6, the first solid film H is thinner than the height of the protrusion W2. Therefore, the upper surface W1 (convex portion W2) is in contact with both the first solid film H and the gas G. As shown in FIG.

6 illustrates the case where the thickness of the first solid film H is not uniform over the upper surface W1 of the substrate W. FIG. That is, FIG. 6 illustrates a case where the formation speed of the first solidified film H varies on the upper surface W1 of the substrate W. As shown in FIG. Variations in the formation speed of the first solidified film are caused by variations in the temperature of the substrate W over the upper surface W1 of the substrate W, for example. The formation speed of the first solidified film H may be uniform over the upper surface W1 of the substrate W.

The first solid film H gradually thickens.

FIG. 7 is a diagram schematically showing the upper surface W1 of the substrate W in the sublimation process. In FIG. 7, the first solid film H is thicker than the height of the protrusion W2.

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. As shown in FIG. A top surface W1 of the substrate W is in contact with the first solid film H. As shown in FIG. However, the upper surface W1 of the substrate W is not in contact with the gas G.

As is clear from FIGS. 6 and 7, when the water vapor transforms into the first solid film H, the upper surface W1 of the substrate W does not contact the liquid. The water vapor transforms into the first solid film H without the upper surface W1 of the substrate W contacting the gas-liquid interface. Therefore, in the condensation process, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface. In the first place, no gas-liquid interface occurs in the condensation process.

Even if the formation speed 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 condensation process.

Step S6: Melting step The first solid film H is melted.

In the melting process, the pressure of the gas G inside the housing 12 is adjusted to the second pressure P2. The second pressure P2 is a pressure at which the first solid film H can be melted.

Here, "melting" and "melting" refer to changing from a solid to a liquid. On the other hand, "sublimation" and "sublimate" refer to changing from a solid to a gas without going through a liquid. When the pressure of the gas G inside the housing 12 is the second pressure P2, the first solid film H is difficult to sublimate.

For example, the second pressure P2 is greater than the triple point pressure of water. When the pressure of the gas G in the housing 12 is higher than the triple point pressure of water, ice (solid-phase water) is difficult to sublimate.

For example, the second pressure P2 is lower than normal pressure. For example, the second pressure P2 is lower than standard atmospheric pressure.

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.

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 to increase the pressure of the gas G in the housing 12 .

The second pressure P2 may be one value. The second pressure P2 may range between two values. The second pressure P2 is preset in the processing information held by the controller 10 .

Furthermore, the substrate W placed on the stage 15 is adjusted to the second temperature T2. Here, after the pressure of the gas G inside the housing 12 is adjusted to the second pressure P2, the substrate W placed on the stage 15 is preferably adjusted to the second temperature T2. 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 the liquid phase under the second pressure P2.

For example, the second temperature T2 is higher than the triple point temperature of water. For example, the second temperature T2 is substantially equal to room temperature.

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.

Specifically, the control unit 10 adjusts the temperature of the substrate W placed on the stage 15 by controlling the temperature adjustment unit 31 . For example, the heating unit 36 heats the substrate W placed on the stage 15 .

The second temperature T2 may be one value. The second temperature T2 may range between two values. The second temperature T2 is preset in the processing information held by the control unit 10 .

FIG. 8 is a diagram schematically showing the upper surface W1 of the substrate W in the melting process. 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. As shown in FIG. Through the substrate W, the first solid film H is heated. The first solid film H is heated to the second temperature T2.

The first solid film H turns into a liquid film J. A liquid film J is formed on the upper surface W1 of the substrate W. As shown in FIG. The upper surface W1 of the substrate W is in contact with the liquid film J. As shown in FIG.

The liquid film J is a liquid phase. The liquid film J is formed by the processing liquid. The treatment liquid forming the liquid film J is water.

In FIG. 8, part of the first solid film H turns into a liquid film J. The upper surface W1 of the substrate W is in contact with both the liquid film J and the first solid film H. However, the upper surface W1 of the substrate W is not in contact with the gas G. This is because the upper surface W1 of the substrate W is covered with the liquid film J and the first solid film H.

8 illustrates the case where the thickness of the liquid film J is not uniform over the upper surface W1 of the substrate W. FIG. That is, FIG. 8 illustrates a case where the formation speed of the liquid film J varies on the upper surface W1 of the substrate W. FIG. Variations in the formation speed of the liquid film J are caused by variations in the temperature of the substrate W over the upper surface W1 of the substrate W, for example. The formation speed of the liquid film J may be uniform over the upper surface W1 of the substrate W.

The first solid film H gradually decreases. The liquid film J gradually increases.

FIG. 9 is a diagram schematically showing the upper surface W1 of the substrate W in the melting process. 9, the entire first solid film H is transformed into a liquid film J. In FIG.

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. As shown in FIG. The upper surface W1 of the substrate W is in contact with the liquid film J. As shown in FIG. However, the upper surface W1 of the substrate W is not in contact with the gas G.

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

Even if the formation speed 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 process.

Step S<b>7 : Second supply step Ammonia gas is supplied to the housing 12 .

Specifically, the control unit 10 controls the supply unit 17b. Thereby, the supply unit 17b supplies ammonia gas to the housing 12 .

FIG. 10 is a diagram schematically showing the upper surface W1 of the substrate W in the second supply step. The gas G contains ammonia gas. Ammonia gas is in the gas phase. That is, ammonia gas is not in liquid phase. Also in the second supply step, the gas G is in the gas phase.

The liquid is not supplied to the substrate W in the second supply process.

The upper surface W1 of the substrate W does not come into contact with the gas G. This is because the upper surface W1 of the substrate W is covered with the liquid film J. FIG. The upper surface W1 of the substrate W is not in contact with the gas-liquid interface K between the liquid film J and the gas G in the second supply step as well.

The liquid film J is in contact with the gas G. The liquid film J is in 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 aqueous ammonia. Ammonia water is also called ammonium hydroxide.

