Substrate processing method, substrate processing apparatus, and processing liquid

Abstract

To provide a substrate processing method, a substrate processing apparatus, and a processing liquid, which can properly dry substrates.SOLUTION: The present invention relates to a substrate processing method, a substrate processing apparatus, and a processing liquid. The substrate processing method includes a processing liquid supply step, a solidified film formation step, and a sublimation step. In the processing liquid supply step, a processing liquid is supplied to a substrate. The processing liquid contains a sublimable substance and a solvent. In the solidified film formation step, the solvent is evaporated from the processing liquid on the substrate. In the solidified film formation step, a solidified film is formed on the substrate. The solidified film contains the sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried as a result of the sublimation of the solidified film. The sublimable substance contains at least one selected from among N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol and N-tert-butylacrylamide.SELECTED DRAWING: Figure 11

Description

[Technical field]

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

[0002] Patent Document 1 discloses a substrate processing method for processing a substrate. Specifically, the substrate processing method of Patent Document 1 includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to a substrate. The processing liquid includes a solvent and a sublimable substance. In the solidified film forming step, the solvent is evaporated and a solidified film is formed on the substrate. The solidified film includes a sublimable substance. In the sublimation step, the solidified film is sublimated. The solidified film changes into a gas without passing through a liquid state. The substrate is dried by the sublimation of the solidified film. Here, the sublimable substance includes at least one of pinacoline oxime, acetophenone oxime, cyclopentanone oxime, and 4-tert-butylphenol. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2022-170681 Summary of the Invention [Problem to be solved by the invention]

[0004] Even with the conventional substrate processing method, there are cases where the substrate cannot be dried properly. For example, even with the conventional substrate processing method, there are cases where the pattern formed on the substrate collapses. When the pattern is fine, the strength of the pattern is weak. For this reason, even with the conventional substrate processing method, there are cases where the fine pattern collapses.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a substrate processing method, a substrate processing apparatus, and a processing liquid that are capable of appropriately drying a substrate. [Means for solving the problem]

[0006] In order to achieve the above object, the present invention has the following configuration: That is, the present invention is a substrate processing method for processing a substrate on which a pattern is formed, comprising a processing liquid supplying step of supplying a processing liquid containing a sublimable substance and a solvent to the substrate, a solidified film forming step of evaporating the solvent from the processing liquid on the substrate to form a solidified film containing the sublimable substance on the substrate, and a sublimation step of sublimating the solidified film, wherein the sublimable substance contains at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide.

[0007] The substrate processing method is for processing a substrate on which a pattern is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid is supplied to a substrate. The processing liquid includes a sublimable substance and a solvent. In the solidified film forming step, the solvent is evaporated from the processing liquid on the substrate. In the solidified film forming step, a solidified film is formed on the substrate. The solidified film includes a sublimable substance. In the sublimation step, the solidified film is sublimated. The substrate is dried by the sublimation of the solidified film.

[0008] Here, the sublimable substance includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, the treatment liquid includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, in the solidified film forming process, the solidified film is suitably formed on the substrate.

[0009] The solidified film contains at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, in the sublimation process, the solidified film is appropriately sublimated. That is, in the sublimation process, the substrate is appropriately dried. Specifically, in the sublimation process, the substrate is dried while the pattern formed on the substrate is appropriately protected.

[0010] As described above, according to the present substrate processing method, the substrate is properly dried.

[0011] In the above-mentioned substrate processing method, the solvent is preferably isopropyl alcohol, which preferably dissolves N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide, and therefore the substrate is more appropriately dried.

[0012] The present invention is a substrate processing apparatus comprising a substrate holding unit that holds a substrate, and a processing liquid supply unit that supplies a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding unit, wherein the sublimable substance contains at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide.

[0013] The substrate processing apparatus includes a substrate holding unit and a processing liquid supply unit. The substrate holding unit holds a substrate. The processing liquid supply unit supplies a processing liquid to the substrate held by the substrate holding unit. The processing liquid includes a sublimable substance and a solvent.

[0014] Here, the sublimable substance includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, the treatment liquid includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, when the treatment liquid is supplied to the substrate, a solidified film is suitably formed on the substrate.

[0015] The solidified film contains at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, the solidified film is appropriately sublimated. That is, the substrate is appropriately dried. Specifically, the substrate is dried while the pattern formed on the substrate is appropriately protected.

[0016] As described above, according to the present substrate processing apparatus, the substrate is appropriately dried.

[0017] In the above-mentioned substrate processing apparatus, the solvent is preferably isopropyl alcohol, which dissolves N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide well, so that the substrate is more appropriately dried.

[0018] The present invention relates to a treatment liquid used for drying a substrate on which a pattern is formed, the treatment liquid including a sublimable substance and a solvent, the sublimable substance including at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide.

[0019] The processing liquid is used for drying the substrate on which the pattern is formed. Specifically, the processing liquid is a drying assistant liquid. The processing liquid contains a sublimable substance and a solvent.

[0020] Here, the sublimable substance includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, the treatment liquid includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, by supplying the treatment liquid to the substrate, a solidified film is suitably formed on the substrate.

[0021] The solidified film contains at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, the solidified film is appropriately sublimated. That is, the substrate is appropriately dried. Specifically, the substrate is dried while the pattern formed on the substrate is appropriately protected.

[0022] As described above, the substrate is appropriately dried using the processing liquid. The processing liquid is useful for drying the substrate.

