Substrate processing method and substrate processing apparatus

Abstract

The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method includes a first gas processing step, a hydrophobizing processing step, and a spreading step. In the first gas processing step, a first gas (G1) is supplied to a substrate (W) in a chamber (3) in a state (D) in which the inside of the chamber (3) is depressurized. The first gas (G1) contains a gas of an organic solvent. The hydrophobizing processing step is performed after the first gas processing step. In the hydrophobizing processing step, the inside of the chamber (3) is in the state (D) in which it is depressurized, and a hydrophobizing agent (H) is supplied to the substrate (W) in the chamber (3). The spreading step is performed after the hydrophobizing processing step. In the spreading step, the inside of the chamber (3) is in the state (D) in which it is depressurized, and a first liquid (L1) is spread to the substrate (W) in the chamber (3). The first liquid (L1) contains a liquid of an organic solvent.

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing method and a substrate processing apparatus. The substrate is, for example, a semiconductor wafer, a substrate for liquid crystal display, a substrate for organic electroluminescence (EL), a substrate for Flat Panel Display (FPD), a substrate for optical display, a substrate for magnetic disk, a substrate for optical disk, a substrate for optical magnetic disk, a substrate for photomask, or a substrate for solar cell. BACKGROUND

[0002] Japanese Patent Laid-Open No. 2018-56155 discloses a substrate processing method of processing a substrate housed in a chamber. The substrate processing method has a first process, a second process, and a third process. In the first process, a vapor of isopropyl alcohol is supplied to the substrate in a state where the inside of the chamber is decompressed. In the second process, a hydrophobic agent is supplied to the substrate in a state where the inside of the chamber is decompressed. The hydrophobic agent hydrophobizes the surface of the substrate. In the third process, a vapor of isopropyl alcohol is supplied to the substrate in a state where the inside of the chamber is decompressed. In the third process, the hydrophobic agent is replaced with isopropyl alcohol on the substrate. SUMMARY

[0003] [PROBLEMS TO BE SOLVED BY THE INVENTION]

[0004] In the conventional substrate processing method, a large amount of particles sometimes adhere to the substrate. The particles on the substrate cause the cleanliness of the substrate to decrease. The particles on the substrate cause the processing quality of the substrate to decrease.

[0005] The present application has been achieved in view of such a situation, and an object thereof is to provide a substrate processing method and a substrate processing apparatus capable of reducing particles on a substrate.

[0006] [MEANS OF SOLVING THE PROBLEM]

[0007] The present inventors and others have intensively studied in order to solve the problem, and as a result, have obtained the following insight. In the second process of the conventional substrate processing method, the hydrophobic agent contacts the substrate and isopropyl alcohol on the substrate. Therefore, particles sometimes generate on the substrate. Moreover, unreacted components of the hydrophobic agent remain on the substrate, and the unreacted components sometimes become the remaining particles. In the third process of the conventional substrate processing method, isopropyl alcohol supplied to the substrate is in a gas phase. Thus, in the third process, the amount of isopropyl alcohol received by the substrate. For example, in the third process, the mass of isopropyl alcohol received by the substrate is small. Since the amount of isopropyl alcohol received by the substrate is small, the particles on the substrate sometimes cannot be properly removed. As a result, a large amount of particles sometimes remain on the substrate.

[0008] Accordingly, the present inventors and others have investigated changing the third process. In the changed third process, instead of supplying isopropyl alcohol vapor to the substrate, the substrate is immersed in isopropyl alcohol liquid stored in a treatment tank. According to the changed third process, particles on the substrate can be more preferably removed.

[0009] However, the present inventors and others have found that the changed third process has a new problem. Specifically, it is difficult to perform the changed third process in a state in which the interior of the chamber is depressurized. In a state in which the interior of the chamber is depressurized, it is difficult to prepare a treatment tank in which isopropyl alcohol is stored.

[0010] The present application is based on these insights, obtained through further intensive investigation, and employs the following structure. That is, the present application is a substrate processing method that processes a plurality of substrates housed in one chamber at a time, the substrate processing method including: a first gas processing process of supplying a first gas that includes an organic solvent to the substrates in the chamber in a state in which the interior of the chamber is depressurized; a hydrophobizing process of supplying a hydrophobizing agent to the substrates in the chamber in a state in which the interior of the chamber is depressurized after the first gas processing process; and a scattering process of scattering a first liquid that includes an organic solvent toward the substrates in the chamber in a state in which the interior of the chamber is depressurized after the hydrophobizing process.

[0011] A substrate processing method is a method of processing a plurality of substrates housed in one chamber at a time. The substrate processing method includes a first gas processing step, a hydrophobizing processing step, and a scattering step. The first gas processing step, the hydrophobizing processing step, and the scattering step are executed in this order. In the first gas processing step, the hydrophobizing processing step, and the scattering step, the inside of the chamber is in a state of being depressurized. In the first gas processing step, a first gas is supplied to the substrates in the chamber. The first gas contains a gas of an organic solvent. The substrates receive the organic solvent of the first gas. The gas of the organic solvent in the first gas dewets on the surfaces of the substrates, and becomes a liquid of the organic solvent on the surfaces of the substrates. In the hydrophobizing processing step, a hydrophobizing agent is supplied to the substrates in the chamber. The substrates receive the hydrophobizing agent. The hydrophobizing agent hydrophobizes the surfaces of the substrates. In the hydrophobizing processing step, the hydrophobizing agent contacts the substrates and the organic solvent on the substrates. Therefore, particles are sometimes generated on the substrates. In the scattering step, a first liquid is scattered to the substrates in the chamber. The first liquid is easily scattered to the substrates in the state of being depressurized in the inside of the chamber. The first liquid contains a liquid of an organic solvent. The substrates receive the first liquid. Since the first liquid is a liquid, the amount of the first liquid received by the substrates in the scattering step is relatively large. For example, the mass of the first liquid received by the substrates in the scattering step is relatively large. Thus, in the scattering step, the first liquid preferably removes the particles on the substrates. Therefore, the amount of the particles on the substrates is preferably reduced. As a result, the cleanliness of the substrates is preferably improved. The processing quality of the substrates is preferably improved.

[0012] As described above, the substrate processing method can preferably reduce the particles on the substrates.

[0013] In the substrate processing method, it is preferable that the scattering step scatter at least either one of droplets of the first liquid and mist of the first liquid. In the scattering step, the first liquid is efficiently supplied to the substrates.

[0014] In the substrate processing method, it is preferable that the scattering step scatter the first liquid by at least either one of a shower head nozzle and a two-fluid nozzle. In the scattering step, the first liquid is efficiently supplied to the substrates.

[0015] In the substrate processing method, it is preferable that, in the scattering step, the substrates are further moved up and down or swung in the chamber. In the scattering step, the first liquid is more uniformly attached to the entire substrates.

[0016] In the substrate processing method, it is preferable that the spreading process includes at least either a first spreading process of spreading the organic solvent diluted as the first liquid or a second spreading process of spreading the organic solvent not diluted as the first liquid. In the first spreading process, the first liquid is the diluted organic solvent. Therefore, the amount of the organic solvent used in the first spreading process is preferably reduced. In the second spreading process, the first liquid is the undiluted organic solvent. Therefore, in the second spreading process, the first liquid has a small surface tension. Thus, in the second spreading process, the first liquid does not cause an intentional force to the substrate. As a result, in the second spreading process, the substrate is preferably protected.

[0017] In the substrate processing method, it is preferable that the second gas processing process of supplying a second gas including an organic solvent gas to the substrate in the chamber in a state where the inside of the chamber is depressurized after the hydrophobic treatment process is further included. In the second gas processing process, the entire substrate is exposed to the second gas. The second gas includes the organic solvent gas. Therefore, in the second gas processing process, the organic solvent derived from the second gas is rapidly attached to the entire substrate. In the second gas processing process, the organic solvent derived from the second gas is uniformly attached to the entire substrate. Thus, in the second gas processing process, the uniformity of the substrate cleanliness over the entire substrate is improved.

[0018] In the substrate processing method, it is preferable that the amount of the first liquid supplied in the spreading process is larger than the amount of the second gas supplied in the second gas processing process. In the spreading process, the amount of the first liquid received by the substrate is larger. Thus, in the spreading process, the first liquid more appropriately removes the particles on the substrate.

[0019] In the substrate processing method, it is preferable that the time for performing the spreading process is longer than the time for performing the second gas processing process. In the spreading process, the amount of the first liquid received by the substrate is larger. Thus, in the spreading process, the particles on the substrate are more preferably removed.

[0020] The substrate processing method preferably further includes a first immersion process of immersing the substrate in a second liquid stored in a processing tank provided in the chamber before the first gas processing process, the substrate being located above the processing tank in the first gas processing process, the hydrophobic treatment process, and the spreading process. The substrate processing method includes the first immersion process. In the first immersion process, the processing tank stores the second liquid. After the first immersion process, the first gas processing process, the hydrophobic treatment process, and the spreading process are performed. In the first gas processing process, the hydrophobic treatment process, and the spreading process, the inside of the chamber is in a reduced pressure state. Thus, the inside of the chamber is in the reduced pressure state from after the first immersion process until the spreading process. When the inside of the chamber is in the reduced pressure state, it is difficult to discharge the second liquid outside the chamber. Thus, it is difficult to replace the second liquid with the first liquid in the processing tank when the inside of the chamber is in the reduced pressure state. Therefore, it is difficult to supply the first liquid to the substrate using the processing tank from after the first immersion process until the spreading process. In the spreading process, the first liquid is spread to the substrate without using the processing tank. Thus, the first immersion process does not limit the performance of the spreading process. Even when the substrate processing method includes the first immersion process, the spreading process is easily performed. Of course, when the substrate processing method includes the first immersion process, the spreading process is significantly useful.

[0021] Further, in the first gas processing process, the hydrophobic treatment process, and the spreading process, the substrate is located above the processing tank. Thus, in the first gas processing process, the substrate preferably receives the first processing gas. In the hydrophobic treatment process, the substrate preferably receives the hydrophobic agent. In the spreading process, the substrate preferably receives the first liquid.

[0022] The substrate processing method preferably further includes a first pressurization process of pressurizing the inside of the chamber from the reduced pressure state to an atmospheric pressure state after the spreading process, and a first liquid discharge process of maintaining the inside of the chamber in the atmospheric pressure state and discharging the second liquid outside the chamber after the first pressurization process. The first pressurization process is performed after the spreading process and before the first liquid discharge process. In the first pressurization process, the inside of the chamber is pressurized from the reduced pressure state to the atmospheric pressure state. Thus, in the first liquid discharge process, the inside of the chamber is easily maintained in the atmospheric pressure state. When the inside of the chamber is in the atmospheric pressure state, the pressure of the gas in the chamber is close to the pressure of the gas outside the chamber. Thus, in the first liquid discharge process, the second liquid in the chamber is easily discharged to the outside of the chamber.

[0023] In the substrate processing method, it is preferable that, in the first draining process, a drain pipe connected in communication with any one of the chamber and the processing tank is opened to an atmosphere outside the chamber, and the second liquid is drained outside the chamber through the drain pipe. In the first draining process, the drain pipe is opened to the atmosphere outside the chamber. As described above, in the first draining process, the inside of the chamber is in an atmospheric pressure state. Thus, in the first draining process, the second liquid in the chamber is easily drained outside the chamber through the drain pipe.

[0024] Here, the second liquid in the chamber includes, for example, the second liquid stored in the processing tank. When the drain pipe is connected in communication with the processing tank, the second liquid stored in the processing tank is drained outside the chamber through the drain pipe. The second liquid in the chamber includes, for example, the second liquid discharged from the processing tank and accumulated in the chamber. When the drain pipe is connected in communication with the chamber, the second liquid accumulated in the chamber is drained outside the chamber through the drain pipe.