After the liquid film J dissolves the ammonia gas, the liquid film J becomes alkaline. The upper surface W1 of the substrate W is in contact with the alkaline liquid film J. As shown in FIG. Therefore, the upper surface W1 of the substrate W has a negative zeta potential. Similarly, the particles B come into contact with the alkaline liquid film J. Therefore, particle B has a negative zeta potential. The zeta potential of the particles B has the same polarity as the zeta potential of the upper surface W1 of the substrate W. FIG. Therefore, the upper surface W1 and the particles B repel each other. The particle B leaves the upper surface W1. The particles B are liberated in the liquid film J. Furthermore, after the particles B have separated from the upper surface W1, the particles B are less likely to reattach to the upper surface W1. Thus, the liquid film J separates the particles B from the upper surface W1.

Step S8: Solidification step The liquid film J is solidified.

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

Here, "freezing" and "solidifying" refer to changing from a liquid to a solid. "Vaporization" and "vaporize," on the other hand, are the 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 difficult to evaporate.

For example, the third pressure P3 is greater than the triple point pressure of water. When the pressure of the gas G in the housing 12 is higher than the pressure at the triple point of water, water (liquid phase water) is difficult to evaporate.

For example, the third pressure P3 is lower than normal pressure. For example, the third pressure P3 is lower than standard atmospheric pressure.

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

The solidification process adjusts the pressure of the gas G inside the housing 12 from the second pressure P2 to the third pressure P3.

Specifically, the control unit 10 adjusts the pressure of the gas G in the housing 12 by controlling the pressure adjustment unit 20 .

The third pressure P3 may be one value. The third pressure P3 may range between two values. The third pressure P3 is preset in the processing information held by the controller 10 .

Furthermore, the substrate W placed on the stage 15 is adjusted to the 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.

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

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 step cools the substrate W placed on the stage 15 from the second temperature T2 to the third temperature T3.

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 .

The third temperature T3 may be one value. The third temperature T3 may range between the two values. The third temperature T3 is preset in the processing information held by the control unit 10 .

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

The liquid film J changes to the second solid film L. The second solid film L is formed on the upper surface W1 of the substrate W. As shown in FIG. A top surface W1 of the substrate W is in contact with the second solid film L. As shown in FIG.

The second solid film L is a solid phase.

In FIG. 11, part of the liquid film J changes to the second solid film L. The upper surface W1 of the substrate W is in contact with both the liquid film J and the second solid film L. As shown in FIG. However, the upper surface W1 of the substrate W is not in contact with the gas G. This is because the upper surface W1 of the substrate W is covered with the liquid film J and the second solid film L.

11 illustrates the case where the thickness of the second solid film L is not uniform over the upper surface W1 of the substrate W. FIG. That is, FIG. 11 exemplifies a case where the formation speed of the second solid film L varies on the upper surface W1 of the substrate W. As shown in FIG. Variations in the formation speed of the second solid film L are caused by variations in the temperature of the substrate W over the upper surface W1 of the substrate W, for example. The formation speed of the second solid film L may be uniform over the upper surface W1 of the substrate W.

The liquid film J gradually decreases. The second solid film L gradually increases.

FIG. 12 is a diagram schematically showing the upper surface W1 of the substrate W in the solidification process. 12, the entire liquid film J is transformed into the second solid film L. In FIG.

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. As shown in FIG. A top surface W1 of the substrate W is in contact with the second solid film L. As shown in FIG. However, the upper surface W1 of the substrate W is not in contact with the gas G.

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 particle B also disappears.

As is clear from FIGS. 11 and 12, when the liquid film J changes to the second solid film L, a gas-liquid interface K occurs. When the liquid film J changes to the second solid film L, a gas-liquid interface K exists. A gas-liquid interface K is located between the liquid film J and the gas G. FIG. However, the upper surface W1 of the substrate W is not in 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, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the solidification step. When the liquid film J disappears, the gas-liquid interface K disappears.

Even if the formation speed 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 process.

Step S9: Charging Step The second solid film L is charged.

Specifically, the control unit 10 controls the electron emission unit 41 . Thereby, the electron emitting section 41 emits electrons toward the second solid film L. As shown in FIG.

FIG. 13 is a diagram schematically showing the upper surface W1 of the substrate W in the charging process. The electron emitter 41 emits electrons M. As shown in FIG. The second solid film L receives electrons M. Therefore, the second solid film L is negatively charged. The electrons M are distributed on the upper surface L1 of the second solid film L. As shown in FIG. Therefore, the upper surface L1 of the second solid film L is negatively charged.

Step S10: Sublimation Step The second solid film L is sublimated.

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

As mentioned above, "sublimation" and "sublimation" refer to changing from a solid to a gas without passing through a liquid. "Melting" and "melting", on the other hand, is the change from a solid to a liquid. When the pressure of the gas G inside the housing 12 is the fourth pressure P4, the second solid film L is difficult to melt.

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

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

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 . A sublimation process reduces the pressure of the gas G of the housing|casing 12 from the 3rd pressure P3 to the 4th pressure P4.

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 part 25 reduces the pressure of the gas G in the housing 12 .

The fourth pressure P4 may be one value. The fourth pressure P4 may range between two values. The fourth pressure P4 is preset in the processing information held by the controller 10 .

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

Specifically, the exhaust unit 25 reduces the pressure of the gas G in the housing 12 and discharges the gas in the housing 12 to the outside of the housing 12 .

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

For example, the fourth temperature T4 is higher than the triple point temperature of water. For example, the fourth temperature T4 is substantially equal to room temperature.

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 . A sublimation process heats the board|substrate W mounted in the stage 15 from 3rd temperature T3 to 4th temperature T4.

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 .

The fourth temperature T4 may be one value. The fourth temperature T4 may range between the two values. The fourth temperature T4 is preset in the processing information held by the controller 10 .

FIG. 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 the fourth pressure P4. The second solid film L is heated by the substrate W. As shown in FIG. The second solid film L is heated through the substrate W. The second solid film L is heated to a fourth temperature T4.