[0023] In the above-mentioned treatment liquid, the solvent is preferably isopropyl alcohol. Isopropyl alcohol dissolves N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol and N-tert-butylacrylamide suitably. Therefore, the substrate is more appropriately dried using the treatment liquid. The treatment liquid is more useful for drying the substrate.

[0024] In the above-mentioned processing liquid, it is preferable that the processing liquid is supplied to the substrate, the solvent is evaporated from the processing liquid on the substrate, a solidified film containing the sublimable substance is formed on the substrate, and then the solidified film is sublimated. When the processing liquid is used in this way, the substrate is more appropriately dried. When the processing liquid is used in these procedures, the processing liquid is more useful for drying the substrate. Effect of the Invention

[0025] According to the substrate processing method, substrate processing apparatus, and processing solution of the present invention, the substrate is properly dried. [Brief description of the drawings]

[0026] [Figure 1] FIG. 2 is a diagram illustrating a schematic view of a portion of a substrate. [Diagram 2] 1 is a plan view showing an inside of a substrate processing apparatus according to an embodiment; [Diagram 3] FIG. 2 is a control block diagram of the substrate processing apparatus. [Figure 4]FIG. 2 is a diagram showing a configuration of a processing unit and a first supply source. [Diagram 5] 3 is a flowchart showing a procedure of a substrate processing method according to an embodiment. [Figure 6] 4A to 4C are diagrams illustrating a substrate in a treatment liquid supplying step. [Figure 7] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 8] 1A to 1C are diagrams illustrating a substrate in a solidified film forming step. [Figure 9] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Figure 10] FIG. 2 is a diagram illustrating a substrate during a sublimation process. [Figure 11] 1 is a table showing the quality of processing performed on substrates in Examples 1-3. [Figure 12] FIG. 13 is a diagram showing a configuration of a processing unit and a first supply source according to a modified embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Hereinafter, a substrate processing method, a substrate processing apparatus, and a processing liquid according to the present invention will be described with reference to the drawings.

[0028] <1. Substrate> The substrate W is, for example, a semiconductor wafer, a substrate for a liquid crystal display, a substrate for an organic EL (Electroluminescence), a substrate for an FPD (Flat Panel Display), a substrate for an optical display, a substrate for a magnetic disk, a substrate for an optical disk, a substrate for a magneto-optical disk, a substrate for a photomask, or a substrate for a solar cell. The substrate W has a thin flat plate shape. The substrate W has a substantially circular shape in a plan view.

[0029] 1 is a diagram illustrating a schematic view of a portion of a substrate W. The substrate W has a pattern P. The pattern P is formed on a surface of the substrate W.

[0030] The pattern P has, for example, an uneven shape. The pattern P has, for example, a convex portion W1 and a concave portion A. The convex portion W1 is a part of the substrate W. The convex portion W1 is a structure. The convex portion W1 is composed of, for example, at least one of a silicon oxide film (SiO2), a silicon nitride film (SiN), and a polysilicon film. The convex portion W1 protrudes upward from the surface of the substrate W, for example. The concave portion A is adjacent to the side of the convex portion W1. The concave portion A is a space. The concave portion A is, for example, open upward. The convex portion W1 corresponds to a wall that partitions the concave portion A.

[0031] <2. Processing liquid (drying aid liquid)> In this specification, the processing liquid used for drying the substrate W is simply called a "processing liquid." The processing liquid has a function of assisting in drying the substrate W. The processing liquid can be called an auxiliary drying liquid.

[0032] The treatment liquid contains a sublimable substance. The sublimable substance has sublimation properties. "Sublimation" refers to the property of a single substance, compound, or mixture to undergo phase transition from a solid to a gas or from a gas to a solid without passing through a liquid state.

[0033] The sublimable substance is, for example, compound a, b, or c. Compound a: N-Methyl-p-toluenesulfonamide Compound B: 2-Methyl-8-quinolinol Compound c: N-tert-Butylacrylamide

[0034] Compound a, i.e., N-methyl-p-toluenesulfonamide, is represented by the following chemical formula (1).

[0035] [ka]

[0036] Compound b, i.e., 2-methyl-8-quinolinol, is represented by the following chemical formula (2).

[0037] [ka]

[0038] Compound c, i.e., N-tert-butylacrylamide, is represented by the following chemical formula (3).

[0039] [ka]

[0040] The sublimable material includes at least one of compounds a, b, and c. For example, the sublimable material includes compound a. For example, the sublimable material includes compounds a and b. For example, the sublimable material includes compound ac.

[0041] For example, the sublimable material includes at least one of compounds b and c. For example, the sublimable material includes compound b. For example, the sublimable material includes compound c. For example, the sublimable material includes compound b and compound c.

[0042] For example, the sublimable substance consists of at least one of the compounds a and b. For example, the sublimable substance consists of only the compound a and b. For example, the sublimable substance consists of only the compound a and b.

[0043] For example, the sublimable substance consists of at least one of compounds b and c. For example, the sublimable substance consists of compound b only. For example, the sublimable substance consists of compound c only. For example, the sublimable substance consists of compounds b and c only.

[0044] For example, the sublimable substance is at least one of compounds a-c. For example, the sublimable substance is compound a. For example, the sublimable substance is compound a and compound b. For example, the sublimable substance is compound a-c.

[0045] For example, the sublimable substance is at least one of compounds b and c. For example, the sublimable substance is compound b. For example, the sublimable substance is compound c. For example, the sublimable substance is compounds b and c.