[0025] In the substrate processing method, it is preferable that, in the first pressurizing process, a mixed gas including an organic solvent and an inert gas is supplied to the substrate in the chamber. The inert gas of the mixed gas rapidly pressurizes the inside of the chamber from a depressurized state to an atmospheric pressure state. The organic solvent of the mixed gas wets the substrate in the chamber by adhering to the substrate. Thus, in the first pressurizing process, the substrate is not dried. In summary, in the first pressurizing process, the substrate in the chamber is not dried, and the inside of the chamber is rapidly pressurized from a depressurized state to an atmospheric pressure state.

[0026] In the substrate processing method, it is preferable that the mixed gas includes at least any one of a gas of the organic solvent and a liquid of the organic solvent. In the case where the mixed gas includes the gas of the organic solvent, the gas of the organic solvent in the mixed gas condenses on the surface of the substrate, and becomes the liquid of the organic solvent on the surface of the substrate. In the case where the mixed gas includes the liquid of the organic solvent, the liquid of the organic solvent in the mixed gas adheres to the surface of the substrate. In either case where the mixed gas includes the gas of the organic solvent or the liquid of the organic solvent, the organic solvent derived from the mixed gas preferably wets the substrate. Thus, the mixed gas preferably prevents the substrate from being dried.

[0027] In the substrate processing method, it is preferable that the method further includes a second immersion process of immersing the substrate in a third liquid stored in the processing tank after the first pressurizing process. In the second immersion process, the third liquid more preferably removes the particles on the substrate. Thus, the particles on the substrate are more preferably reduced.

[0028] In the substrate processing method, it is preferable that the atmosphere in the chamber contain an organic solvent from the first pressurization process until the substrate is immersed in the third liquid. The organic solvent contained in the atmosphere in the chamber from the first pressurization process until the substrate is immersed in the third liquid wets the substrate. Thus, the substrate is not dried from the first pressurization process until the second immersion process. The substrate is not dried after the scattering process and before the second immersion process. Therefore, the substrate is processed with a proper quality in the second immersion process.

[0029] In the substrate processing method, it is preferable that the third liquid be either a diluted organic solvent or pure water. When the third liquid is a diluted organic solvent, the third liquid appropriately removes particles on the substrate. When the third liquid is pure water, the third liquid also appropriately removes particles on the substrate.

[0030] The present application is a substrate processing apparatus including: a chamber that houses a plurality of substrates; a depressurization unit that depressurizes an inside of the chamber; a first supply unit that supplies a first gas containing an organic solvent to the substrates in the chamber; a second supply unit that supplies a hydrophobic agent to the substrates in the chamber; a scattering unit that scatters a first liquid containing an organic solvent to the substrates in the chamber; and a control section that controls the depressurization unit, the first supply unit, the second supply unit, and the scattering unit to perform a first gas processing in which the first supply unit supplies the first gas to the substrates in a state in which the inside of the chamber is depressurized by the depressurization unit, a hydrophobic processing in which the second supply unit supplies the hydrophobic agent to the substrates in a state in which the inside of the chamber is depressurized by the depressurization unit, and a scattering processing in which the scattering unit scatters the first liquid to the substrates in a state in which the inside of the chamber is depressurized by the depressurization unit.

[0031] The control section is configured to execute the first gas treatment, the hydrophobic treatment, and the scattering treatment. In the first gas treatment, the hydrophobic treatment, and the scattering treatment, the reduced pressure unit sets the inside of the chamber to a reduced pressure state. In the first gas treatment, the first supply unit supplies a first gas to the substrate inside the chamber. The first gas includes a gas of an organic solvent. The substrate receives the organic solvent of the first gas. In the hydrophobic treatment, the second supply unit supplies a hydrophobic agent to the substrate inside the chamber. The substrate receives the hydrophobic agent. The hydrophobic agent hydrophobizes the surface of the substrate. In the hydrophobic treatment, the hydrophobic agent contacts the substrate and the organic solvent on the substrate. Therefore, on the substrate, particles are sometimes generated. In the scattering treatment, the scattering unit scatters a first liquid to the substrate inside the chamber. In the reduced pressure state of the inside of the chamber, the scattering unit also easily scatters the first liquid to the substrate. The first liquid includes a liquid of an organic solvent. The substrate receives the first liquid. The amount of the first liquid that the substrate receives in the scattering treatment is relatively large. For example, the mass of the first liquid that the substrate receives in the scattering treatment is relatively large. Thus, in the scattering treatment, the first liquid preferably removes the particles on the substrate. Therefore, the amount of the particles on the substrate is preferably reduced. As a result, the cleanliness of the substrate is preferably improved. The processing quality of the substrate is preferably improved.

[0032] As described above, the substrate processing apparatus can preferably reduce the particles on the substrate. BRIEF DESCRIPTION OF DRAWINGS

[0033] In order to explain the application, several embodiments, which are presently considered to be preferred, are illustrated. It should be understood, however, that the application is not limited to the structures and measures shown in the drawings.

[0034] Figure 1 is a front view showing the inside of a substrate processing apparatus of a first embodiment.

[0035] Figure 2 is a control block diagram of a substrate processing apparatus.

[0036] Figure 3 is a flowchart showing the flow of a substrate processing method of the first embodiment.

[0037] Figures 4A to 4E are diagrams respectively schematically showing a substrate processing apparatus that performs the substrate processing method of the first embodiment.

[0038] Figure 5 is a front view showing the inside of a substrate processing apparatus of a second embodiment.

[0039] Figure 6 is a flowchart showing the flow of a substrate processing method of the second embodiment.

[0040] Figure 7 is a flowchart showing the flow of a substrate processing method of the second embodiment.

[0041] Figures 8A to 8E FIG. 1 is a view schematically showing a substrate processing apparatus which carries out a substrate processing method of a first embodiment.

[0042] Figures 9A to 9E FIG. 2 is a view schematically showing a substrate processing apparatus which carries out a substrate processing method of a second embodiment.

[0043] Figures 10A to 10E FIG. 3 is a view schematically showing a substrate processing apparatus which carries out a substrate processing method of a third embodiment.

[0044] Figures 11A to 11C FIG. 4 is a view schematically showing a substrate processing apparatus which carries out a substrate processing method of a fourth embodiment.

[0045] [Explanation of Symbols]

[0046] 1: Substrate processing apparatus

[0047] 3: Chamber

[0048] 5: Space

[0049] 11: Processing tank

[0050] 12a: Opening

[0051] 12b: Discharge port

[0052] 13: Holding portion

[0053] 15: Lifting mechanism

[0054] 21, 61, 71: Supply unit

[0055] 22, 32, 42, 52, 52a, 52b, 62, 72: Discharge portion

[0056] 23, 33, 43, 53, 53a, 53b, 63, 67, 73, 77, 82: Pipe

[0057] 24, 34, 44, 54, 54a, 54b, 64, 68, 74, 78: Valve

[0058] 25, 35, 45, 55, 55a, 55b, 65, 69, 75, 79: Supply source

[0059] 31: Supply unit (second supply unit)

[0060] 41: Supply unit (first supply unit)

[0061] 51: Supply unit (scattering unit)

[0062] 81: Pressure reduction unit

[0063] 83: exhaust pump

[0064] 89: pressure sensor

[0065] 91: drain unit

[0066] 92: drain valve

[0067] 95: liquid discharge unit

[0068] 96: pipe (liquid discharge pipe)

[0069] 97: discharge valve

[0070] 101: control unit

[0071] D: reduced pressure state

[0072] Gl: first gas

[0073] G2: second gas

[0074] G3: third gas

[0075] H: hydrophobic agent

[0076] J: normal pressure state

[0077] K: mixed gas

[0078] Ll: first liquid

[0079] Lla: dilute first liquid (diluted organic solvent)

[0080] Llb: non-dilute first liquid (undiluted organic solvent)

[0081] L2: second liquid

[0082] L3: third liquid

[0083] N: inert gas

[0084] Pl: first position

[0085] P2: second position

[0086] S1 to S5, Sll to S20, S21 to S29: steps

[0087] W: substrate

[0088] X, Y, Z: directions DETAILED DESCRIPTION

[0089] Hereinafter, a substrate processing method and a substrate processing apparatus according to the present application will be described with reference to the accompanying drawings.

[0090] <1. First Embodiment>

[0091] <1-1. Outline of substrate processing apparatus>

[0092] Figure 1 Fig. 1 is a front view showing the inside of a substrate processing apparatus 1 according to a first embodiment. The substrate processing apparatus 1 processes a substrate W. The processing performed by the substrate processing apparatus 1 includes a drying process. The processing performed by the substrate processing apparatus 1 can further include a cleaning process. The substrate processing apparatus 1 is classified as a batch type. The substrate processing apparatus 1 processes a plurality of substrates W at a time.

[0093] The substrate W is, for example, a semiconductor wafer, a substrate for liquid crystal display, a substrate for organic electroluminescence (EL), a substrate for flat panel display (FPD), a substrate for optical display, a substrate for magnetic disk, a substrate for optical disk, a substrate for optical magnetic disk, a substrate for photomask, or a substrate for solar cell.

[0094] The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in plan view.

[0095] The substrate W has a surface. The surface of the substrate W includes at least any one of a silicon oxide film, a polysilicon film, a silicon nitride film, and a metal film.

[0096] Although not shown, the substrate W has a pattern. The pattern is formed on the surface of the substrate W. The pattern has a concave-convex shape. The surface of the substrate W on which the pattern is formed is referred to as a pattern formation surface.

[0097] The substrate processing apparatus 1 includes a chamber 3. The chamber 3 houses a plurality of substrates W. The chamber 3 houses a plurality of substrates W at a time. The substrates W are arranged inside the chamber 3. Specifically, the chamber 3 is a container that divides a space 5. The space 5 corresponds to the inside of the chamber 3. The substrates W are arranged in the space 5.

[0098] The chamber 3 is configured to be openable and closable. When the chamber 3 is opened, the space 5 is opened. When the chamber 3 is opened, the chamber 3 allows the substrates W to move between the space 5 and the outside of the chamber 3. When the chamber 3 is closed, the space 5 is closed. That is, the chamber 3 is configured to be closable.

[0099] The substrate processing apparatus 1 includes a processing tank 11. The processing tank 11 is provided in the chamber 3. The processing tank 11 stores a processing liquid. The processing tank 11 is open upward.

[0100] The substrate processing apparatus 1 includes a holding section 13. The holding section 13 is provided inside the chamber 3. The holding section 13 holds a plurality of substrates W at a time. The holding section 13 holds each substrate W in a substantially vertical posture. When the holding section 13 holds the substrate W, the pattern formation surface of the substrate W is substantially vertical. When the holding section 13 holds a plurality of substrates W, the plurality of substrates W are aligned in a row along the direction X. The direction X is horizontal. The direction X is substantially perpendicular to the pattern formation surface of the substrate W.

[0101] Figure 1 In addition to the direction X, a direction Y and a direction Z are indicated. The direction Y is horizontal. The direction Y is perpendicular to the direction X. The direction Z is vertical. The direction Z is perpendicular to the direction X. The direction Z is perpendicular to the direction Y. The direction Z is appropriately called a vertical direction Z.

[0102] The substrate processing apparatus 1 includes a lifting mechanism 15. The lifting mechanism 15 lifts the holding section 13. The lifting mechanism 15 moves the holding section 13 along the vertical direction Z, for example. When the lifting mechanism 15 lifts the holding section 13, the substrate W held by the holding section 13 is lifted integrally with the holding section 13.

[0103] The lifting mechanism 15 moves the substrate W to a first position PI and a second position P2. Figure 1 In the figure, the substrate W in the first position PI is indicated by a solid line. Figure 1 In the figure, the substrate W in the second position P2 is indicated by a broken line. The first position PI is inside the chamber 3. The first position PI is above the processing bath 11. When the substrate W is in the first position PI, the entire substrate W is not in contact with the processing liquid inside the processing bath 11. The second position P2 is inside the chamber 3. The second position P2 is below the first position PI. The second position P2 is inside the processing bath 11. When the substrate W is in the second position P2, the entire substrate W is immersed in the processing liquid inside the processing bath 11.