The second solid film L turns into gas without passing through liquid. The gas that has changed from the second solid film L is in the gas phase. The gas G includes gas that has changed from the second solid film L. As shown in FIG. The exhaust part 25 exhausts the gas G to the outside of the housing 12 .

The upper surface L1 of the second solid film L is lowered. The upper surface L1 of the second solid film L is lowered while the upper surface L1 of the second solid film L remains negatively charged. When the upper surface L1 of the second solid film L is lowered to the same height position as the particles B, the particles B are negatively charged. In other words, when the particles B are exposed on the upper surface L1 of the second solid film L, the particles B are negatively charged. When the particles B are negatively charged, the particles B and the upper surface L1 of the second solid film L repel each other. Therefore, the particles B are easily separated from the second solid film L. The particles B, for example, fly from the second solid film L into the gas G inside the housing 12 .

In FIG. 14, part of the second solid film L is sublimated. The upper surface W1 of the substrate W is in contact with at least one of the second solid film L and the gas G. As shown in FIG. For example, the upper surface W1 of the substrate W is in contact with both the second solid film L and the gas G. However, the upper surface W1 of the substrate W does not contact the liquid.

14 illustrates the case where the thickness of the second solid film L is not uniform over the upper surface W1 of the substrate W. FIG. That is, FIG. 14 exemplifies a case where the sublimation speed of the second solid film L varies on the upper surface W1 of the substrate W. As shown in FIG. Variations in the sublimation rate of the second solid film L are caused by variations in the temperature of the substrate W over the upper surface W1 of the substrate W, for example. The sublimation rate of the second solid film L may be uniform over the upper surface W1 of the substrate W.

FIG. 15 is a diagram schematically showing the upper surface W1 of the substrate W in the sublimation process. In FIG. 15, the entire second solid film L is sublimated.

The second solid film L is removed from the substrate W without the second solid film L changing into liquid. The substrate W is dried without the second solid film L changing to liquid.

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

As is clear from FIGS. 14 and 15, when the second solid film L turns into gas, the upper surface W1 of the substrate W does not contact the liquid. The upper surface W1 of the substrate W does not contact the gas-liquid interface K, and the second solid film L sublimates. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the sublimation process. In the first place, the gas-liquid interface K does not occur in the sublimation process.

Even if the sublimation speed 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 contact the gas-liquid interface K in the sublimation process.

Step S11: Collection Step The collection unit 45 collects the charged particles B. FIG.

The collection step is preferably performed in parallel with the sublimation step. The period during which the collection step is performed preferably overlaps at least part of the period during which the sublimation step is performed. For example, the collection process begins at the same time as the sublimation process.

Specifically, the control unit 10 controls the collection unit 45 . Electrode 46 thus has a positive potential.

See Figure 14. The electrode 46 attracts the charged particles B. The electrode 46 attracts the particles B exposed from the second solid film L. Particle B moves toward electrode B. Particle B moves upward, for example.

See Figure 15. All particles B contained in the second solid film L are collected by the electrode 46 . All the particles B contained in the second solid film L are removed from the substrate W.

<4. Effect of Embodiment>
The substrate processing method includes a placing step. In the mounting step, the substrate W is mounted in a substantially horizontal posture within the housing 12 . In the mounting step, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. As shown in FIG.

The substrate processing method includes a first supply step. The first supply step supplies water vapor to the housing 12 . In the first supply step, the upper surface W1 of the substrate W is in contact with water vapor. Water vapor is in the gas phase. That is, water vapor is not in liquid phase. The first supply step does not supply the substrate W with liquid. Therefore, in the first supply step, the upper surface W1 of the substrate W does not contact the liquid. Therefore, the upper surface W1 of the substrate W does not contact the gas-liquid interface K in the first supply step.

The substrate processing method includes a sublimation process. In the condensation process, water vapor condenses within the housing 12 . Thereby, the coagulation process forms the first solid film H. As shown in FIG. The first solid film H covers the upper surface W1 of the substrate W. As shown in FIG. In the condensation process, water vapor transforms into the first solid film H without passing through liquid. The upper surface W1 of the substrate W is in contact with the first solid film H in the condensation process. The first solid film H is a solid phase. That is, the first solid film H is not in liquid phase. Therefore, when the water vapor transforms into the first solid film H, the upper surface W1 of the substrate W does not contact the liquid. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K, and the water vapor condenses (changes) into the first solid film H. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the condensation process.

The substrate processing method includes a melting step. In the melting step, the first solid film H is melted. Thus, the melting step forms a liquid film J. FIG. The liquid film J covers the upper surface W1 of the substrate W. As shown in FIG. The first solid film H transforms into a liquid film J in the melting process. The upper surface W1 of the substrate W is in contact with the liquid film J in the melting process. The liquid film J is a liquid phase. As described above, the first solid film H formed in the condensation process covers the upper surface W1 of the substrate W. As shown in FIG. Therefore, when the first solid film H changes to the liquid film J, the upper surface W1 of the substrate W does not come into contact with the gas G. As shown in FIG. Therefore, the first solid film H melts into the liquid film J without the upper surface W1 of the substrate W coming into contact with the gas-liquid interface K. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the melting process.

In summary, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the mounting process, the first supply process, the condensation process, and the melting process. Therefore, the surface tension of the liquid film J does not act on the upper surface W1 of the substrate W substantially. 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.

It should be noted that in the conventional technology in which the nozzle discharges the processing liquid onto the upper surface W1 of the substrate W, the substrate W comes into contact with the gas-liquid interface K when the upper surface W1 of the substrate W starts to come into contact with the processing liquid. That is, in the conventional technology, there is a moment when the substrate W comes into contact with the gas-liquid interface K. At this moment, the surface tension of the processing liquid acts on the upper surface W1 of the substrate W. As shown in FIG. Therefore, in the prior art, the upper surface W1 of the substrate W is subjected to relatively large forces.

In the substrate processing method, water vapor is condensed to form a first solid film H covering the upper surface W1 of the substrate W, and then the first solid film H is melted to form a liquid film J covering the upper surface W1 of the substrate W. . Therefore, overflow of the processing liquid from the substrate W can be suitably suppressed. The amount of processing liquid overflowing from the substrate W is preferably reduced. That is, it is possible to suitably suppress the loss of the treatment 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 relatively little 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 the conventional method.