[0046] The treatment liquid includes a solvent. The solvent is, for example, a liquid. The solvent dissolves the sublimable substance. The sublimable substance in the treatment liquid is dissolved in the solvent. That is, the treatment liquid includes a solvent and a sublimable substance dissolved in the solvent. The sublimable substance corresponds to a solute of the treatment liquid.

[0047] The solvent can, for example, change from a liquid to a gas. The solvent can evaporate from a liquid.

[0048] The solvent has a relatively high vapor pressure at room temperature. For example, the vapor pressure of the solvent at room temperature is preferably higher than the vapor pressure of the sublimable substance at room temperature.

[0049] Here, normal temperature includes room temperature. Normal temperature is, for example, a temperature in the range of 5° C. or more and 35° C. or less. Normal temperature is, for example, a temperature in the range of 10° C. or more and 30° C. or less. Normal temperature is, for example, a temperature in the range of 20° C. or more and 25° C. or less.

[0050] The solvent is, for example, an organic solvent. The solvent is, for example, an alcohol.

[0051] The solvent includes, for example, isopropyl alcohol (IPA). The solvent consists, for example, of isopropyl alcohol. The solvent is, for example, isopropyl alcohol.

[0052] For example, the solvent is not water. The processing liquid includes a sublimable material and a solvent (but excluding water).

[0053] The processing liquid is, for example, made up of only a sublimable substance and a solvent.The processing liquid is, for example, made up of only a sublimable substance and a solvent (excluding water).

[0054] The processing liquid is, for example, composed only of at least one of the compounds a and c and isopropyl alcohol. The processing liquid is, for example, composed only of the compound a and isopropyl alcohol. The processing liquid is, for example, composed only of the compound a and isopropyl alcohol.

[0055] The processing liquid is, for example, composed only of at least one of compounds b and c and isopropyl alcohol. The processing liquid is, for example, composed only of compound b and isopropyl alcohol. The processing liquid is, for example, composed only of compound c and isopropyl alcohol. The processing liquid is, for example, composed only of compounds b and c and isopropyl alcohol.

[0056] The volume of the sublimable substance contained in the treatment liquid is smaller than the volume of the solvent contained in the treatment liquid.

[0057] The concentration CON of the sublimable substance in the processing liquid is the ratio of the volume of the sublimation agent to the volume of the processing liquid. The volume of the processing liquid is the sum of the volume of the solute and the volume of the solvent. Therefore, the concentration CON may be called the "volume concentration of the sublimable substance in the processing liquid."

[0058] For example, if the entire solute is a sublimable substance, the volume of the solute is equal to the volume of the sublimable substance. Therefore, the concentration CON of the sublimable substance in the treatment liquid is calculated by the following formula: CON=V1 / (V1+V2)*100 [Vol%] where V1 is the volume of the sublimable material and V2 is the volume of the solvent.

[0059] For example, the concentration CON of the sublimable substance in the treatment liquid is preferably 1 [Vol %] or more and 20 [Vol %] or less.

[0060] When the sublimable substance is compound a (i.e., N-methyl-p-toluenesulfonamide), the concentration CON is more preferably 1.96 [Vol%] or more. When the sublimable substance is compound a, the concentration CON is more preferably 12.50 [Vol%] or less.

[0061] When the sublimable substance is compound b (i.e., 2-methyl-8-quinolinol), the concentration CON is more preferably 5.88 [Vol%] or more. When the sublimable substance is compound b, the concentration CON is more preferably 9.09 [Vol%] or less.

[0062] When the sublimable substance is compound c (i.e., N-tert-butylacrylamide), the concentration CON is more preferably 1.96 [Vol%] or more. When the sublimable substance is compound c, the concentration CON is more preferably 2.44 [Vol%] or less.

[0063] <3. Overview of substrate processing equipment> 2 is a plan view showing the inside of the substrate processing apparatus 1 according to the embodiment. The substrate processing apparatus 1 performs processing on a substrate W. The processing in the substrate processing apparatus 1 includes a drying processing.

[0064] The substrate processing apparatus 1 includes an indexer unit 3 and a processing block 7. The processing block 7 is connected to the indexer unit 3. The indexer unit 3 supplies a substrate W to the processing block 7. The processing block 7 processes the substrate W. The indexer unit 3 retrieves the substrate W from the processing block 7.

[0065] For convenience, in this specification, the direction in which the indexer unit 3 and the processing block 7 are aligned is referred to as the "front-rear direction X." The front-rear direction X is horizontal. Within the front-rear direction X, the direction from the processing block 7 toward the indexer unit 3 is referred to as the "front." The direction opposite to the front is referred to as the "rear." The horizontal direction perpendicular to the front-rear direction X is referred to as the "width direction Y." One direction in the "width direction Y" is referred to as the "right" as appropriate. The direction opposite to the right is referred to as the "left." The direction perpendicular to the horizontal direction is referred to as the "vertical direction Z." In each figure, for reference, front, back, right, left, top, and bottom are indicated as appropriate.

[0066] The indexer unit 3 includes a plurality of (e.g., four) carrier placement units 4. Each carrier placement unit 4 places one carrier C thereon. The carrier C stores a plurality of substrates W. The carrier C is, for example, a Front Opening Unified Pod (FOUP), a Standard Mechanical Interface (SMIF), or an Open Cassette (OC).