[0104] The substrate processing apparatus 1 includes a supply unit 21, a supply unit 31, a supply unit 41, a supply unit 51, and a supply unit 61. The supply unit 21 supplies an inert gas to the chamber 3. The supply unit 31 supplies a hydrophobic agent to the chamber 3. The supply unit 41 supplies a processing gas to the chamber 3. The supply unit 51 supplies a first liquid to the chamber 3. The supply unit 61 supplies a second liquid to the processing bath 11.

[0105] When the substrate W is in the first position PI, the supply unit 21 supplies the inert gas to the substrate W. When the substrate W is in the first position PI, the supply unit 31 supplies the hydrophobic agent to the substrate W. When the substrate W is in the first position PI, the supply unit 41 supplies the processing gas to the substrate W. When the substrate W is in the first position PI, the supply unit 51 supplies the first liquid to the substrate W.

[0106] The supply unit 41 is an example of a first supply unit in the present application. The supply unit 31 is an example of a second supply unit in the present application. The supply unit 51 is an example of a scattering unit in the present application.

[0107] The inert gas supplied by the supply unit 21 is, for example, nitrogen.

[0108] The hydrophobic agent supplied by the supply unit 31 is described. The hydrophobic agent hydrophobizes the surface of the substrate W. The hydrophobic agent modifies the surface of the substrate W to be hydrophobic. The hydrophobic agent makes the contact angle of the surface of the substrate W with water large. The hydrophobic agent forms a hydrophobic film on the surface of the substrate W. The surface of the substrate W is coated with the hydrophobic agent. The hydrophobic agent is also called a surface modifier. The hydrophobic agent is also called a water repellent agent.

[0109] The hydrophobic agent contains, for example, at least any one of a silicon-based hydrophobic agent and a metal-based hydrophobic agent. The silicon-based hydrophobic agent hydrophobizes silicon. The silicon-based hydrophobic agent hydrophobizes a compound containing silicon. The silicon-based hydrophobic agent is, for example, a silane coupling agent. The silane coupling agent contains, for example, at least any one of hexamethyl disilazane (HMDS), tetramethylsilane (TMS), a fluorinated alkyl chlorosilane, an alkyl disilazane, and a non-chlorine-based hydrophobic agent. The non-chlorine-based hydrophobic agent contains, for example, at least any one of dimethylsilyl dimethylamine, dimethylsilyl diethylamine, hexamethyl disilazane, tetramethyl disilazane, bis(dimethyl amino)dimethylsiloxane, N,N-dimethyl amino trimethylsilane, N-(trimethylsilyl)dimethylamine, and an organosilane compound. The metal-based hydrophobic agent hydrophobizes metal. The metal-based hydrophobic agent hydrophobizes a compound containing metal. The metal-based hydrophobic agent contains, for example, at least any one of an amine having a hydrophobic group and an organosilicon compound.

[0110] The hydrophobic agent can further include a solvent. For example, the solvent can dilute at least either one of the silicon-based hydrophobic agent and the metal-based hydrophobic agent. It is preferable that the solvent is miscible with the organic solvent. The solvent includes at least either one of isopropyl alcohol (IPA) and propylene glycol monomethyl ether acetate (PGMEA), for example.

[0111] The hydrophobic agent includes at least either one of a gas of the hydrophobic agent and a liquid of the hydrophobic agent. The supply unit 31 supplies at least either one of the gas of the hydrophobic agent and the liquid of the hydrophobic agent. For example, the gas of the hydrophobic agent is a vapor of the hydrophobic agent.

[0112] The processing gas supplied by the supply unit 41 is described. The processing gas includes a gas of an organic solvent. For example, the gas of the organic solvent is a vapor of the organic solvent. For example, the concentration of the organic solvent in the processing gas is high. For example, the processing gas substantially includes only the gas of the organic solvent. For example, the processing gas substantially does not contain water (water vapor). It is preferable that the organic solvent of the processing gas has a hydrophilic property. For example, the organic solvent of the processing gas is isopropyl alcohol (IPA).

[0113] The processing gas does not contain the hydrophobic agent.

[0114] The first liquid supplied by the supply unit 51 is described. The first liquid includes a liquid of an organic solvent. For example, the first liquid substantially includes only the liquid of the organic solvent. For example, the first liquid is a raw liquid of the organic solvent. For example, the first liquid is a liquid of the organic solvent that is not diluted. For example, the first liquid substantially does not contain water. Alternatively, the first liquid is a liquid of the organic solvent that is diluted. For example, the first liquid is the organic solvent diluted by pure water. For example, the first liquid is a mixed liquid of pure water and the organic solvent. For example, the organic solvent of the first liquid is isopropyl alcohol (IPA).

[0115] The first liquid does not contain the hydrophobic agent.

[0116] The second liquid supplied by the supply unit 61 is described. For example, the second liquid is a rinse liquid. For example, the second liquid is pure water (de ionized water (DIW)).

[0117] The structures of the supply unit 21, the supply unit 31, the supply unit 41, the supply unit 51, and the supply unit 61 are exemplified.

[0118] The supply unit 21 includes an emitting portion 22, a pipe 23, and a valve 24. The emitting portion 22 emits an inert gas. The pipe 23 is connected to the emitting portion 22. The pipe 23 is further connected to a supply source 25. The supply source 25 stores the inert gas. The valve 24 is provided to the pipe 23. When the valve 24 is opened, the inert gas flows from the supply source 25 to the emitting portion 22 through the pipe 23. When the valve 24 is opened, the emitting portion 22 emits the inert gas. When the valve 24 is closed, the inert gas does not flow from the supply source 25 to the emitting portion 22 through the pipe 23. When the valve 24 is closed, the emitting portion 22 does not emit the inert gas.

[0119] Similarly, the supply unit 31, the supply unit 41, the supply unit 51, the supply unit 61 respectively include an emitting portion 32, an emitting portion 42, an emitting portion 52, an emitting portion 62, a pipe 33, a pipe 43, a pipe 53, a pipe 63, and a valve 34, a valve 44, a valve 54, a valve 64. The emitting portion 32 emits a water repellent agent. The emitting portion 42 emits a treatment gas. The emitting portion 52 emits a first liquid. The emitting portion 62 emits a second liquid. The pipe 33, the pipe 43, the pipe 53, the pipe 63 are respectively connected to the emitting portion 32, the emitting portion 42, the emitting portion 52, the emitting portion 62. The pipe 33, the pipe 43, the pipe 53, the pipe 63 are respectively connected to a supply source 35, a supply source 45, a supply source 55, a supply source 65. The supply source 35 stores the water repellent agent. The supply source 45 stores the treatment gas. The supply source 55 stores the first liquid. The supply source 65 stores the second liquid. The valve 34, the valve 44, the valve 54, the valve 64 are respectively provided to the pipe 33, the pipe 43, the pipe 53, the pipe 63. The valve 34, the valve 44, the valve 54, the valve 64 respectively control the emission performed by the emitting portion 32, the emitting portion 42, the emitting portion 52, the emitting portion 62.

[0120] The emitting portion 22, the emitting portion 32, the emitting portion 42, the emitting portion 52, the emitting portion 62 are respectively provided in the chamber 3. The emitting portion 22, the emitting portion 32, the emitting portion 42, the emitting portion 52 are respectively arranged at a position higher than the processing tank 11. The emitting portion 22 is arranged at both sides of the substrate W at the first position P1 in the direction Y. The emitting portion 32, the emitting portion 42, the emitting portion 52 are also arranged similarly to the emitting portion 22. The emitting portion 62 is arranged in the processing tank 11.

[0121] The emitting portion 22 includes a tubular member. The tubular member extends in the direction X. The tubular member has a plurality of emission ports (not shown). The plurality of emission ports are arranged in the direction X. The emitting portion 22 blows the inert gas from the plurality of emission ports. The emitting portion 32, the emitting portion 42 have a structure similar to that of the emitting portion 22.

[0122] The ejection section 52 scatters the first liquid into the chamber 3. For example, the ejection section 52 scatters at least either one of liquid droplets of the first liquid and liquid mist of the first liquid into the chamber 3. For example, the ejection section 52 scatters the first liquid in a wide angle. For example, the ejection section 52 distributes the first liquid in a wide range.

[0123] For example, the ejection section 52 includes a plurality of (for example, twenty) showerhead nozzles. The plurality of showerhead nozzles are arranged in two rows in the direction X. Each of the showerhead nozzles has a plurality of ejection ports (not shown). Each of the showerhead nozzles ejects the first liquid from the plurality of ejection ports. Each of the showerhead nozzles ejects the first liquid in a shower-like manner. Each of the showerhead nozzles scatters a large amount of liquid droplets of the first liquid.

[0124] The supply source 45 can further generate the processing gas in addition to storing the processing gas. Although not shown, the supply source 45 includes, for example, a tank and a heater. The tank is communicatively connected to the pipe 43. The tank stores the liquid of the organic solvent. The heater heats the liquid of the organic solvent in the tank. In the tank, the liquid of the organic solvent is vaporized to become the vapor of the organic solvent. That is, the processing gas is generated in the tank.

[0125] The substrate processing apparatus 1 includes a decompression unit 81. The decompression unit 81 decompresses the inside of the chamber 3. Specifically, the decompression unit 81 discharges the gas in the chamber 3 to the outside of the chamber 3. Here, when the decompression unit 81 decompresses the inside of the chamber 3, the pressure of the gas in the chamber 3 can or can not continuously decrease. When the decompression unit 81 decompresses the inside of the chamber 3, the pressure of the gas in the chamber 3 can be maintained, for example, within a prescribed negative pressure range.

[0126] The structure of the decompression unit 81 is exemplified. The decompression unit 81 includes a pipe 82 and an exhaust pump 83. The pipe 82 and the exhaust pump 83 are provided outside the chamber 3. The pipe 82 is communicatively connected to the chamber 3. The exhaust pump 83 is provided to the pipe 82. The exhaust pump 83 is, for example, a vacuum pump. When the decompression unit 81 is operated, the exhaust pump 83 discharges the gas in the chamber 3 to the outside of the chamber 3 via the pipe 82. When the decompression unit 81 is stopped, the exhaust pump 83 does not discharge the gas in the chamber 3 to the outside of the chamber 3.

[0127] Figure 2 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control section 101. The control section 101 controls each element of the substrate processing apparatus 1. Specifically, the control section 101 controls the elevation mechanism 15. The control section 101 controls the supply unit 21, the supply unit 31, the supply unit 41, the supply unit 51, and the supply unit 61. The control section 101 controls the valve 24, the valve 34, the valve 44, the valve 54, and the valve 64. The control section 101 controls the decompression unit 81. The control section 101 controls the exhaust pump 83.

[0128] The control section 101 is realized by a central arithmetic processing device (Central Processing Unit (CPU)) that performs various processes, a storage medium such as a Random Access Memory (RAM) that is a work area of the arithmetic processing, and a fixed disk, and the like. The control section 101 has various information that is stored in advance in the storage medium. The information that the control section 101 has is, for example, processing information for controlling the substrate processing device 1. The processing information is also called a processing program library.

[0129] <1-2. Action Example of Substrate Processing Device>

[0130] In a device (not shown) that is different from the substrate processing device 1, a wet etching process is performed on the substrate W. The wet etching process is, for example, a process of supplying an etching liquid to the substrate W. Subsequently, the substrate W is carried to the substrate processing device 1. The chamber 3 is opened. The plurality of substrates W enters the chamber 3. The holding section 13 receives the plurality of substrates W. In a state in which the chamber 3 houses the substrates W, the chamber 3 is closed.

[0131] In a state in which the chamber 3 is closed, the substrate processing device 1 performs a substrate processing method on the substrates W. The substrate processing method is a process of processing the plurality of substrates W housed in the chamber 3 at one time. A specific substrate processing method is exemplified below.