The condensation process maintains the pressure of the gas G inside the housing 12 at a first pressure P1 at which water vapor can condense. Therefore, the condensation process can suitably suppress the condensation of water vapor.

The condensation process cools the water vapor. For this reason, in the sublimation process, water vapor is suitably condensed.

In the melting process, the pressure of the gas G inside the housing 12 is kept at the second pressure P2 at which the first solid film H can be melted. Therefore, the sublimation of the first solid film H can be suitably suppressed in the melting step.

The melting step heats the first solid film H. Therefore, in the melting step, the first solid film H is preferably melted.

The sublimation process cools the substrate W. Thus, the condensation process cools the water vapor through the substrate W. FIG. In the condensation process, the upper surface W1 of the substrate W is in contact with water vapor. Therefore, the water vapor is efficiently cooled. Therefore, the condensation process can form the first solid film H efficiently.

The condensation process cools the substrate W to a first temperature T1 at which water vapor condenses onto the upper surface W1 of the substrate W. Therefore, in the condensation process, water vapor can be suitably condensed (changed) into the first solid film H. In the condensation step, the water vapor is favorably condensed on the first solid film H.

The melting process heats the substrate W. Therefore, the melting step heats the first solid film H through the substrate W. FIG. The upper surface W1 of the substrate W is in contact with the first solid film H in the melting process. Therefore, the first solid film H is efficiently heated. Therefore, the melting process can form the liquid film J efficiently.

The melting step heats the substrate W to the second temperature T2 at which the first solid film H melts. Therefore, the melting step can suitably melt the first solid film H into the liquid film J. FIG.

In the condensation process, the pressure of the gas G inside the housing 12 is lower than the triple point pressure of water. Therefore, in the condensation process, condensation of water vapor can be suitably suppressed.

In the melting process, the pressure of the gas G inside the housing 12 is higher than the triple point pressure of water. Therefore, in the melting step, sublimation of the first solid film H can be suitably suppressed.

The substrate processing method includes an adjustment process. The adjusting step adjusts the pressure of the gas G inside the housing 12 to the first pressure P1. The adjusting step adjusts the temperature of the substrate W to the first temperature T1. The conditioning step is performed before the condensation step. Therefore, the sublimation process can be started smoothly. Therefore, the time required for the substrate processing method can be shortened.

The adjustment process is executed before the first supply process. Therefore, the condensation step can be started immediately after the first supply step is started. Therefore, the time required for the substrate processing method can be further shortened.

The substrate processing method includes a solidification step. In the solidification step, the liquid film J is solidified. Thereby, the solidification step forms the second solid film L. As shown in FIG. A second solid film L is formed on the upper surface W1 of the substrate W. As shown in FIG. The liquid film J transforms into a second solid film L in the solidification process. The upper surface W1 of the substrate W is in contact with the second solid film L in the solidification step. The second solid film L is a solid phase. As described above, the liquid film J formed in the melting process covers the upper surface W1 of the substrate W. As shown in FIG. Therefore, when the liquid film J changes to the second solid film L, the upper surface W1 of the substrate W does not come into contact with the gas G. FIG. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K, and the liquid film J solidifies. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the solidification process.

The substrate processing method includes a sublimation process. In the sublimation step, the second solid film L is sublimated. In the sublimation process, the second solid film L changes into a gas phase without going through a liquid state. Therefore, when the second solid film L sublimates, the upper surface W1 of the substrate W does not contact the liquid. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K, and the second solid film L sublimates. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the sublimation process.

The second solid film leaves from the substrate W as the second solid film L sublimes. The substrate W is dried by the sublimation of the second solid film L.

In summary, the upper surface W1 of the substrate W does not contact the gas-liquid interface K in the solidification process and the sublimation process. Therefore, according to the substrate processing method, the substrate W can be dried while the upper surface W1 of the substrate W is properly protected. Therefore, the substrate processing method can process the substrate W more appropriately.

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

The solidification process cools the liquid film J. Therefore, in the solidification step, the liquid film J is suitably solidified.

In the sublimation process, 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, the melting of the second solid film L can be suitably suppressed in the sublimation process.

The sublimation process heats the second solid film L. Therefore, in the sublimation step, the second solid film L sublimates favorably.

The solidification process cools the substrate W. Thus, the solidification step cools the liquid film J through the substrate W. FIG. The upper surface W1 of the substrate W is in contact with the liquid film J in the solidification process. Therefore, the liquid film J is efficiently cooled. Therefore, the solidification step can form the second solid film L efficiently.

The solidification step cools the substrate W to the third temperature T3 at which the liquid film J solidifies. Therefore, the solidification process can solidify the liquid film J suitably.

The substrate W is heated in the sublimation process. Therefore, the second solid film L is heated through the substrate W in the sublimation process. The upper surface W1 of the substrate W is in contact with the second solid film L in the sublimation process. Therefore, the second solid film L is efficiently heated. Therefore, the sublimation process can sublimate the second solid film L efficiently.

In the sublimation process, the substrate W is heated to the fourth temperature T4 at which the second solid film L sublimes. Therefore, the sublimation process can sublimate the second solid film L favorably.

The sublimation process discharges the gas G inside the housing 12 to the outside of the housing 12 . Therefore, in the sublimation step, the second solid film L sublimates more favorably. The second solid film L can be more preferably removed from the substrate W in the sublimation step.

In the solidification process, the pressure of the gas G inside the housing 12 is higher than the triple point pressure of water. Therefore, in the solidification step, evaporation of the liquid film J can be suitably suppressed.

In the sublimation process, the pressure of the gas G inside the housing 12 is lower than the triple point pressure of water. Therefore, in the sublimation process, the melting of the second solid film L can be suitably suppressed.