[0067] The indexer unit 3 includes a transport mechanism 5. The transport mechanism 5 is disposed behind the carrier placement unit 4. The transport mechanism 5 transports the substrate W. The transport mechanism 5 is accessible to the carrier C placed on the carrier placement unit 4. The transport mechanism 5 is approachable to the carrier C placed on the carrier placement unit 4. The transport mechanism 5 includes a hand 5a and a hand drive unit 5b. The hand 5a supports the substrate W. The hand drive unit 5b is connected to the hand 5a. The hand drive unit 5b moves the hand 5a. The hand drive unit 5b moves the hand 5a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand drive unit 5b rotates the hand 5a, for example, in a horizontal plane.

[0068] The processing block 7 includes a transport mechanism 8. The transport mechanism 8 transports the substrate W. The transport mechanism 8 and the transport mechanism 5 are capable of transferring the substrate W to each other. The transport mechanism 8 includes a hand 8a and a hand driver 8b. The hand 8a supports the substrate W. The hand driver 8b is connected to the hand 8a. The hand driver 8b moves the hand 8a. The hand driver 8b moves the hand 8a, for example, in the front-rear direction X, the width direction Y, and the vertical direction Z. The hand driver 8b rotates the hand 8a, for example, in a horizontal plane.

[0069] The processing block 7 includes a plurality of processing units (chambers) 11. The processing units 11 are disposed to the sides of the transport mechanism 8. Each processing unit 11 performs processing on the substrate W.

[0070] The processing unit 11 includes a substrate holding section 13. The substrate holding section 13 is configured to hold a substrate W. The substrate holding section 13 includes, for example, at least one of a vacuum chuck, a Bernoulli chuck, and a mechanical chuck. The vacuum chuck and the Bernoulli chuck each suction-hold the substrate W. The vacuum chuck suction-holds, for example, the center of the substrate W. The Bernoulli chuck also suction-holds, for example, the center of the substrate W. The mechanical chuck grips the substrate W. The mechanical chuck grips an edge of the substrate W. The mechanical chuck includes, for example, a plurality of chuck pins. Each chuck pin contacts an edge surface of the substrate W to hold the substrate W.

[0071] The transport mechanism 8 is accessible to each processing unit 11. The transport mechanism 8 is approachable to each processing unit 11. The transport mechanism 8 can deliver the substrate W to the substrate holding portion 13. The transport mechanism 8 can take the substrate W from the substrate holding portion 13.

[0072] 3 is a control block diagram of the substrate processing apparatus 1. The substrate processing apparatus 1 includes a control unit 10. The control unit 10 is capable of communicating with the transport mechanisms 5 and 8 and the processing unit 11. The control unit 10 controls the transport mechanisms 5 and 8 and the processing unit 11.

[0073] The control unit 10 is realized by a central processing unit (CPU) that executes various processes, a random-access memory (RAM) that serves as a working area for the processes, a storage medium such as a fixed disk, etc. The control unit 10 has various information that is stored in advance in the storage medium. The information held by the control unit 10 is, for example, transport condition information for controlling the transport mechanisms 5 and 8. The information held by the control unit 10 is, for example, processing condition information for controlling the processing unit 11. The processing condition information is also called a processing recipe.

[0074] With reference to Fig. 2, an example of the operation of the substrate processing apparatus 1 will be briefly described.

[0075] The transport mechanisms 5 and 8 transport the substrate W from the carrier C to the processing unit 11. Specifically, the transport mechanism 5 unloads the substrate W from the carrier C. Then, the transport mechanism 5 transports the substrate W from the carrier C to the transport mechanism 8. The transport mechanism 8 transports the substrate W from the transport mechanism 5 to the processing unit 11. The transport mechanism 8 delivers the substrate W to the substrate holder 13 of the processing unit 11.

[0076] The processing unit 11 processes the substrate W. The processing unit 11 processes the substrate W held by the substrate holder 13. The processing unit 11 performs a drying process on the substrate W, for example.

[0077] After the processing units 11 process the substrate W, the transport mechanisms 5 and 8 transport the substrate W from each processing unit 11 to the carrier C. Specifically, the transport mechanism 8 takes the substrate W from the substrate holder 13 of the processing unit 11. The transport mechanism 8 transports the substrate W from the processing unit 11 to the transport mechanism 5. The transport mechanism 5 transports the substrate W from the transport mechanism 8 to the carrier C. The transport mechanism 5 loads the substrate W into the carrier C.

[0078] <4. Configuration of processing unit 11> 4 is a diagram showing the configuration of the processing units 11. Each processing unit 11 has the same structure. The processing units 11 are classified as single-wafer processing units. That is, each processing unit 11 processes only one substrate W at a time.

[0079] The processing unit 11 includes a housing 12. The housing 12 has a substantially box shape. The substrate W is processed inside the housing 12.

[0080] The inside of the housing 12 is kept at room temperature. The temperature of the gas inside the housing 12 is also kept at room temperature. Therefore, the substrate W is processed in an environment at room temperature.

[0081] The inside of the housing 12 is kept at normal pressure. The gas pressure inside the housing 12 is kept at normal pressure. Therefore, the substrate W is processed in a normal pressure environment.

[0082] Here, normal pressure includes standard atmospheric pressure (1 atm, 101325 Pa). Normal pressure is, for example, an atmospheric pressure in the range of 0.7 atm or more and 1.3 atm or less. In this specification, pressure values ​​are indicated as absolute pressures based on absolute vacuum.