[0132] Figure 3 is a flowchart that shows a flow of the substrate processing method of the first embodiment. The substrate processing method includes a first immersion process, a first gas processing process, a hydrophobic treatment process, a scattering process, and a drying process. The first immersion process, the first gas processing process, the hydrophobic treatment process, the scattering process, and the drying process are executed in this order.

[0133] Figure 4A is a view that schematically shows the substrate processing device 1 in the first immersion process. Figure 4B is a view that schematically shows the substrate processing device 1 in the first gas processing process. Figure 4C is a view that schematically shows the substrate processing device 1 in the hydrophobic treatment process. Figure 4D is a view that schematically shows the substrate processing device 1 in the scattering process. Figure 4E is a view that schematically shows the substrate processing device 1 in the drying process. Figures 4A to 4E The substrate processing device 1 is schematically shown in each of the following views. For example, Figures 4A to 4E The holding section 13 and the lift mechanism 15 are omitted from the views. In the following description, each element of the substrate processing device 1 is operated by the control of the control section 101.

[0134] Step S1: First Immersion Process

[0135] Reference Figure 4A The processing tank 11 stores the second liquid L2 supplied from the supply unit 61. The lifting mechanism 15 moves the substrate W to the second position P2. The substrate W is immersed in the second liquid L2 in the processing tank 11.

[0136] Step S2: First gas processing step (first gas processing)

[0137] Reference Figure 4B The supply unit 41 supplies the processing gas into the chamber 3. In this specification, the processing gas supplied to the chamber 3 in the first gas processing step is appropriately referred to as "first gas G1". The pressure reducing unit 81 operates. That is, the pressure reducing unit 81 reduces the pressure inside the chamber 3. Figure 4B The "VAC" in the text indicates that the decompression unit 81 is operating. The interior of chamber 3 is in a decompressed state (D). When the interior of chamber 3 is in a decompressed state (D), the gas pressure inside chamber 3 is negative. An atmosphere of first gas G1 is formed inside chamber 3. The lifting mechanism 15 moves the substrate W from the second position P2 to the first position P1. The substrate W is lifted from the second liquid L2 in the processing tank 11. Under the decompressed state (D) inside chamber 3, the supply unit 41 supplies the first gas G1 to the substrate W inside chamber 3. The substrate W is exposed to the first gas G1. The organic solvent gas contained in the first gas G1 condenses on the surface of the substrate W. That is, the organic solvent gas contained in the first gas G1 becomes a liquid organic solvent on the surface of the substrate W. The liquid organic solvent from the first gas G1 adheres to the substrate W. The organic solvent from the first gas G1 removes the second liquid L2 from the substrate W. Since the interior of chamber 3 is in a depressurized state D, the second liquid L2 is rapidly replaced by an organic solvent on the substrate W. The organic solvent originating from the first gas G1 covers the surface of the substrate W.

[0138] Step S3: Hydrophobic treatment process (hydrophobic treatment)

[0139] Reference Figure 4CThe substrate W is located at the first position P1. The depressurizing unit 81 is in operation. The inside of the chamber 3 is kept in the depressurized state D. The supply unit 41 stops the supply of the first gas G1. The supply unit 31 supplies the hydrophobic agent H to the substrate W in the chamber 3. The hydrophobic agent H adheres to the substrate W. In the case where the supply unit 31 supplies the gas of the hydrophobic agent H, the gas of the hydrophobic agent H dewets on the surface of the substrate W, and the surface of the substrate W becomes the liquid of the hydrophobic agent H. In the case where the supply unit 31 supplies the liquid of the hydrophobic agent H, the liquid of the hydrophobic agent H adheres to the surface of the substrate W. Since the inside of the chamber 3 is in the depressurized state D, the liquid of the organic solvent is rapidly replaced with the hydrophobic agent H on the substrate W. The hydrophobic agent H covers the surface of the substrate W. The hydrophobic agent H hydrophobizes the substrate W.

[0140] A part of the hydrophobic agent H on the substrate W becomes a hydrophobic film. The hydrophobic film is formed on the surface of the substrate W. Another part of the hydrophobic agent H on the substrate W becomes an unreacted component of the hydrophobic agent H. The unreacted component of the hydrophobic agent H does not react and remains on the substrate W as is. The unreacted component of the hydrophobic agent H is also called a residual component of the hydrophobic agent H or a remaining component of the hydrophobic agent H. Further, another part of the hydrophobic agent H on the substrate W sometimes becomes a particle. The particle is also called a foreign matter. The particle derived from the hydrophobic agent H is generated, for example, due to the contact of the hydrophobic agent H with the organic solvent. The particle derived from the hydrophobic agent H is generated, for example, due to the contact of the hydrophobic agent H with the substrate W. Further, the unreacted component of the hydrophobic agent H sometimes becomes the particle derived from the hydrophobic agent H.

[0141] Step S4: Spreading Process (Spreading Treatment)

[0142] Reference Figure 4D The substrate W is located at the first position P1. The depressurizing unit 81 is in operation. The inside of the chamber 3 is kept in the depressurized state D. The supply unit 31 stops the supply of the hydrophobic agent H. The supply unit 51 spreads the first liquid L1 to the substrate W in the chamber 3. The supply unit 51 spreads, for example, at least either one of the droplets of the first liquid L1 and the mist of the first liquid L1. The supply unit 51 spreads the first liquid L1, for example, by a shower head nozzle. The first liquid L1 adheres to the substrate W. The first liquid L1 removes the unreacted hydrophobic agent H on the substrate W. The first liquid L1 also removes the particle derived from the hydrophobic agent H on the substrate W. Since the inside of the chamber 3 is in the depressurized state D, the first liquid L1 is rapidly replaced with the hydrophobic agent H on the substrate. Since the inside of the chamber 3 is in the depressurized state D, the particle derived from the hydrophobic agent H is also rapidly removed from the substrate W. The first liquid L1 covers the surface of the substrate W.

[0143] In the scattering process, the lifting mechanism 15 can also stop the substrate W at the first position Pl. Alternatively, in the scattering process, the lifting mechanism 15 can also move the substrate W up and down. For example, the lifting mechanism 15 can also move the substrate W up and down in the vicinity of the first position Pl. For example, the lifting mechanism 15 can also move the substrate W up and down in the vertical direction Z. Alternatively, the lifting mechanism 15 can further include a not-illustrated mechanism that swings the substrate W. The lifting mechanism 15 can also swing the substrate W by the mechanism. In the case where the substrate W is moved up and down or swung, the entire substrate W preferably receives the first liquid LI. In the case where the substrate W is moved up and down or swung, the first liquid LI is more uniformly attached to the entire surface of the substrate W.

[0144] Step S5: Drying process

[0145] The substrate W is located at the first position Pl. The decompression unit 81 is in operation. The inside of the chamber 3 is kept in the decompressed state D. The supply unit 51 stops the scattering of the first liquid LI. The supply unit 21 supplies the inert gas N to the substrate W. The substrate W is exposed to the inert gas N. The inert gas N removes the first liquid LI on the substrate W. By removing the first liquid LI from the substrate W, the substrate W is dried.

[0146] Here, the substrate W is hydrophobized. Therefore, when the first liquid LI is removed from the substrate W, the force of the first liquid on the substrate W is small. Since the inside of the chamber 3 is in the decompressed state D, the first liquid LI is removed from the substrate W in a short time. Therefore, when the first liquid LI is removed from the substrate W, the force of the first liquid on the substrate W is smaller. Therefore, when the first liquid LI is removed from the substrate W, the substrate W is preferably protected. When the first liquid LI is removed from the substrate W, the pattern on the substrate W is preferably protected. For example, when the first liquid LI is removed from the substrate W, collapse of the pattern can be preferably prevented.

[0147] Although illustration is omitted, after the drying process, the inside of the chamber 3 is subjected to pressurization. For example, the supply unit 61 supplies the inert gas N, and the decompression unit 81 stops operation. Thereby, the pressure in the chamber 3 rises. The inside of the chamber 3 becomes an atmospheric pressure state from the decompressed state D.

[0148] The atmospheric pressure state is described. The inside of the chamber 3 being in the atmospheric pressure state means that the pressure of the gas in the chamber 3 is atmospheric pressure. The atmospheric pressure is not a specific value, but a range defined by two different values. The atmospheric pressure is higher than the pressure of the gas in the chamber 3 when the inside of the chamber 3 is in the decompressed state D. The atmospheric pressure is close to the pressure of the gas outside the chamber 3. For example, the atmospheric pressure is substantially equal to the pressure of the gas outside the chamber 3. For example, the atmospheric pressure includes standard atmospheric pressure (one atmosphere, 101325 Pa).

[0149] After the chamber 3 becomes the normal pressure state, the chamber 3 is opened. Also, the substrate W in the chamber 3 is carried out to the outside of the chamber 3.

[0150] <1-3. Effects of the first embodiment>

[0151] The substrate processing method includes a first gas processing step, a hydrophobic treatment step, and a spreading step. In the first gas processing step, the inside of the chamber 3 is in the reduced pressure state D, and the first gas G1 is supplied to the substrate W in the chamber 3. The first gas G1 includes a gas of an organic solvent. The hydrophobic treatment step is performed after the first gas processing step. In the hydrophobic treatment step, the inside of the chamber 3 is in the reduced pressure state D, and the hydrophobic agent H is supplied to the substrate W in the chamber 3. The spreading step is performed after the hydrophobic treatment. In the spreading step, the inside of the chamber 3 is in the reduced pressure state D, and the first liquid L1 is spread to the substrate W in the chamber 3. In the reduced pressure state D of the inside of the chamber 3, the first liquid L1 is also easily spread to the substrate W. The first liquid L1 includes a liquid of an organic solvent. Since the first liquid is a liquid, the density of the first liquid L1 is relatively large. For example, the density of the first liquid L1 is larger than the density of the first gas G1. Therefore, the amount of the first liquid L1 received by the substrate W in the spreading step is relatively large. For example, the mass of the first liquid L1 received by the substrate W in the spreading step is relatively large. Thus, in the spreading step, the particles on the substrate W are preferably removed. Therefore, the amount of the particles on the substrate W is preferably reduced. As a result, the cleanliness of the substrate W is preferably improved. The processing quality of the substrate W is preferably improved.

[0152] In the hydrophobic treatment step, sometimes the particles originating from the hydrophobic agent H are generated on the substrate W. At this time, in the spreading step, the first liquid L1 also preferably removes the particles originating from the hydrophobic agent H on the substrate W.

[0153] As described above, the substrate processing method of the first embodiment can preferably reduce the particles on the substrate W.

[0154] In the spreading step, at least either one of the droplets of the first liquid L1 and the mist of the first liquid L1 is spread. Therefore, in the spreading step, the first liquid L1 is efficiently supplied to the substrate W. For example, both the consumption amount of the first liquid L1 can be suppressed and the first liquid L1 can be attached to the entire substrate W.

[0155] In the spreading step, the first liquid L1 is spread by the showerhead nozzle. Therefore, in the spreading step, the first liquid L1 is efficiently supplied to the substrate W. For example, both the consumption amount of the first liquid L1 can be suppressed and the first liquid L1 can be attached to the entire substrate W.

[0156] The substrate processing method includes a first immersion process. The first immersion process is performed before the first gas processing process. In the first immersion process, the substrate W is immersed in the second liquid L2 stored in the processing tank 11. The processing tank 11 is provided in the chamber 3. After the first immersion process, the first gas processing process, the hydrophobic treatment process, and the spreading process are performed. In the first gas processing process, the hydrophobic treatment process, and the spreading process, the inside of the chamber 3 is in the reduced-pressure state D. Therefore, after the first immersion process, until the spreading process, the inside of the chamber 3 is in the reduced-pressure state D. When the inside of the chamber 3 is in the reduced-pressure state D, it is difficult to discharge the second liquid L2 to the outside of the chamber 3. Thus, when the inside of the chamber 3 is in the reduced-pressure state D, it is difficult to replace the second liquid L2 with the first liquid L1 in the processing tank 11. Therefore, after the first immersion process, until the spreading process, it is difficult to supply the first liquid L1 to the substrate W using the processing tank 11. In the spreading process, the first liquid L1 is spread to the substrate W without using the processing tank 11. Therefore, the first immersion process does not limit the execution of the spreading process. Even in the case where the substrate processing method includes the first immersion process, the spreading process is easily performed. Of course, in the case where the substrate processing method includes the first immersion process, the spreading process is significantly useful.