The substrate processing method includes a second supply step. A 2nd supply process supplies ammonia gas. Ammonia gas is in the gas phase. Therefore, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K in the second supply step. Therefore, in the second supply step, the ammonia gas can be supplied to the housing 12 while the upper surface W1 of the substrate W is properly protected.

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

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

In the charging process, the second solid film L is negatively charged. Therefore, the particle B is also negatively charged. Therefore, electrostatic repulsion is generated between the negatively charged second solid film L and the negatively charged particles B. FIG. Therefore, particles B can be preferably removed.

The substrate processing method includes a collection step. The collecting step collects the charged particles B. FIG. Therefore, the collecting step can preferably remove the charged particles B from the substrate W. FIG.

The substrate W has a pattern R. The pattern R is formed on the upper surface W1 of the substrate W. As shown in FIG. 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. FIG. 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 the processing liquid to the pattern R while suitably suppressing the pattern R from collapsing. For example, the substrate processing method can suitably prevent the pattern R from collapsing and supply the processing liquid to the pattern R. For example, the substrate processing method can supply the processing liquid to the pattern R while suitably suppressing collapse of the protrusions W2. For example, the substrate processing method can supply the processing liquid to the pattern R while suitably preventing the protrusion W2 from collapsing.

The substrate processing apparatus 1 includes a housing 12 and a pressure adjustment section 20. The pressure adjuster 20 adjusts the pressure of the gas G inside the housing 12 . The housing 12 can be sealed. Therefore, the pressure adjustment unit 20 can adjust the pressure of the gas G inside the housing 12 appropriately.

The substrate processing apparatus 1 includes a stage 15, a supply section 17a, a temperature adjustment section 31, and a control section 10. The stage 15 is installed inside the housing 12 . A stage 15 supports the substrate W. FIG. The stage 15 mounts the substrate W in a substantially horizontal posture. The supply unit 17 a supplies water vapor into the housing 12 . The temperature adjuster 31 adjusts the temperature of the substrate W placed on the stage 15 . The control unit 10 controls the supply unit 17 a, the pressure adjustment unit 20 and the temperature adjustment unit 31 . Specifically, the control unit 10 controls the supply unit 17 a , the supply unit 17 c , the exhaust unit 25 and the temperature adjustment unit 31 .

The control unit 10 supplies water vapor to the housing 12 from the supply unit 17a. When the supply unit 17a supplies water vapor to the housing 12, the upper surface W1 of the substrate W does not contact the gas-liquid interface K. As shown in FIG.

The control unit 10 condenses water vapor by controlling the pressure adjustment unit 20 and the temperature adjustment unit 31 to form the first solid film H covering the upper surface W1 of the substrate W placed on the stage 15 . Therefore, when the water vapor transforms into the first solid film H, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. FIG.

The control unit 10 melts the first solid film H by controlling the pressure adjustment unit 20 and the temperature adjustment unit 31 to form a liquid film J covering the upper surface W1 of the substrate W placed on the stage 15. . Therefore, when the first solid film H changes to the liquid film J, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. FIG.

In summary, the control unit 10 controls the supply unit 17a, the pressure adjustment unit 20, and the temperature adjustment unit 31 so as to supply water vapor to the housing 12, condense the water vapor, and melt the first solid film H. do. Therefore, the substrate processing apparatus 1 can form the 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.

The substrate processing apparatus 1 forms the first solid film H covering the upper surface W1 of the substrate W by condensing water vapor. The substrate processing apparatus 1 melts the first solid film H to form a liquid film J covering the upper surface W1 of the substrate W. As shown in FIG. Therefore, overflow of the processing liquid from the substrate W can be suitably suppressed. The amount of processing liquid overflowing from the substrate W is preferably reduced. That is, it is possible to suitably suppress the loss of the treatment 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 amount of processing liquid used in the substrate processing apparatus 1 is relatively small. For example, the amount of processing liquid used in the substrate processing apparatus 1 is less than the amount of processing liquid used in the conventional apparatus.

The control unit 10 solidifies the liquid film J by controlling the pressure adjustment unit 20 and the temperature adjustment unit 31 to form the second solid film L on the upper surface W1 of the substrate W placed on the stage 15. . Therefore, when the liquid film J changes to the second solid film L, the upper surface W1 of the substrate W does not come into contact with the gas-liquid interface K. FIG.

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

In summary, the control unit 10 controls the pressure adjustment unit 20 and the temperature adjustment unit 31 so that the liquid film J is solidified and the second solid film L is sublimated. Therefore, the substrate processing apparatus 1 can remove the liquid film J 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. 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. FIG. Therefore, the substrate processing apparatus 1 can process the substrate W more appropriately.

The substrate processing apparatus 1 includes a supply section 17b. The supply unit 17b supplies the housing 12 with ammonia gas. The control unit 10 supplies the ammonia gas into the housing 12 and causes the liquid film J to dissolve the ammonia gas by controlling the supply unit 17b. Thus, 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. FIG. The substrate processing apparatus 1 can adjust the composition 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. FIG.

The temperature adjustment unit 31 is attached to the stage 15. Therefore, the temperature adjuster 31 can suitably adjust the temperature of the substrate W placed on the stage 15 .

The substrate processing apparatus 1 includes an electron emitting section 41 . The electron emitter 41 emits electrons into the housing 12 . Therefore, the second solid film L can be suitably charged.

The substrate processing apparatus 1 includes electrodes 46 . Electrode 46 is installed within housing 12 . A positive voltage is applied to the electrode 46 . Therefore, the electrode 46 can preferably collect the negatively charged particles B. FIG.

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

(1) In the embodiment, one kind of gas (water vapor) was condensed in the condensation process. In embodiments, the condensation process condensed a gas consisting of one component (water vapor). However, it is not limited to this. For example, in the condensation process, multiple types of gases may be condensed. For example, in a sublimation process, a gas containing multiple components may be sublimated. For example, in the sublimation step, at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas may be sublimated. According to this modified embodiment, the 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.