[0083] The above-mentioned substrate holding section 13 is installed inside the housing 12. The substrate holding section 13 holds one substrate W. The substrate holding section 13 holds the substrate W in a substantially horizontal position.

[0084] The substrate holding part 13 is located below the substrate W held by the substrate holding part 13. The substrate holding part 13 contacts at least one of the lower surface of the substrate W and the peripheral edge part of the substrate W. The lower surface of the substrate W is also called the backside of the substrate W. The substrate holding part 13 does not contact the upper surface of the substrate W.

[0085] The processing unit 11 includes a rotation drive unit 14. At least a portion of the rotation drive unit 14 is installed inside the housing 12. The rotation drive unit 14 is connected to the substrate holding unit 13. The rotation drive unit 14 rotates the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates integrally with the substrate holding unit 13. The substrate W held by the substrate holding unit 13 rotates around a rotation axis B. The rotation axis B passes through the center of the substrate W, for example, and extends in the vertical direction Z.

[0086] The processing unit 11 includes a supply unit 15. The supply unit 15 supplies a liquid or a gas to the substrate W held by the substrate holding unit 13. Specifically, the supply unit 15 supplies the liquid or the gas to the upper surface of the substrate W held by the substrate holding unit 13.

[0087] The supply unit 15 includes a first supply unit 15a, a second supply unit 15b, a third supply unit 15c, a fourth supply unit 15d, and a fifth supply unit 15e. The first supply unit 15a supplies the above-mentioned processing liquid. The second supply unit 15b supplies a chemical liquid. The third supply unit 15c supplies a rinse liquid. The fourth supply unit 15d supplies a replacement liquid. The fifth supply unit 15e supplies a drying gas.

[0088] The first supply unit 15a is an example of the treatment liquid supply unit of the present invention.

[0089] As described above, the inside of the housing 12 is at normal temperature and pressure. Therefore, the processing liquid is used in an environment of normal temperature and pressure.

[0090] The chemical liquid supplied by the second supply unit 15b is, for example, an etching liquid, which includes, for example, at least one of hydrofluoric acid (HF) and buffered hydrofluoric acid (BHF).

[0091] The rinsing liquid supplied by the third supply unit 15c is, for example, deionized water (DIW).

[0092] The substitute liquid supplied by the fourth supply unit 15d is, for example, an organic solvent, or isopropyl alcohol.

[0093] The dry gas supplied by the fifth supply unit 15e is, for example, at least one of air and an inert gas. The air is, for example, compressed air. The inert gas is, for example, nitrogen gas. The dry gas preferably has a dew point lower than room temperature.

[0094] The first supply unit 15a includes a nozzle 16a. Similarly, the second to fifth supply units 15b-15e include nozzles 16b-16e, respectively. The nozzles 16a-16e are each installed inside the housing 12. The nozzle 16a ejects a processing liquid. The nozzle 16b ejects a chemical liquid. The nozzle 16c ejects a rinsing liquid. The nozzle 16d ejects a replacement liquid. The nozzle 16e ejects a drying gas.

[0095] The first supply unit 15a includes a pipe 17a and a valve 18a. The pipe 17a is connected to the nozzle 16a. The valve 18a is provided on the pipe 17a. When the valve 18a is open, the nozzle 16a discharges the processing liquid. When the valve 18a is closed, the nozzle 16a does not discharge the processing liquid. Similarly, the second to fifth supply units 15b-15e include pipes 17b-17e and valves 18b-18e, respectively. The pipes 17b-17e are connected to the nozzles 16b-16e, respectively. The valves 18b-18e are provided on the pipes 17b-17e, respectively. The valves 18b-18e control the discharge of the chemical liquid, the rinse liquid, the replacement liquid, and the drying gas, respectively.

[0096] At least a portion of the pipe 17a may be provided outside the housing 12. The pipes 17b-17e may be arranged similarly to the pipe 17a. The valve 18a may be provided outside the housing 12. The valves 18b-18e may be arranged similarly to the valve 18a.

[0097] The substrate processing apparatus 1 includes a first supply source 19a. The first supply source 19a is connected to the first supply unit 15a. The first supply source 19a is connected to, for example, a pipe 17a. The first supply source 19a communicates with the first supply unit 15a. The first supply source 19a supplies a processing liquid to the first supply unit 15a.

[0098] The second supply unit 15b is connected to the second supply source 19b. For example, the pipe 17b is connected to the second supply source 19b. The second supply unit 15b is connected to the second supply source 19b. The second supply source 19b sends a chemical liquid to the second supply unit 15b. Similarly, the third to fifth supply units 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. For example, the pipes 17c-17e are connected to the third to fifth supply sources 19c-19e, respectively. The third to fifth supply units 15c-15e are connected to the third to fifth supply sources 19c-19e, respectively. The third supply source 19c sends a rinse liquid to the third supply unit 15c. The fourth supply source 19d sends a replacement liquid to the fourth supply unit 15d. The fifth supply source 19e sends a drying gas to the fifth supply unit 15e.

[0099] The first supply source 19a is provided outside the housing 12. Similarly, the second to fifth supply sources 19b to 19e are provided outside the housing 12, respectively.

[0100] The first supply source 19a may supply the processing liquid to a plurality of processing units 11. Alternatively, the first supply source 19a may supply the processing liquid to only one processing unit 11. The same applies to the second to fifth supply sources 19b to 19e.