[0157] In the first gas processing process, the hydrophobic treatment process, and the spreading process, the substrate W is located above the processing tank 11. Specifically, in the first gas processing process, the hydrophobic treatment process, and the spreading process, the substrate W is located at the first position P1. Therefore, in the first gas processing process, the substrate W preferably receives the first gas G1. In the hydrophobic treatment process, the substrate W preferably receives the hydrophobic agent H. In the spreading process, the substrate W preferably receives the first liquid L1.

[0158] The substrate processing apparatus 1 includes a chamber 3, a supply unit 31, a supply unit 41, a supply unit 51, a depressurization unit 81, and a control section 101. The chamber 3 houses a plurality of substrates W. The supply unit 31 supplies a hydrophobic agent H to the substrates W in the chamber 3. The supply unit 41 supplies a first gas G1 to the substrates W in the chamber 3. The supply unit 51 supplies a first liquid L1 to the substrates W in the chamber 3. The depressurization unit 81 depressurizes the inside of the chamber 3. The control section 101 controls the supply unit 31, the supply unit 41, the supply unit 51, and the depressurization unit 81 so that they perform a first gas processing, a hydrophobic processing, and a scattering processing. In the first gas processing, the depressurization unit 81 depressurizes the inside of the chamber 3, and the supply unit 41 supplies the first gas G1 to the substrates W. In the hydrophobic processing, the depressurization unit 81 depressurizes the inside of the chamber 3, and the supply unit 31 supplies the hydrophobic agent H to the substrates W. In the scattering processing, the depressurization unit 81 depressurizes the inside of the chamber 3, and the supply unit 51 scatters the first liquid L1 to the substrates W. Even when the depressurization unit 81 depressurizes the inside of the chamber 3, the supply unit 51 can preferably scatter the first liquid L1 to the substrates W. In the scattering processing, the first liquid L1 preferably removes the particles on the substrates W. Therefore, the amount of the particles on the substrates W is preferably reduced. As a result, the cleanliness of the substrates W is preferably improved. The processing quality of the substrates W is preferably improved.

[0159] In the hydrophobic processing, sometimes the particles derived from the hydrophobic agent H are generated on the substrates W. At this time, in the scattering processing, the first liquid L1 can preferably remove the particles derived from the hydrophobic agent H on the substrates W.

[0160] As described above, the substrate processing apparatus 1 of the first embodiment can preferably reduce the particles on the substrates W.

[0161] <2. Second Embodiment>

[0162] The second embodiment will be described with reference to the drawings. In addition, the same reference numerals are assigned to the same structures as those of the first embodiment, and thus detailed description will be omitted.

[0163] <2-1. Outline of Substrate Processing Apparatus>

[0164] Figure 5 is a front view showing the inside of the substrate processing apparatus 1 of the second embodiment. The supply unit 51 supplies two kinds of first liquids L1. Hereinafter, one of the first liquids L1 will be referred to as "diluted first liquid L1a". The other first liquid will be referred to as "non-diluted first liquid L1b".

[0165] The diluted first liquid Lla is a diluted organic solvent. The diluted first liquid Lla is an organic solvent diluted by pure water. The diluted first liquid Lla is a mixture of pure water and an organic solvent. The organic solvent of the diluted first liquid Lla is, for example, isopropyl alcohol (IPA).

[0166] The non-diluted first liquid Llb is an undiluted organic solvent. The non-diluted first liquid Llb is a liquid containing substantially only an organic solvent. The non-diluted first liquid Llb is a raw liquid of an organic solvent. The non-diluted first liquid Llb contains substantially no water. The organic solvent of the non-diluted first liquid Llb is, for example, isopropyl alcohol (IPA).

[0167] The structure of the supply unit 51 is exemplified. The supply unit 51 includes a spouting portion 52a, a spouting portion 52b. The spouting portions 52a, 52b are respectively arranged in the chamber 3. The spouting portions 52a, 52b are respectively arranged at positions higher than the processing tank 11. The spouting portion 52a is arranged on both sides of the substrate W at the first position Pl in the direction Y. The spouting portion 52a has a structure similar to that of the spouting portion 52 in the first embodiment. The spouting portion 52a scatters the diluted first liquid Lla into the chamber 3. Likewise, the spouting portion 52b is arranged on both sides of the substrate W at the first position Pl in the direction Y. The spouting portion 52b scatters the non-diluted first liquid Llb into the chamber 3. The spouting portion 52b has a structure similar to that of the spouting portion 52 in the first embodiment.

[0168] The supply unit 51 includes a pipe 53a and a valve 54a. The pipe 53a is connected to the spouting portion 52a. The pipe 53a is further connected to a supply source 55a. The supply source 55a stores the diluted first liquid Lla. The valve 54a is provided to the pipe 53a. The valve 54a controls the scattering of the diluted first liquid Lla by the spouting portion 52a. Likewise, the supply unit 51 includes a pipe 53b and a valve 54b. The pipe 53b is connected to the spouting portion 52b. The pipe 53b is further connected to a supply source 55b. The supply source 55b stores the non-diluted first liquid Llb. The valve 54b is provided to the pipe 53b. The valve 54b controls the scattering of the non-diluted first liquid Llb by the spouting portion 52b.

[0169] The supply unit 61 supplies a third liquid L3 to the processing tank 11 in addition to the second liquid L2. The third liquid L3 is a diluted organic solvent. The third liquid L3 is, for example, an organic solvent diluted by pure water. The third liquid L3 is, for example, a mixture of pure water and an organic solvent.

[0170] The structure of the supply unit 61 is exemplified. The supply unit 61 includes a pipe 67 and a valve 68. The pipe 67 is connected to the spouting portion 62. The pipe 67 is further connected to a supply source 69. The supply source 69 stores the third liquid L3. The valve 68 is provided to the pipe 67. The valve 68 controls the spouting of the third liquid L3 by the spouting portion 62.

[0171] The substrate processing apparatus 1 includes a supply unit 71. The supply unit 71 supplies a mixed gas to the chamber 3. The supply unit 71 supplies the mixed gas to the substrate W when the substrate W is at the first position PI.

[0172] The mixed gas is described. The mixed gas contains an organic solvent and an inert gas. The mixed gas is a mixture of the organic solvent and the inert gas. The mixed gas contains at least either a gas of the organic solvent or a liquid of the organic solvent. That is, the organic solvent of the mixed gas is at least either a gas phase or a liquid phase. The gas of the organic solvent in the mixed gas is, for example, a vapor of the organic solvent. The liquid of the organic solvent in the mixed gas is, for example, at least either a droplet of the organic solvent or a mist of the organic solvent. The organic solvent of the mixed gas is, for example, isopropyl alcohol (IPA). The inert gas of the mixed gas is, for example, nitrogen.

[0173] A structure of the supply unit 71 is exemplified. The supply unit 71 includes a spouting portion 72. The spouting portion 72 is disposed in the chamber 3. The spouting portion 72 is arranged at a position higher than the processing tank 11. The spouting portion 72 is arranged in the direction Y on both sides of the substrate W at the first position PI. The spouting portion 72 spouts the mixed gas into the chamber 3. The spouting portion 72 contains a plurality of (for example, twenty) dual-fluid nozzles. The plurality of dual-fluid nozzles are arranged in two rows in the direction X. Each dual-fluid nozzle mixes the organic solvent and the inert gas to generate the mixed gas. For example, each dual-fluid nozzle generates at least either a droplet of the organic solvent or a mist of the organic solvent. Each dual-fluid nozzle has one spouting outlet (not shown). Each dual-fluid nozzle spouts the mixed gas from the spouting outlet. Each dual-fluid nozzle blows both the organic solvent and the inert gas from the spouting outlet. Each dual-fluid nozzle blows both the organic solvent and the inert gas from the spouting outlet at the same time. Each dual-fluid nozzle does not independently blow the organic solvent and the inert gas. Each dual-fluid nozzle spouts at least either a droplet of the organic solvent or a mist of the organic solvent together with the inert gas.

[0174] The supply unit 71 includes a pipe 73, a pipe 77, and a valve 74, a valve 78. The pipe 73, the pipe 77 are connected to the spouting portion 72, respectively. The pipe 73 is further connected to a supply source 75. The supply source 75 stores the organic solvent. The valve 74 is provided to the pipe 73. The valve 74 controls the supply of the organic solvent to the spouting portion 72. The pipe 77 is further connected to a supply source 79. The supply source 79 stores the inert gas. The valve 78 is provided to the pipe 77. The valve 78 controls the supply of the inert gas to the spouting portion 72. When the valve 74, the valve 78 are opened at the same time, the spouting portion 72 spouts the mixed gas.

[0175] The substrate processing apparatus 1 has a pressure sensor 89. The pressure sensor 89 is disposed in the chamber 3. The pressure sensor 89 detects the pressure of the gas in the chamber 3.

[0176] The processing tank 11 has an opening 12a and a discharge port 12b. The opening 12a is disposed at the upper part of the processing tank 11. The opening 12a is large enough. When the substrate W moves between a first position P1 and a second position P2, the substrate W passes through the opening 12a. The discharge port 12b is disposed at the bottom of the processing tank 11.

[0177] The substrate processing apparatus 1 includes a dump unit 91. The dump unit 91 discharges the processing liquid from the processing tank 11. A chamber 3 receives the processing liquid discharged from the processing tank 11. The processing liquid discharged from the processing tank 11 accumulates at the bottom of the chamber 3. The dump unit 91 includes a dump valve 92. The dump valve 92 is disposed inside the chamber 3. The dump valve 92 is mounted at the bottom of the processing tank 11. The dump valve 92 is connected to a discharge port 12b. When the dump valve 92 is open, the dump unit 91 allows the processing liquid to flow from the inside of the processing tank 11 to the outside of the processing tank 11 through the dump valve 92. When the dump valve 92 is closed, the dump unit 91 allows the processing tank 11 to store the processing liquid.

[0178] The substrate processing apparatus 1 includes a drainage unit 95. The drainage unit 95 drains the processing liquid from the chamber 3 to the outside of the chamber 3. The drainage unit 95 includes a pipe 96 and a drain valve 97. The pipe 96 is located outside the chamber 3 and is connected to the chamber 3. The pipe 96 has a first end and a second end. The first end of the pipe 96 is connected to the bottom of the chamber 3. The pipe 96 extends downward from the chamber 3. The second end of the pipe 96 is open to the atmosphere outside the chamber 3. The drain valve 97 is located on the pipe 96. The drain valve 97 opens and closes the pipe 96. When the drain valve 97 is open, the pipe 96 is open to the outside of the chamber 3. When the drain valve 97 is open, the interior of the chamber 3 is open to the outside of the chamber 3 through the pipe 96. When the drain valve 97 is open, the drain unit 95 allows the processed liquid in chamber 3 to flow out to the outside of chamber 3 through pipe 96. When the drain valve 97 is closed, the inside of chamber 3 is isolated from the outside of chamber 3. When the drain valve 97 is closed, the drain unit 95 allows the inside of chamber 3 to be in a depressurized state D.

[0179] Pipe 96 is an example of a drain pipe in this invention.

[0180] Although not shown in the diagram, control unit 101 controls valve 68. Control unit 101 controls supply unit 71. Control unit 101 controls valves 74 and 78. Control unit 101 acquires the detection results from pressure sensor 89. Control unit 101 controls leakage unit 91 and drainage unit 95. Control unit 101 controls leakage valve 92 and discharge valve 97.