For example, according to the liquid film J derived from water vapor, the substrate W can be rinsed. The substrate W can be cleaned by the liquid film J derived from at least one of ammonia gas, methylamine gas, dimethylamine gas, and trimethylamine gas. For example, the particles B can be preferably removed from the upper surface W1 of the substrate W by the liquid film J. The substrate W can be oxidized by the liquid film J derived from the hydrogen peroxide gas. For example, the upper surface W1 of the substrate W can be oxidized by the liquid film J.

When multiple types of gases condense, the multiple types of gases may condense at the same time. When multiple types of gases condense, the multiple types of gases do not have to condense at the same time. For example, if multiple gases are condensed, the multiple gases may be condensed in the same condensation process. Alternatively, each of the multiple gases may be sublimated in different sublimation processes.

Two modified embodiments will be described.

(1-1) FIG. 16 is a flow chart showing the procedure of the substrate processing method of the modified embodiment. The same steps as in the embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. The substrate processing method of the modified embodiment differs from the substrate processing method of the embodiment in steps S4-S6.

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 supplied to the housing 12 at the same time. Therefore, the gas G inside the housing 12 contains water vapor and ammonia gas.

Specifically, the supply unit 17a and the supply unit 17b may supply water vapor and ammonia gas to the housing 12, respectively. Alternatively, the configuration of the supply unit 17 a may be changed so as to supply a mixed gas of water vapor and ammonia gas to the housing 12 .

In the condensation step (step S5), water vapor and ammonia gas are condensed to form the first solid film H.

In the condensation process, the pressure of the gas G in the housing 12 is adjusted to the first pressure P1. In the condensation process, the substrate W placed on the stage 15 is adjusted to the first temperature T1. Here, the first pressure P1 and the first temperature T1 are appropriately selected and changed according to the type of gas to be condensed. The first pressure P1 and the first temperature T1 are appropriately selected and changed according to the components of the gas to be condensed. The first pressure P1 and the first temperature T1 are appropriately selected and changed according to the composition of the gas to be condensed. For example, the first pressure P1 is a pressure at which water vapor and ammonia gas can condense. For example, the first temperature T1 is the temperature at which water vapor and ammonia gas condense under the first pressure P1.

In the melting step (step S6), the first solid film H melts and becomes a liquid film J. The liquid film J is formed of a treatment liquid derived from water vapor and ammonia gas. That is, the liquid film J contains aqueous ammonia. Therefore, in the melting process, the liquid film J can be used to clean the substrate W. FIG. For example, the melting step can separate the particles B from the top surface W1 of the substrate W. FIG.

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

Similarly, the third pressure P3 and the third temperature T3 in the solidification process are also appropriately selected and changed according to the components of the liquid film J. The third pressure P3 and the third temperature T3 in the solidification step are also appropriately selected and changed according to the composition of the liquid film J. The fourth pressure P4 and the fourth temperature T4 in the sublimation step are also appropriately selected and changed according to the components of the second solid film L. The fourth pressure P4 and the fourth temperature T4 in the sublimation step are also appropriately selected and changed according to the composition of the second solid film L.

In this modified embodiment, the second supply step (step S7) may be omitted.

In this modified embodiment, the supply section 17a and the supply section 17b are examples of the first supply section of the present invention. Water vapor and ammonia gas are examples of the first process gas in the present invention.

(1-2) FIG. 17 is a flow chart showing the procedure of the substrate processing method of the modified embodiment. The same steps as in the embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. The substrate processing method of the modified embodiment differs from the substrate processing method of the embodiment in steps S4-S6.

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

In the first supply step of step S4a, water vapor is supplied to the housing 12.

In the condensation process of step S5a, water vapor condenses.

FIG. 18 is a diagram schematically showing the upper surface W1 of the substrate W in the solidification process of step S5a. The water vapor contained in the gas G inside the housing 12 changes to the first solid film Ha without passing through liquid.

　Ammonia gas is supplied to the housing 12 in the first supply step of step S4b.

After the condensation process of step S5a, the condensation process of step S5b is performed. In the condensation process of step S5b, the ammonia gas is condensed.

FIG. 19 is a diagram schematically showing the upper surface W1 of the substrate W in the condensation process of step S5b. The ammonia gas contained in the gas G inside the housing 12 changes to the first solid film Hb without passing through liquid. The first solid film Hb is laminated on the first solid film Ha. The entire top surface W1 of the substrate W is covered with the first solid film Ha and the first solid film Hb.

In this way, the water vapor condenses first. After the water vapor condenses, the ammonia gas condenses. Incidentally, the ammonia gas may be condensed first, and then the water vapor may be condensed.

In the melting step (step S6), the entire first solid film Ha and first solid film Hb are melted to form the liquid film J. The liquid film J is formed of a treatment liquid derived from water vapor and ammonia gas. That is, the liquid film J contains aqueous ammonia. Therefore, in the melting process, the liquid film J can be used to clean the substrate W. FIG. For example, the melting step can separate the particles B from the top surface W1 of the substrate W. FIG.

In this modified embodiment, the second supply step (step S7) may be omitted.

(2) In the embodiment, one type of gas (ammonia gas) was dissolved in the liquid film J in the second supply step. In the embodiment, gas composed of one component (ammonia gas) was dissolved in the liquid film J in the second supply step. However, it is not limited to this. For example, multiple types of gases may be dissolved in the liquid film J in the second supply step. For example, gas containing multiple components may be dissolved in the liquid film J in the second supply step. For example, at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas may dissolve in the liquid film J in the second supply step. According to this modified embodiment, the 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.

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 at the same time. When multiple types of gases are dissolved in the liquid film J, the multiple types of gases do not have to be dissolved in the liquid film J at the same time. 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, a plurality of types of gases may be dissolved in the liquid film J in different second supply steps.

Two modified embodiments will be described.

(2-1) FIG. 20 is a diagram showing the configuration of the processing unit 11 according to the modified embodiment. In addition, detailed description is abbreviate|omitted by attaching|subjecting the same code|symbol about the same structure as embodiment.