[0101] The second supply source 19b may be a component of the substrate processing apparatus 1. For example, the second supply source 19b may be a chemical tank provided in the substrate processing apparatus 1. Alternatively, the second supply source 19b may not be a component of the substrate processing apparatus 1. For example, the second supply source 19b may be a utility facility installed outside the substrate processing apparatus 1. Similarly, the third to fifth supply sources 19c-19e may each be a component of the substrate processing apparatus 1. Alternatively, the third to fifth supply sources 19c-19e may each be a component of the substrate processing apparatus 1.

[0102] The processing unit 11 may further include a cup (not shown). The cup is installed inside the housing 12. The cup is disposed around the substrate holder 13. The cup receives liquid splashed from the substrate W held by the substrate holder 13.

[0103] Please refer to Fig. 3. The control unit 10 controls the rotary drive unit 14. The control unit 10 controls the supply unit 15. The control unit 10 controls the valves 18a-18e.

[0104] 5. Configuration of first supply source 19a See Figure 4. The first source 19a also produces a processing liquid.

[0105] An example of the configuration of the first supply source 19a is shown below. The first supply source 19a is divided into a production unit 21 and a pumping unit 31. The production unit 21 produces a treatment liquid. The pumping unit 31 sends the treatment liquid to the first supply section 15a.

[0106] The production unit 21 includes a tank 22 and supply parts 23a and 23b. The supply part 23a supplies a sublimable substance to the tank 22. The supply part 23b supplies a solvent to the tank 22. The sublimable substance and the solvent are mixed in the tank 22. In the tank 22, the sublimable substance and the solvent become a processing liquid g.

[0107] The tank 22 is placed in an environment of normal temperature. The tank 22 is placed in an environment of normal pressure. Therefore, the processing liquid g is produced in an environment of normal temperature. The processing liquid g is produced in an environment of normal pressure.

[0108] Furthermore, the production unit 21 stores the processing liquid g. Specifically, the processing liquid g is stored in a tank 22. Therefore, the processing liquid g is stored in an environment at room temperature. The processing liquid g is stored in an environment at normal pressure.

[0109] The supply unit 23a includes, for example, a pipe 24a and a valve 25a. The pipe 24a is connected to the tank 22. The pipe 24a is connected to the tank 22. The valve 25a is provided on the pipe 24a. When the valve 25a is open, the supply unit 23a supplies the sublimable substance to the tank 22. When the valve 25a is closed, the supply unit 23a does not supply the sublimable substance to the tank 22. Similarly, the supply unit 23b includes a pipe 24b and a valve 25b. The pipe 24b is connected to the tank 22. The pipe 24b is connected to the tank 22. The valve 25b is provided on the pipe 24b. The valve 25b controls the supply of the solvent to the tank 22.

[0110] Furthermore, the amount of the sublimable substance in the tank 22 is controlled by the valve 25a. The amount of the solvent in the tank 22 is controlled by the valve 25b. Thus, the concentration CON of the sublimable substance in the treatment liquid g in the tank 22 is controlled by the valves 25a and 25b.

[0111] Each of the valves 25a and 25b may include, for example, a flow control valve. Each of the valves 25a and 25b may include, for example, a flow control valve and an on-off valve.

[0112] The supply unit 23a is connected to the supply source 26a. For example, the pipe 24a is connected to the supply source 26a. The supply unit 23a is connected to the supply source 26a. The supply source 26a sends a sublimable substance to the supply unit 23a. Similarly, the supply unit 23b is connected to the supply source 26b. For example, the pipe 24b is connected to the supply source 26b. The supply unit 23b is connected to the supply source 26b. The supply source 26b sends a solvent to the supply unit 23b.

[0113] The pumping unit 31 includes a pipe 32 and a joint 33. The pipe 32 is connected to the tank 22. The pipe 32 communicates with the tank 22. The joint 33 is connected to the pipe 32. The joint 33 is further connected to the pipe 17a. The pipe 32 is connected to the pipe 17a via the joint 33. The pipe 32 communicates with the pipe 17a via the joint 33. Therefore, the tank 22 is connected to the first supply unit 15a via the pipe 32 and the joint 33. The tank 22 communicates with the first supply unit 15a via the pipe 32 and the joint 33. Therefore, the tank 22 is connected to the nozzle 16a. The tank 22 communicates with the nozzle 16a.

[0114] The pumping unit 31 further includes a pump 34 and a filter 35. The pump 34 is provided in the piping 32. When the pump 34 is operating, the pump 34 sends the processing liquid g from the tank 22 to the first supply section 15a. When the pump 34 stops operating, the pump 34 does not send the processing liquid g from the tank 22 to the first supply section 15a. The filter 35 is provided in the piping 32. The processing liquid g passes through the filter 35. The filter 35 filters the processing liquid g. The filter 35 removes foreign matter from the processing liquid g.

[0115] Refer to Fig. 3. The control unit 10 is capable of communicating with the first supply source 19a. The control unit 10 controls the first supply source 19a. The control unit 10 controls the generation unit 21. The control unit 10 controls the supply units 23a, 23b. The control unit 10 controls the valves 25a, 25b. The control unit 10 controls the pumping unit 31. The control unit 10 controls the pump 34.

[0116] The control unit 10 has processing solution condition information for controlling the first supply source 19a. The processing solution condition information includes, for example, a target value for the concentration CON of the sublimable substance in the processing solution g. The processing solution condition information is stored in advance in a storage medium of the control unit 10.