[0181] <2-2. Example of operation of substrate processing apparatus>

[0182] Figure 6 、 Figure 7 are flowcharts each schematically showing a flow of a substrate processing method according to the second embodiment. The substrate processing method includes steps Sll to S29. Steps Sll to S17 are executed in this order. Steps S18 to S20 are executed after step S17 and before step S21. Steps S21 to S29 are executed in this order.

[0183] Figures 8A to 8E 、 Figures 9A to 9E 、 Figures 10A to 10E 、 Figures 11A to 11C are diagrams each schematically showing the substrate processing apparatus 1 in steps Sll to S21, S23 to S29. Figures 8A to 8E and the like each briefly show the substrate processing apparatus 1.

[0184] Step Sll: First supply process

[0185] Referring to Figure 8A . The substrate W is located at the first position Pl. The inside of the chamber 3 is in the normal pressure state J. The supply unit 61 supplies the second liquid L2 to the processing tank 11. The drain valve 92 is closed. The processing tank 11 stores the second liquid L2. Subsequently, the supply unit 61 stops the supply of the second liquid L2.

[0186] Step S12: First immersion process

[0187] Referring to Figure 8B . The inside of the chamber 3 is in the normal pressure state J. The lift mechanism 15 moves the substrate W from the first position Pl to the second position P2. The substrate W is immersed in the second liquid L2 in the processing tank 11.

[0188] Step S13: Atmosphere forming process

[0189] Referring to Figure 8C . The substrate W is located at the second position P2 and is immersed in the second liquid L2 in the processing tank 11. The supply unit 21 supplies the inert gas N into the chamber 3. The decompression unit 81 starts operation. The exhaust valve 97 is closed. The inside of the chamber 3 is changed from the normal pressure state J to the decompressed state D. The atmosphere of the inert gas N is formed in the chamber 3.

[0190] Step S14: Atmosphere forming process

[0191] Referring to Figure 8DThe substrate W is located at the second position P2 and is immersed in the second liquid L2 in the processing tank 11. The decompression unit 81 is in operation. The inside of the chamber 3 is kept in the decompressed state D. The supply unit 21 stops the supply of the inert gas N. The supply unit 41 supplies the first gas G1 into the chamber 3. An atmosphere of the first gas G1 is formed in the chamber 3.

[0192] Step S15: First gas processing step (first gas processing)

[0193] Referring to Figure 8E The decompression unit 81 is in operation. The inside of the chamber 3 is kept in the decompressed state D. The supply unit 41 supplies the first gas G1 into the chamber 3. The lifting mechanism 15 moves the substrate W from the second position P2 to the first position P1. The substrate W is lifted from the second liquid L2 in the processing tank 11. The substrate W is exposed to the first gas G1. The gas of the organic solvent contained in the first gas G1 becomes the liquid of the organic solvent on the surface of the substrate W. The organic solvent derived from the first gas G1 removes the second liquid L2 on the substrate W. The liquid of the organic solvent derived from the first gas G1 covers the surface of the substrate W.

[0194] Step S16: Drainage step

[0195] Referring to Figure 9A The substrate W is located at the first position P1. The supply unit 41 supplies the first gas G1 to the substrate W in the chamber 3. The decompression unit 81 is in operation. The inside of the chamber 3 is kept in the decompressed state D. The drainage valve 92 is opened. The drainage unit 91 drains the second liquid L2 from the processing tank 11. The discharge valve 97 is closed. The second liquid L2 is accumulated in the bottom of the chamber 3.

[0196] Step S17: Hydrophobic treatment step (hydrophobic treatment)

[0197] Referring to Figure 9B The substrate W is located at the first position P1. The decompression unit 81 is in operation. The inside of the chamber 3 is kept in the decompressed state D. The supply unit 41 stops the supply of the first gas G1. The supply unit 31 supplies the hydrophobic agent H to the substrate W in the chamber 3. The hydrophobic agent H adheres to the substrate W. On the substrate W, the hydrophobic agent H is substituted for the organic solvent derived from the first gas G1. The hydrophobic agent H covers the surface of the substrate W. The hydrophobic agent H hydrophobizes the substrate W. A part of the hydrophobic agent H on the substrate W becomes the hydrophobic film. Another part of the hydrophobic agent H on the substrate W becomes the unreacted component of the hydrophobic agent H. Further, another part of the hydrophobic agent H on the substrate W sometimes becomes the particle.

[0198] Subsequently, the supply unit 31 stops the supply of the hydrophobic agent H.

[0199] Step S18: Second gas processing step

[0200] Referring to Figure 9C The substrate W is located at the first position Pl. The depressurizing unit 81 is in operation. The inside of the chamber 3 is kept in the depressurized state D. The supply unit 41 supplies the processing gas to the substrate W in the chamber 3. In this specification, the processing gas supplied to the chamber 3 in the second gas processing step is appropriately called "second gas G2". The gas of the organic solvent contained in the second gas G2 becomes the liquid of the organic solvent on the surface of the substrate W. The organic solvent derived from the second gas G2 removes the unreacted hydrophobic agent H on the substrate W. The organic solvent derived from the second gas G2 also removes the particles derived from the hydrophobic agent H on the substrate W. The liquid of the organic solvent derived from the second gas G2 covers the surface of the substrate W. Subsequently, the supply unit 41 stops the supply of the second gas G2.

[0201] Step S19: First spreading step (spreading processing)

[0202] Referring to Figure 9D The substrate W is located at the first position Pl. The depressurizing unit 81 is in operation. The inside of the chamber 3 is kept in the depressurized state D. The supply unit 51 spreads the diluted first liquid Lla to the substrate W in the chamber 3. The diluted first liquid Lla adheres to the substrate W. The diluted first liquid Lla removes the unreacted hydrophobic agent H on the substrate W. The diluted first liquid Lla also removes the particles derived from the hydrophobic agent H on the substrate W. The diluted first liquid Lla covers the surface of the substrate W.

[0203] In the first spreading step, the lifting mechanism 15 can also stop the substrate W at the first position Pl. Alternatively, in the first spreading step, the lifting mechanism 15 can also move the substrate W up and down. For example, the lifting mechanism 15 can also move the substrate W up and down in the vicinity of the first position Pl. For example, the lifting mechanism 15 can also move the substrate W up and down in the vertical direction Z. Alternatively, the lifting mechanism 15 can further include a not-shown mechanism that swings the substrate W. The lifting mechanism 15 can also swing the substrate W by the mechanism. In the case where the substrate W is moved up and down or swung, the entire substrate W preferably receives the diluted first liquid Lla. In the case where the substrate W is moved up and down or swung, the diluted first liquid Lla more uniformly adheres to the entire surface of the substrate W.

[0204] Subsequently, the supply unit 51 stops the spreading of the diluted first liquid Lla.

[0205] Step S20: Second spreading step (spreading processing)

[0206] Referring to Figure 9EThe substrate W is located at the first position Pl. The depressurizing unit 81 is in operation. The inside of the chamber 3 is kept in the depressurized state D. The supply unit 51 spreads the non-diluted first liquid Llb to the substrate W in the chamber 3. The non-diluted first liquid Llb adheres to the substrate W. The non-diluted first liquid Llb removes the unreacted hydrophobic agent H on the substrate W. The non-diluted first liquid Llb also removes the particles derived from the hydrophobic agent H on the substrate W. The non-diluted first liquid Llb covers the surface of the substrate W.

[0207] In the second spreading process, the lifting mechanism 15 can also stop the substrate W at the first position Pl. Alternatively, in the second spreading process, the lifting mechanism 15 can also move the substrate W up and down. For example, the lifting mechanism 15 can also move the substrate W up and down in the vicinity of the first position Pl. For example, the lifting mechanism 15 can also move the substrate W up and down in the vertical direction Z. Alternatively, the lifting mechanism 15 can further include a not-shown mechanism that swings the substrate W. The lifting mechanism 15 can also swing the substrate W by the mechanism. In the case where the substrate W is moved up and down or swung, the entire substrate W preferably receives the non-diluted first liquid Llb. In the case where the substrate W is moved up and down or swung, the non-diluted first liquid Llb more uniformly adheres to the entire surface of the substrate W.

[0208] Subsequently, the supply unit 51 stops the spreading of the non-diluted first liquid Llb.

[0209] Here, the second gas treatment process, the first spreading process, and the second spreading process can also be executed in any order. For example, the first spreading process can also be executed before the second gas treatment process. For example, the first spreading process can also be executed after the second gas treatment process. For example, the first spreading process can also be executed simultaneously with the second gas treatment process. Likewise, for example, the second spreading process can also be executed at least either before or after the first spreading process. For example, the second spreading process can also be executed simultaneously with the first spreading process. For example, the second gas treatment process can also be executed at least either before or after the second spreading process. For example, the second gas treatment process can also be executed simultaneously with the second spreading process.

[0210] Here, the first dispersing process and the second dispersing process are collectively referred to as a dispersing process. The amount of the diluted first liquid Lla supplied by the supply unit 51 in the first dispersing process is referred to as an amount Mla. The amount of the non-diluted first liquid Llb supplied by the supply unit 51 in the second dispersing process is referred to as an amount Mlb. The sum of the amount Mla and the amount Mlb is referred to as an amount Ml. The amount Ml corresponds to the amount of the first liquid Ll supplied by the supply unit 51 in the dispersing process. The amount of the second gas G2 supplied by the supply unit 41 in the second gas treatment process is referred to as an amount M2. The amount Ml is greater than the amount M2. The amount Ml is, for example, twice or more the amount M2. The amount Mla is, for example, greater than the amount M2. The amount Mla is, for example, twice or more the amount M2. The amount Mlb is, for example, greater than the amount M2. The amount Mlb is, for example, twice or more the amount M2.

[0211] The amount Ml, the amount Mla, the amount Mlb, and the amount M2 are, for example, each a mass. The amount Ml, the amount Mla, the amount Mlb, and the amount M2 are, for example, each a volume. In the case where the amount Ml, the amount Mla, the amount Mlb, and the amount M2 are each a volume, the amount M2 is set to a value converted into a liquid. For example, the amount M2 is the volume of a liquid obtained by condensing the second gas G2. For example, the amount M2 is the volume of a liquid used for generating the second gas G2.

[0212] The time for which the first dispersing process is performed is referred to as a time Tla. The time for which the second dispersing process is performed is referred to as a time Tlb. The sum of the time Tla and the time Tlb is referred to as a time Tl. The time Tl corresponds to the time for which the dispersing process is performed. The time for which the second gas treatment process is performed is referred to as a time T2. The time Tl is longer than the time T2. The time Tla is, for example, longer than the time T2. The time Tlb is, for example, longer than the time T2.

[0213] The amount Ml per unit time is referred to as a flow rate Rl. The amount Mla per unit time is referred to as a flow rate Rla. The amount Mlb per unit time is referred to as a flow rate Rlb. The amount M2 per unit time is referred to as a flow rate R2. The flow rate Rl is, for example, a value obtained by dividing the amount Ml by the time Tl. The flow rate Rla is, for example, a value obtained by dividing the amount Mla by the time Tla. The flow rate Rlb is, for example, a value obtained by dividing the amount Mlb by the time Tlb. The flow rate R2 is, for example, a value obtained by dividing the amount M2 by the time T2. The flow rate Rl is greater than the flow rate R2. The flow rate Rl is, for example, twice or more the flow rate R2. The flow rate Rla is, for example, greater than the flow rate R2. The flow rate Rla is, for example, twice or more the flow rate R2. The flow rate Rlb is, for example, greater than the flow rate R2. The flow rate Rlb is, for example, twice or more the flow rate R2.