The processing unit 11 includes a supply section 17d in addition to the supply sections 17a to 17c. The supply portion 17d is also connected to the housing 12 . The supply portion 17 d also communicates with the housing 12 . The supply unit 17 d supplies gas to the housing 12 . The gas supplied by the supply unit 17d is hydrogen peroxide gas. Hydrogen peroxide gas is in the gas phase.

The supply unit 17d is connected to the supply source 21d. The supply portion 17d communicates with the supply source 21d. Supply source 21d delivers hydrogen peroxide gas to supply 17d. Supply source 21d may be an element of substrate processing apparatus 1 . The supply source 21 d may not be an element of the substrate processing apparatus 1 .

The supply unit 17d is connected to the blowout unit 23. The supply portion 17 d communicates with the blowout portion 23 .

The supply unit 17d includes a pipe 18d and a valve 19d. 19 d of valves are provided in 18 d of piping. The tubing 18d has a first end connected to the source 21d. A first end of the pipe 18d communicates with the supply source 21d. The pipe 18 d has a second end connected to the blowout portion 23 . A second end of the pipe 18 d communicates with the blowout portion 23 . When the valve 19 d is opened, the supply section 17 d supplies hydrogen peroxide gas to the housing 12 through the blowout section 23 . When the valve 19d is closed, the supply portion 17d does not supply hydrogen peroxide gas to the housing 12.

For convenience, refer to Figure 4. Note that detailed description 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.

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 supplied to the housing 12 at the same time. Therefore, the gas G inside the housing 12 contains ammonia gas and hydrogen peroxide gas.

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

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. Since the liquid film J contains ammonia water, the liquid film J can clean the substrate W. FIG. For example, the liquid film J can preferably remove the particles B from the upper surface W1 of the substrate W. FIG. Since the liquid film J contains the hydrogen peroxide solution, the liquid film J can oxidize the substrate W. As shown in FIG. For example, the liquid film J can oxidize the top surface W1 of the substrate W. FIG.

In this modified embodiment, the supply section 17b and the supply section 17d are examples of the second supply section of the present invention. Ammonia gas and hydrogen peroxide gas are examples of the second process gas in the present invention.

(2-2) FIG. 21 is a flow chart showing the procedure of the substrate processing method of the modified embodiment. The same steps as in the embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. The substrate processing method of the modified embodiment includes steps S7a and S7b instead of step S7.

In the second supply step of step S7a, hydrogen peroxide gas is supplied to the housing 12. In the second supply step of step S7a, the liquid film J melts the hydrogen peroxide gas. As a result, the liquid film J contains the hydrogen peroxide solution. Since the liquid film J contains the hydrogen peroxide solution, the liquid film J can oxidize the substrate W. As shown in FIG. For example, the liquid film J can oxidize the top surface W1 of the substrate W. FIG.

After the second supply process of step S7a, the second supply process of step S7b is performed. Ammonia gas is supplied to the housing 12 in the second supply step of step S7b. In the second supply step of step S7b, the liquid film J melts the ammonia gas. As a result, the liquid film J contains aqueous ammonia in addition to aqueous hydrogen peroxide. Since the liquid film J contains ammonia water, the liquid film J can further clean the substrate W. FIG. For example, the liquid film J can preferably remove the particles B from the upper surface W1 of the substrate W. FIG.

In this way, the hydrogen peroxide gas is dissolved in the liquid film J first. 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.

(3) The embodiment includes a second supply step. However, it is not limited to this. The second supply step may be omitted. For example, the second supply step may be omitted as in a modified embodiment shown in FIG. 16 or 17. FIG.

(4) In the embodiment, the adjustment process is executed before the first supply process. However, it is not limited to this. For example, the adjustment step may be performed after the first supply step. For example, the conditioning step may be performed after the first feeding step and before the sublimation step.

(5) In the embodiment, the substrate processing method includes an adjustment process. However, it is not limited to this. The adjustment process may be omitted. For example, either the first supply step or the sublimation step may perform an operation equivalent to the adjustment step. For example, in the first supply 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 process, 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.

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

(7) The embodiment includes a collection step. However, it is not limited to this. The collecting step may be omitted. For example, as shown in FIGS. 17 and 21, the substrate processing method may not include a collection step. A repulsive force can be generated between the negatively charged second solid film L and the negatively charged particles B only by the charging process. Therefore, the particles B can be scattered from the second solid film L. Therefore, the particles B can be preferably removed from the substrate W even if the collection step is omitted.

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

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

(10) In the embodiment, the supply unit 17a supplies one type of gas to the housing 12. In the embodiment, the supply part 17a supplied the gas consisting of one component to the housing 12 . However, it is not limited to this. For example, the supply unit 17a may supply a mixed gas containing two or more types of gases to the housing 12 . For example, the supply unit 17 a may supply a mixed gas containing multiple components to the housing 12 . For example, the supply unit 17 a may supply a mixed gas containing at least two of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas to the housing 12 . The supply portion 17b may also be changed in the same manner as the supply portion 17a.

(11) In the embodiment, the

supply units

17a, 17b, and 17c are all connected to the common blowout unit 23. The

supply parts

17a, 17b, 17c all communicated with a common blowout part 23. As shown in FIG. However, it is not limited to this. The

supply units

17a, 17b, and 17c may be connected to different blowout units, respectively. Each of the

supply portions

17a, 17b, and 17c may communicate with different blowout portions.

(12) In the embodiment, a specific configuration of the temperature adjustment section 31 is illustrated. For example, the temperature adjustment section 31 includes a cooling pipe 33 and an electric heater 37 . However, it is not limited to this. The configuration of the temperature adjustment unit 31 may be changed as appropriate. For example, the temperature adjuster 31 may include a Peltier element that generates heat and absorbs heat. For example, the temperature adjustment unit 31 may include thermoelectric elements that generate heat and absorb heat.