[0117] 6. Operational Example of First Supply Source 19a and Processing Unit 11 5 is a flowchart showing the procedure of the substrate processing method of the embodiment. The substrate processing method includes step S1 and steps S11-S18. Step S1 is performed by the first supply source 19a. Steps S11-S18 are substantially performed by the processing unit 11. Step S1 is performed in parallel with steps S11-S18. The first supply source 19a and the processing unit 11 operate according to the control of the control unit 10.

[0118] Each of steps S1, S11-S18 will be described with reference to FIG.

[0119] Step S1: Processing solution generation process In the treatment liquid generating step, a treatment liquid g is generated.

[0120] The production unit 21 produces a processing liquid g. Specifically, the supply unit 23a supplies a sublimable substance to the tank 22. The supply unit 23b supplies a solvent to the tank 22. The sublimable substance and the solvent are mixed in the tank 22. That is, the processing liquid g is produced in the tank 22. The processing liquid g is stored in the tank 22.

[0121] The control unit 10 controls the valves 25a and 25b, thereby adjusting the concentration CON of the sublimable substance in the processing solution g in the tank 22 to a target value defined in the processing solution condition information.

[0122] Step S11: Rotation start process The substrate holding unit 13 holds the substrate W. The substrate W is held in a substantially horizontal position. The rotation drive unit 14 rotates the substrate holding unit 13. As a result, the substrate W held by the substrate holding unit 13 starts to rotate.

[0123] In steps S12-S17 described below, the substrate W, for example, continues to rotate.

[0124] Step S12: Chemical solution supply process In the chemical supplying step, the chemical is supplied to the substrate W.

[0125] The second supply unit 15b supplies the chemical liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18b opens. The nozzle 16b ejects the chemical liquid. The chemical liquid is supplied to the upper surface of the substrate W. For example, the chemical liquid etches the substrate W. For example, the chemical liquid removes a native oxide film from the substrate W.

[0126] Thereafter, the second supply unit 15b stops supplying the chemical liquid to the substrate W. Specifically, the valve 18b closes. The nozzle 16b stops discharging the chemical liquid.

[0127] Step S13: Rinse liquid supply process In the rinsing liquid supplying step, a rinsing liquid is supplied to the substrate W.

[0128] The third supply unit 15c supplies the rinsing liquid to the substrate W held by the substrate holding unit 13. Specifically, the valve 18c opens. The nozzle 16c ejects the rinsing liquid. The rinsing liquid is supplied to the upper surface of the substrate W. For example, the rinsing liquid cleans the substrate W. For example, the rinsing liquid removes a chemical liquid from the substrate W.

[0129] Thereafter, the third supply unit 15c stops supplying the rinsing liquid to the substrate W. Specifically, the valve 18c closes. The nozzle 16c stops discharging the rinsing liquid.

[0130] Step S14: Replacement liquid supply process In the replacement liquid supplying step, the replacement liquid is supplied to the substrate W.

[0131] The fourth supply unit 15d supplies the replacement liquid to the substrate W held by the substrate holder 13. Specifically, the valve 18d opens. The nozzle 16d ejects the replacement liquid. The replacement liquid is supplied to the upper surface of the substrate W. The replacement liquid removes the rinsing liquid from the substrate W. The rinsing liquid on the substrate W is replaced with the replacement liquid.

[0132] Thereafter, the fourth supply unit 15d stops supplying the replacement liquid to the substrate W. Specifically, the valve 18d closes. The nozzle 16d stops discharging the replacement liquid.

[0133] Step S15: Processing liquid supply process In the processing liquid supplying step, the processing liquid g is supplied to the substrate W.

[0134] The pressure-feeding unit 31 supplies the processing liquid g to the first supply section 15a. The first supply section 15a supplies the processing liquid g to the substrate W held by the substrate holding section 13. Specifically, the pump 34 sends the processing liquid g from the tank 22 to the first supply section 15a. The valve 18a opens. The nozzle 16a ejects the processing liquid g. The processing liquid g is supplied to the upper surface of the substrate W. The processing liquid g removes the replacement liquid from the substrate W. The replacement liquid on the substrate W is replaced with the processing liquid g.

[0135] Thereafter, the pressure-feeding unit 31 stops supplying the processing liquid g to the first supply section 15a. The first supply section 15a stops supplying the processing liquid g to the substrate W. Specifically, the pump 34 stops. The valve 18a closes. The nozzle 16a stops discharging the processing liquid g.

[0136] 6 is a diagram illustrating a substrate W in a processing liquid supplying step. When the substrate W is held by the substrate holding part 13, the pattern P is located on the upper surface of the substrate W. When the substrate W is held by the substrate holding part 13, the pattern P faces upward. When the substrate W is held by the substrate holding part 13, the convex part W1 extends upward.

[0137] The processing liquid g on the substrate W forms a liquid film G. The liquid film G is located on the substrate W. The liquid film G contacts the substrate W. The liquid film G covers the substrate W. The liquid film G covers the upper surface of the substrate W.

[0138] The entire pattern P is immersed in the liquid film G. The entire protrusion W1 is immersed in the liquid film G. The recess A is filled with the liquid film G. The entire recess A is filled with only the liquid film G.