[0214] Step S21: First pressurizing process

[0215] Reference Signs List Figure 10AThe substrate W is located at the first position P1. The decompression unit 81 stops operating. The supply unit 71 supplies the mixed gas K to the substrate W inside the chamber 3. Thereby, the inside of the chamber 3 is pressurized from the decompressed state D to the normal pressure state J. Specifically, the inert gas of the mixed gas K rapidly pressurizes the inside of the chamber 3 from the decompressed state D to the normal pressure state J. In other words, the inert gas of the mixed gas K rapidly increases the pressure of the gas inside the chamber 3. This is because the inert gas is difficult to condense.

[0216] The organic solvent of the mixed gas K wets the substrate W. For example, when the mixed gas K includes a gas of the organic solvent, the gas of the organic solvent included in the mixed gas K dew condenses on the surface of the substrate W, and becomes a liquid of the organic solvent on the surface of the substrate W. For example, when the mixed gas K includes a liquid of the organic solvent, the liquid of the organic solvent included in the mixed gas K adheres to the surface of the substrate W. Therefore, in the first pressurization process, the substrate W is not dried. The inside of the chamber 3 becomes the normal pressure state J without drying the substrate W.

[0217] In the first pressurization process, the lifting mechanism 15 can also stop the substrate W at the first position P1. Alternatively, in the first pressurization process, the lifting mechanism 15 can also move the substrate W up and down. For example, the lifting mechanism 15 can also move the substrate W up and down in the vicinity of the first position P1. For example, the lifting mechanism 15 can also move the substrate W up and down in the vertical direction Z. Alternatively, the lifting mechanism 15 can further include an unillustrated mechanism that swings the substrate W. The lifting mechanism 15 can also swing the substrate W by the mechanism. In the case where the substrate W is moved up and down or swung, the entire substrate W preferably receives the mixed gas K. In the case where the substrate W is moved up and down or swung, the organic solvent of the mixed gas K more uniformly adheres to the entire surface of the substrate W.

[0218] Step S22: Determination Process

[0219] The control section 101 determines whether or not the inside of the chamber 3 has become the normal pressure state J on the basis of the detection result of the pressure sensor 89. For example, the control section 101 acquires a measured value of the pressure of the gas inside the chamber 3 on the basis of the detection result of the pressure sensor 89. The control section 101 compares the measured value with a reference value. The reference value is set in advance before the execution of the substrate processing method. The reference value is included in the processing information possessed by the control section 101. When the measured value is less than the reference value, the control section 101 does not determine that the inside of the chamber 3 has become the normal pressure state J. When the measured value is the reference value or more, the control section 101 determines that the inside of the chamber 3 has become the normal pressure state J. If the control section 101 does not determine that the inside of the chamber 3 has become the normal pressure state J, the process returns to step S21, and the first pressurization process is continued. If the control section 101 determines that the inside of the chamber 3 has become the normal pressure state J, the first pressurization process is ended, and the process proceeds to step S23.

[0220] Step S23: First draining process

[0221] Referring to Figure 10B The substrate W is located at the first position PI. The supply unit 71 supplies the mixed gas K to the substrate W in the chamber 3. The decompression unit 81 is in the stop. The inside of the chamber 3 is kept in the normal pressure state J. The atmosphere in the chamber 3 contains the organic solvent derived from the mixed gas K. The draining unit 95 drains the second liquid L2 in the chamber 3 to the outside of the chamber 3. Specifically, the drain valve 97 opens the pipe 96 to the atmosphere outside the chamber 3. The second liquid L2 accumulated in the chamber 3 is drained to the outside of the chamber 3 through the pipe 96. The second liquid L2 flows from the inside of the chamber 3 to the outside of the chamber 3 through the pipe 96.

[0222] Step S24: Second supply process

[0223] Referring to Figure 10C The substrate W is located at the first position PI. The supply unit 71 supplies the mixed gas K to the substrate W in the chamber 3. The decompression unit 81 is in the stop. The inside of the chamber 3 is kept in the normal pressure state J. The atmosphere in the chamber 3 contains the organic solvent derived from the mixed gas K. The drain valve 92 is closed. The supply unit 61 supplies the third liquid L3 to the treatment tank 11. The treatment tank 11 stores the third liquid L3.

[0224] Step S25: Second immersion process

[0225] Referring to Figure 10D The supply unit 71 supplies the mixed gas K to the substrate W in the chamber 3. The decompression unit 81 is in the stop. The inside of the chamber 3 is kept in the normal pressure state J. The atmosphere in the chamber 3 contains the organic solvent derived from the mixed gas K. The lifting mechanism 15 moves the substrate W from the first position PI to the second position P2. The substrate W is immersed in the third liquid L3 in the treatment tank 11. The third liquid L3 cleans the substrate W. For example, the third liquid L3 removes the unreacted hydrophobic agent H on the substrate W. For example, the third liquid L3 also removes the particles derived from the hydrophobic agent H on the substrate W.

[0226] The liquid discharge unit 95 discharges the third liquid L3 in the chamber 3 to the outside of the chamber 3. The liquid discharge unit 95 discharges the third liquid L3 overflowing from the treatment tank 11 to the outside of the chamber 3. Specifically, the supply unit 61 continuously supplies the third liquid L3 to the treatment tank 11. The drain valve 92 is closed. The third liquid L3 overflows from the opening 12a of the treatment tank 11. When the third liquid L3 overflows from the treatment tank 11, the hydrophobic agent removed from the substrate W also overflows from the treatment tank 11. When the third liquid L3 overflows from the treatment tank 11, the particles derived from the hydrophobic agent H removed from the substrate W also overflows from the treatment tank 11. The third liquid L3 overflowing from the treatment tank 11 is accumulated at the bottom of the chamber 3. The exhaust valve 97 is opened. The pipe 96 is opened to the atmosphere outside the chamber 3. The third liquid L3 accumulated at the bottom of the chamber 3 flows to the outside of the chamber 3 through the pipe 96.

[0227] Step S26: Atmosphere forming process

[0228] Referring to Figure 10E The substrate W is located at the second position P2 and is immersed in the third liquid L3 in the treatment tank 11. The supply unit 61 stops the supply of the third liquid L3. The exhaust valve 97 is closed. The supply unit 71 stops the supply of the mixed gas K. The supply unit 41 supplies the treatment gas into the chamber 3. In this specification, the treatment gas supplied into the chamber 3 after the second immersion process is appropriately called "third gas G3". The depressurization unit 81 starts operation. The inside of the chamber 3 becomes the depressurized state D from the normal pressure state J. The atmosphere of the third gas G3 is formed in the chamber 3.

[0229] Step S27: Third gas treatment process

[0230] Referring to Figure 11A The depressurization unit 81 is in operation. The inside of the chamber 3 is maintained in the depressurized state D. The supply unit 41 supplies the third gas G3 into the chamber 3. The lifting mechanism 15 moves the substrate W from the second position P2 to the first position P1. The substrate W is lifted from the third liquid L3 in the treatment tank 11. The supply unit 41 supplies the third gas G3 to the substrate W. The gas of the organic solvent contained in the third gas G3 becomes the liquid of the organic solvent on the surface of the substrate W. The organic solvent derived from the third gas G3 removes the third liquid L3 on the substrate W. The liquid of the organic solvent derived from the third gas G3 covers the surface of the substrate W.

[0231] Step S28: Drying process

[0232] Referring to Figure 11BThe substrate W is located at the first position PI. The depressurizing unit 81 is in operation. The inside of the chamber 3 is kept in the depressurized state D. The supply unit 41 stops the supply of the third gas G3. The supply unit 21 supplies the inert gas N to the substrate W. The inert gas N removes the organic solvent on the substrate W. The substrate W is dried.

[0233] Step S29: Second pressurizing process

[0234] Referring to Figure 11C The substrate W is located at the first position PI. The supply unit 21 supplies the inert gas N. The depressurizing unit 81 stops operation. The inside of the chamber 3 is pressurized from the depressurized state D to the normal pressure state J.

[0235] <2-3. Effects of the second embodiment>

[0236] With the second embodiment, the same effects as the first embodiment are exerted. For example, with the substrate processing method of the second embodiment, the particles on the substrate W are preferably reduced. Further, with the second embodiment, the following effects are exerted.

[0237] The scattering process includes a first scattering process and a second scattering process. In the first scattering process, the first liquid LI is the diluted first liquid Lla. In the first scattering process, the diluted first liquid Lla is scattered as the first liquid LI. Thus, the amount of the organic solvent used in the first scattering process is preferably reduced. In the second scattering process, the first liquid LI is the non-diluted first liquid Lib. In the second scattering process, the non-diluted first liquid Lib is scattered as the first liquid LI. The non-diluted first liquid Lib is substantially free of water. Thus, the non-diluted first liquid Lib has a small surface tension. As a result, in the second scattering process, the non-diluted first liquid Lib does not cause an intentional force to the substrate W. As a result, in the second scattering process, the substrate W is preferably protected. In the second scattering process, the pattern formed on the surface of the substrate W is preferably protected.

[0238] The substrate processing method includes a second gas treatment process. The second gas treatment process is performed after the hydrophobic treatment process. In the second gas treatment process, the inside of the chamber 3 is in the depressurized state D, and the second gas G2 is supplied to the substrate W in the chamber 3. The second gas G2 includes a gas of an organic solvent. In the second gas treatment process, the entire substrate W is exposed to the second gas G2. Thus, in the second gas treatment process, the organic solvent derived from the second gas G2 is rapidly attached to the entire substrate W. In the second gas treatment process, the organic solvent derived from the second gas G2 is uniformly attached to the entire substrate W. As a result, in the second gas treatment process, the uniformity of the cleanliness of the substrate W throughout the entire substrate W is improved.

[0239] The amount Ml of the first liquid Ll supplied in the scattering process is greater than the amount M2 of the second gas G2 supplied in the second gas treatment process. Thus, in the scattering process, the first liquid Ll more appropriately removes the particles on the substrate W.

[0240] The time Tl for performing the scattering process is longer than the time T2 for performing the second gas treatment process. Thus, in the scattering process, the particles on the substrate W are more appropriately removed.

[0241] The flow rate Rl of the first liquid Ll in the scattering process is greater than the flow rate R2 of the second gas G2 in the second gas treatment process. Thus, in the scattering process, the first liquid Ll more appropriately removes the particles on the substrate W.

[0242] The substrate processing method includes a first pressurization process and a first liquid discharge process. The first pressurization process is performed after the scattering process. In the first pressurization process, the inside of the chamber 3 is pressurized from the depressurized state D to the normal pressure state J. The first liquid discharge process is performed after the first pressurization process. In the first liquid discharge process, the inside of the chamber 3 is kept in the normal pressure state J, and the second liquid L2 is discharged to the outside of the chamber 3. When the inside of the chamber 3 is in the normal pressure state J, the pressure of the gas in the chamber 3 approaches the pressure of the gas outside the chamber 3. Therefore, in the first liquid discharge process, the second liquid L2 in the chamber 3 is easily discharged to the outside of the chamber 3.

[0243] In the first liquid discharge process, the pipe 96 is open to the atmosphere outside the chamber 3. The pipe 96 is communicatively connected to the chamber 3. As described above, in the first liquid discharge process, the inside of the chamber 3 is in the normal pressure state J. Therefore, in the first liquid discharge process, the second liquid L2 flows from the inside of the chamber 3 to the outside of the chamber 3 through the pipe 96 by the self-weight of the second liquid L2. In the first liquid discharge process, the second liquid L2 naturally flows from the inside of the chamber 3 to the outside of the chamber 3 through the pipe 96. In the first liquid discharge process, the second liquid L2 does not need to be forcibly sent from the inside of the chamber 3 to the outside of the chamber 3. Thus, in the first liquid discharge process, the second liquid L2 in the chamber 3 is easily discharged to the outside of the chamber 3 through the pipe 96.

[0244] In the first pressurization process, the mixed gas K is supplied to the substrate W in the chamber 3. The mixed gas K contains the organic solvent and the inert gas. Therefore, in the first pressurization process, the substrate W is not dried. In the first pressurization process, the substrate W in the chamber 3 is not dried, and the inside of the chamber 3 is rapidly pressurized from the depressurized state D to the normal pressure state J.