(13) In the embodiment, the substrate W has the pattern R formed on the upper surface W1 of the substrate W. However, it is not limited to this. For example, the substrate W may not have the pattern R. For example, the pattern R does not have to be formed on the upper surface W1 of the substrate W. FIG. For example, the substrate W may have a top surface W1 on which the pattern R is not formed. Also in these modified embodiments, the substrate processing method and the substrate processing apparatus 1 described above can form the liquid film J on the upper surface W1 of the substrate W while protecting the upper surface W1 of the substrate W. FIG. Therefore, also in these modified embodiments, the substrate W can be appropriately processed by the substrate processing method and the substrate processing apparatus 1 .

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

DESCRIPTION OF SYMBOLS 1... Substrate processing apparatus 10... Control part 11... Processing unit 12... Case 13... Processing space 15... Stage (substrate mounting part)
17a ... supply unit (first supply unit/second supply unit)
17b ... supply unit (second supply unit)
17c ... supply unit (pressure adjustment unit)
20... Pressure adjustment part 25... Exhaust part (pressure adjustment part)
REFERENCE SIGNS LIST 31: Temperature control unit 32: Cooling unit 36: Heating unit 41: Electron emitting unit 43: Electron beam source 45: Collecting unit 46: Electrode P1: First pressure (pressure at which the first processing gas can condense)
P2 … Second pressure (pressure at which the first solid film can be melted)
P3 ... Third pressure (pressure at which the liquid film can be solidified)
P4 ... fourth pressure (pressure at which the second solid film can be sublimated)
T1 ... first temperature (temperature at which the first process gas condenses under the first pressure)
T2 ... second temperature (temperature at which the first solid film H melts under the second pressure)
T3 ... third temperature (temperature at which the liquid film solidifies under the third pressure)
T4 ... fourth temperature (temperature at which the second solid film sublimates under the fourth pressure)
A... Concave part B... Particle G... Gas in housing H, Ha, Hb... First solid film J... Liquid film K... Gas-liquid interface L... Second solid film R... Pattern W... Substrate W1... Upper surface of substrate W2... Convex part

Claims

A substrate processing method for processing a substrate,
a placing step of placing the substrate in a substantially horizontal posture in the housing;
a first supply step of supplying a first processing gas to the housing;
a condensation step of condensing the first process gas to form a first solid film covering the top 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;
A substrate processing method comprising:
In the substrate processing method according to claim 1,
The condensation step includes cooling the first processing gas while maintaining the pressure of the gas in the housing at a pressure at which the first processing gas can be condensed;
The melting step heats 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.
In the substrate processing method according to claim 1,
the step of condensing comprises cooling the substrate to a temperature at which the first process gas condenses onto the top surface of the substrate;
The melting step heats the substrate to a temperature at which the first solid film melts.
The substrate processing method according to claim 1,
The substrate processing method, wherein the first processing gas includes at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas.
The substrate processing method according to claim 1,
wherein the first processing gas is water vapor;
in the condensation step, the pressure of the gas in the housing is less than the triple point pressure of water;
In the melting step, the pressure of the gas within the housing is higher than the triple point pressure of the water.
In the substrate processing method according to claim 1,
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:
In the substrate processing method according to claim 6,
The solidification step includes cooling the liquid film while maintaining the pressure of the gas in the housing at a pressure that allows the liquid film to solidify,
In the substrate processing method, the sublimation step heats the second solid film while maintaining the pressure of the gas in the housing at a pressure at which the second solid film can sublimate.
In the substrate processing method according to claim 6,
The solidification step includes cooling the substrate to a temperature at which the liquid film solidifies,
The substrate processing method, wherein the sublimation step heats the substrate to a temperature at which the second solid film sublimates.
The substrate processing method according to claim 6,
The substrate processing method according to claim 1, wherein the sublimation step discharges the gas inside the housing to the outside of the housing.
The substrate processing method according to claim 6,
wherein the first processing gas is water vapor;
In the solidification step, the pressure of the gas within the housing is greater than the pressure at the triple point of water,
In the sublimation step, the pressure of the gas within the housing is lower than the pressure of the triple point of water.
The substrate processing method according to claim 6,
a charging step of charging the second solid film;
A substrate processing method.
The substrate processing method according to claim 1,
a second supply step of supplying a second processing gas to the housing;
with
The substrate processing method, wherein the liquid film dissolves the second processing gas.
The substrate processing method according to claim 12,
The substrate processing method, wherein the second processing gas includes at least one of water vapor, ammonia gas, methylamine gas, dimethylamine gas, trimethylamine gas, and hydrogen peroxide gas.
The substrate processing method according to claim 1,
a collecting step of collecting the charged particles;
A substrate processing method.
The substrate processing method according to claim 1,
The substrate processing method, wherein the substrate has a pattern formed on the upper surface of the substrate.
A substrate processing apparatus,
a sealable enclosure; and
a substrate placement unit installed in the housing for placing the substrate in a substantially horizontal posture;
a first supply unit that supplies a first processing gas into the housing;
a pressure adjustment unit that adjusts the pressure of the gas in the housing;
a temperature adjustment 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;
with
The control unit
supplying the first processing gas from the first supply unit to the housing;
forming a first solid film covering the upper surface of the substrate placed on the substrate placing part by condensing the first processing gas by controlling the pressure adjusting part and the temperature adjusting part;
A substrate processing apparatus for forming a liquid film covering the upper surface of a substrate placed on the substrate placing part by melting the first solid film by controlling the pressure adjusting part and the temperature adjusting part.
In the substrate processing apparatus according to claim 16,
The control unit
solidifying 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 mounted on the substrate mounting unit;
A substrate processing apparatus for sublimating the second solid film by controlling the pressure adjustment unit and the temperature adjustment unit.
In the substrate processing apparatus according to claim 17,
an electron emitting unit that emits electrons into the housing;
with
The substrate processing apparatus, wherein the control unit negatively charges the second solid film by the electron emission unit.
In the substrate processing apparatus according to claim 16,
a second supply unit that supplies a second processing gas to the housing;
with
The control unit
A substrate processing apparatus for supplying the second processing gas from the second supply unit to the housing and dissolving the second processing gas in the liquid film.
In the substrate processing apparatus according to claim 16,
an electrode installed in the housing and to which a positive voltage is applied;
A substrate processing apparatus.