[0245] The mixed gas contains at least either one of the gas of the organic solvent and the liquid of the organic solvent. Therefore, the organic solvent derived from the mixed gas K preferably wets the substrate W. Thus, the mixed gas K preferably prevents the substrate from being dried.

[0246] The substrate processing method includes a second immersion process. The second immersion process is performed after the first draining process. In the second immersion process, the substrate W is immersed in the third liquid L3 stored in the processing tank 11. Therefore, in the second immersion process, the substrate W receives a large amount of the third liquid L3. In the second immersion process, the third liquid L3 more preferably removes particles on the substrate W. Thus, the particles on the substrate W are more preferably reduced. As a result, the cleanliness of the substrate W is more preferably improved. The processing quality of the substrate W is more preferably improved.

[0247] From the first pressurization process until the substrate W is immersed in the third liquid L3, the atmosphere in the chamber 3 contains the organic solvent. Therefore, from the first pressurization process until the substrate W is immersed in the third liquid L3, the organic solvent contained in the atmosphere in the chamber 3 wets the substrate W. Thus, from the first pressurization process until the second immersion process, the substrate W is not dried. The substrate W is not dried after the spreading process and before the second immersion process. Therefore, in the second immersion process, the substrate W is processed with an appropriate quality.

[0248] The third liquid L3 is a diluted organic solvent. Therefore, the third liquid L3 appropriately removes particles on the substrate W.

[0249] The present application is not limited to the first embodiment and the second embodiment, and can be modified as follows.

[0250] (1) In the first embodiment and the second embodiment, the ejection section 52 includes the showerhead nozzle. However, the present application is not limited thereto. For example, the ejection section 52 can include the dual-fluid nozzle. For example, the ejection section 52 can include at least either one of the showerhead nozzle and the dual-fluid nozzle. The dual-fluid nozzle of the ejection section 52 has, for example, substantially the same structure as that of the dual-fluid nozzle of the ejection section 72. The dual-fluid nozzle of the ejection section 52, for example, ejects at least either one of the droplets of the first liquid L1 and the mist of the first liquid L1 together with the inert gas. Thus, the dual-fluid nozzle of the ejection section 52 more preferably spreads the first liquid L1.

[0251] (2) In the second embodiment, the spreading process includes the first spreading process and the second spreading process. However, the present application is not limited thereto. For example, the spreading process can omit either one of the first spreading process and the second spreading process. For example, the spreading process can include at least either one of the first spreading process and the second spreading process.

[0252] (3) In the second embodiment, the pipe 96 of the liquid draining unit 95 is communicatively connected to the chamber 3. However, the present application is not limited thereto. For example, the pipe 96 can be communicatively connected to the processing tank 11. Specifically, the first end of the pipe 96 can be connected to the processing tank 11. In this modified embodiment, when the pipe 96 is opened to the atmosphere outside the chamber 3, the processing liquid in the processing tank 11 is drained outside the chamber 3 through the pipe 96.

[0253] (4) In the second embodiment, the third liquid L3 is a diluted organic solvent. However, it is not limited thereto. The third liquid L3 can be, for example, pure water (DIW). When the third liquid L3 is pure water, the third liquid L3 also appropriately removes particles on the substrate W.

[0254] (5) In the first embodiment and the second embodiment, the structures of the supply unit 21, the supply unit 31, the supply unit 41, the supply unit 51, the supply unit 61, and the supply unit 71 are illustrated. However, it is not limited thereto. The structures of the supply unit 21, the supply unit 31, the supply unit 41, the supply unit 51, the supply unit 61, and the supply unit 71 can be appropriately changed.

[0255] In the first embodiment and the second embodiment, the inert gas N, the hydrophobic agent H, the first gas G1, the first liquid L1, and the mixed gas K are sprayed from different spray portions 22, 32, 42, 52, 72. However, it is not limited thereto. At least two of the inert gas N, the hydrophobic agent H, the first gas G1, the first liquid L1, and the mixed gas K can be sprayed from the same spray portion.

[0256] In the second embodiment, the diluted first liquid L1a and the non-diluted first liquid L1b are sprayed from different spray portions 52a, 52b. However, it is not limited thereto. The diluted first liquid L1a and the non-diluted first liquid L1b can be sprayed from the same spray portion.

[0257] The supply unit 61 supplies the generated third liquid L3 to the processing tank 11. However, it is not limited thereto. The supply unit 61 can generate the third liquid L3 in the processing tank 11. For example, the supply unit 61 can independently supply an organic solvent that is not diluted and pure water to the processing tank 11.

[0258] The spray portion 72 (a two-fluid nozzle) generates the mixed gas K. However, it is not limited thereto. The spray portion 72 can not generate the mixed gas K. For example, the spray portion 72 can be communicatively connected to a supply source that stores the mixed gas K. For example, the supply source that stores the mixed gas K can further generate the mixed gas K. For example, the supply source that stores the mixed gas K can generate the mixed gas K by mixing a vapor of an organic solvent and an inert gas.

[0259] (6) In the first embodiment and the second embodiment, the flow of the substrate processing method is illustrated. However, it is not limited thereto. The flow of the substrate processing method can be appropriately changed.

[0260] For example, the substrate processing method of the first embodiment and the second embodiment includes the first immersion process. However, it is not limited thereto. The first immersion process can be omitted.

[0261] For example, in the second embodiment, the supply unit 71 supplies the mixed gas K into the chamber 3 from the first pressurization process until the second immersion process. However, the present application is not limited to this. For example, the supply unit 71 can supply the mixed gas K into the chamber 3 from the first pressurization process until the substrate W is immersed in the third liquid L3 in the processing tank 11. Also, the supply unit 71 can stop the supply of the mixed gas K after the substrate W is immersed in the third liquid L3 in the processing tank 11. According to the present modified embodiment, the atmosphere in the chamber 3 preferably contains the organic solvent of the mixed gas K from the first pressurization process until the substrate W is immersed in the third liquid L3 in the processing tank 11. Therefore, according to the present modified embodiment, the atmosphere in the chamber 3 preferably contains the organic solvent of the mixed gas K from the first pressurization process until the second immersion process.

[0262] Alternatively, the supply unit 71 can stop the supply of the mixed gas K after the first pressurization process. For example, the supply unit 71 can stop the supply of the mixed gas K in the first liquid discharge process, the second supply process, and the second immersion process. In the first pressurization process, the atmosphere of the mixed gas K is formed in the chamber 3. In the first liquid discharge process, the second supply process, and the second immersion process, the inside of the chamber 3 is not depressurized. In the first liquid discharge process, the second supply process, and the second immersion process, the gas in the chamber 3 is not discharged to the outside of the chamber 3. Therefore, the atmosphere of the mixed gas K remains in the chamber 3 from the first pressurization process until the second immersion process. Thus, according to the present modified embodiment, the atmosphere in the chamber 3 preferably contains the organic solvent of the mixed gas K from the first pressurization process until the second immersion process.

[0263] (7) For the first to third embodiments and each of the modified embodiments described in (1) to (6), each structure can be further replaced with the structure of another modified embodiment or combined with the structure of another modified embodiment, and the like, and appropriately changed.

[0264] The present application can be implemented in other embodiments without departing from the spirit or essential characteristics thereof, and, accordingly, specific shapes, configurations and the like disclosed herein are not to be understood as limiting the scope of the application. The disclosure is to be considered merely as illustrative of the principles of the application, and not in limitation thereof. Accordingly, the scope of the application is to be understood only as set forth in the following claims.

Claims

1. A substrate processing method, comprising processing multiple substrates housed in a cavity at one time, the substrate processing method comprising: In the first immersion process, the substrate is immersed in a second liquid stored in a processing tank, which is disposed in the chamber. In the first gas treatment step, after the first impregnation step, a first gas containing an organic solvent is supplied to the substrate inside the chamber under reduced pressure. In the hydrophobic treatment process, after the first gas treatment process, a hydrophobic agent is supplied to the substrate inside the chamber under reduced pressure; and In the dispersing process, after the hydrophobic treatment process, under reduced pressure inside the chamber, a first liquid containing an organic solvent is dispersed onto the substrate within the chamber. In the first gas treatment process, the hydrophobic treatment process, and the dispersing process, the substrate is located above the treatment tank.

2. The substrate processing method according to claim 1, wherein... The dispersing process disperses at least one of the first liquid droplets and the first liquid mist.

3. The substrate processing method according to claim 1, wherein... The dispersing process involves dispersing the first liquid using at least one of a spray nozzle and a dual-fluid nozzle.

4. The substrate processing method according to claim 1, wherein... In the dispersing process, the substrate is then moved up and down or oscillated within the cavity.

5. The substrate processing method according to claim 1, wherein... The dispersing process includes at least one of a first dispersing process and a second dispersing process. The first dispersing step involves dispersing an organic solvent that has been diluted into the first liquid. The second dispersing step is to disperse the organic solvent that has not been diluted into the first liquid.

6. The substrate processing method according to claim 1, further comprising: In the second gas treatment step, after the hydrophobic treatment step, a second gas containing an organic solvent is supplied to the substrate inside the chamber under reduced pressure.

7. The substrate processing method according to claim 6, wherein... The amount of the first liquid supplied in the dispersing process is greater than the amount of the second gas supplied in the second gas treatment process.

8. The substrate processing method according to claim 6, wherein The time required to perform the dispersing process is longer than the time required to perform the second gas treatment process.

9. The substrate processing method according to claim 1, further comprising: The first pressurization step involves pressurizing the interior of the chamber from a depressurized state to a normal pressure state after the dispersing process. as well as In the first drainage process, after the first pressurization process, the interior of the chamber is maintained at normal pressure, and the second liquid is discharged outside the chamber.

10. The substrate processing method according to claim 9, wherein... In the first drainage process, the drainage pipe connected to either the chamber or the processing tank is opened to the atmosphere outside the chamber, and the second liquid is discharged to the outside of the chamber through the drainage pipe.

11. The substrate processing method according to claim 9, wherein In the first pressurization process, a mixed gas containing organic solvent and inert gas is supplied to the substrate in the chamber.

12. The substrate processing method according to claim 11, wherein... The mixed gas contains at least one of the gaseous form of the organic solvent and the liquid form of the organic solvent.

13. The substrate processing method according to claim 9, further comprising: The second immersion process involves immersing the substrate in a third liquid stored in the processing tank after the first pressurization process.

14. The substrate processing method according to claim 13, wherein... From the first pressurization step until the substrate is immersed in the third liquid, the atmosphere in the chamber contains an organic solvent.

15. The substrate processing method according to claim 13, wherein... The third liquid is either a diluted organic solvent or pure water.

16. A substrate processing apparatus, comprising: A chamber that houses multiple substrates; A processing tank is disposed within the chamber to store the second liquid; A pressure reduction unit depressurizes the interior of the chamber; The first supply unit supplies a first gas containing an organic solvent to the substrate in the chamber; The second supply unit supplies the hydrophobic agent to the substrate inside the cavity; A dispensing unit that dispenses a first liquid containing an organic solvent into the substrate within the chamber; and The control unit controls the pressure reduction unit, the first supply unit, the second supply unit, and the distribution unit to perform the first impregnation treatment, the first gas treatment, the hydrophobic treatment, and the distribution treatment. In the first immersion process, the substrate is immersed in the second liquid stored in the processing tank. In the first gas processing, under reduced pressure by the pressure-reducing unit inside the chamber, the first supply unit supplies the first gas to the substrate. In the hydrophobic treatment, the second supply unit supplies the hydrophobic agent to the substrate inside the chamber under reduced pressure via the pressure-reducing unit. In the dispersion process, under reduced pressure inside the chamber via the pressure-reducing unit, the dispersion unit disperses the first liquid onto the substrate. In the first gas treatment, the hydrophobic treatment, and the dispersion treatment, the substrate is located above the treatment tank.

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