[0139] The liquid film G has an upper surface G1. The upper surface G1 is located at a higher position than the pattern P. The entire upper surface G1 is located at a higher position than the entire pattern P. The upper surface G1 does not intersect with the pattern P. Specifically, the upper surface G1 is located at a higher position than the convex portion W1. The entire upper surface G1 is located at a higher position than the entire convex portion W1. The upper surface G1 does not intersect with the convex portion W1.

[0140] The substitute liquid has already been removed from the substrate W by the processing liquid g. Therefore, the substitute liquid does not exist on the substrate W. The substitute liquid does not remain in the recess A.

[0141] Gas J exists above the liquid film G. Pattern P does not contact gas J. Pattern P is not exposed to gas J. Convex portion W1 does not contact gas J. Convex portion W1 is not exposed to gas J.

[0142] The gas J contacts the liquid film G. The gas J contacts the upper surface G1. The upper surface G1 corresponds to a gas-liquid interface between the liquid film G and the gas J.

[0143] For this reason, in the processing liquid supplying process, the pattern P does not intersect with the gas-liquid interface between the liquid film G and the gas J. In the processing liquid supplying process, the convex portion W1 does not intersect with the gas-liquid interface between the liquid film G and the gas J. For this reason, in the processing liquid supplying process, the pattern P is not subjected to the surface tension of the processing liquid g. In the processing liquid supplying process, the convex portion W1 is not subjected to the surface tension of the processing liquid g.

[0144] In the processing liquid supplying step, the height position of the upper surface G1 may further be adjusted. For example, the height position of the upper surface G1 may be adjusted while the nozzle 16a is supplying the processing liquid g to the substrate W. For example, the height position of the upper surface G1 may be adjusted after the nozzle 16a stops supplying the processing liquid g. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation speed of the substrate W. For example, the height position of the upper surface G1 may be adjusted by adjusting the rotation time of the substrate W.

[0145] Here, adjusting the height position of the upper surface G1 corresponds to adjusting the thickness H of the liquid film G. The thickness H of the liquid film G is, for example, the distance in the vertical direction Z between the lower end W1a of the convex portion W1 and the upper surface G1.

[0146] Step S16: Solidified film formation process In the solidified film forming process, the solvent evaporates from the processing liquid g on the substrate W. In the solidified film forming process, the solvent evaporates from the liquid film G. In the solidified film forming process, a solidified film is formed on the substrate W. The solidified film includes a sublimable material.

[0147] 7 is a diagram showing a substrate W in a solidified film forming process. As described above, the solvent has a relatively high vapor pressure. At room temperature, the vapor pressure of the solvent is higher than the vapor pressure of the sublimable substance. Therefore, the solvent smoothly evaporates from the processing liquid g on the substrate W. The solvent smoothly evaporates from the liquid film G. The solvent smoothly changes from liquid to gas.

[0148] When the solvent evaporates from the processing liquid g on the substrate W, the solvent leaves the processing liquid g on the substrate W. When the solvent evaporates from the liquid film G, the solvent leaves the liquid film G. As the solvent evaporates from the liquid film G, the amount of solvent contained in the liquid film G decreases. As the amount of solvent contained in the liquid film G decreases, the concentration CON of the sublimable substance in the liquid film G increases.

[0149] Eventually, the sublimable substance in the liquid film G starts to precipitate on the substrate W. That is, the sublimable substance changes from a solute in the processing liquid g to a solid-phase sublimable substance. The solid-phase sublimable substance forms a solidified film K. The solidified film K does not contain a solvent. The solidified film K is solid. The solidified film K is formed on the substrate W.

[0150] Due to the precipitation of the sublimable substance, the liquid film G gradually changes into a solidified film K. Due to the precipitation of the sublimable substance, the solidified film K gradually increases in thickness. Due to the evaporation of the solvent and the precipitation of the sublimable substance, the liquid film G gradually decreases in thickness.

[0151] For example, first, the upper part of the liquid film G turns into a solidified film K. The solidified film K is located above the liquid film G. The solidified film K covers an upper surface G1 of the liquid film G.

[0152] When the solidified film K covers the entire upper surface G1, the solidified film K separates the liquid film G from the gas J. The gas-liquid interface between the liquid film G and the gas J disappears. Specifically, after the solidified film K covers the entire upper surface G1, the liquid film G does not come into contact with the gas J. The upper surface G1 does not come into contact with the gas J. The upper surface G1 does not correspond to a gas-liquid interface. The liquid film G comes into contact with the solidified film K. The upper surface G1 comes into contact with the solidified film K. The solidified film K comes into contact with the gas J.

[0153] Therefore, in the solidified film forming process, the pattern P does not intersect with the gas-liquid interface. In the solidified film forming process, the convex portion W1 does not intersect with the gas-liquid interface. Therefore, in the solidified film forming process, the pattern P is not subjected to the surface tension of the treatment liquid g. In the solidified film forming process, the convex portion W1 is not subjected to the surface tension of the treatment liquid g.

[0154] As the solidified film K increases, the height position of the upper surface G1 gradually decreases. As the solidified film K increases, the thickness H of the liquid film G gradually decreases.

[0155] Eventually, the upper surface G1 is lowered to the same height position as the pattern P. The upper surface G1 is lowered to the same height position as the protrusion W1. Therefore, the upper surface G1 intersects with the pattern P. The upper surface G1 intersects with the protrusion W1.

[0156] As described above, the upper surface G1 no longer corresponds to an air-liquid interface. Therefore, even when the upper surface G1 intersects with the pattern P, the pattern P is not subjected to the surface tension of the processing liquid g. Even when the upper surface G1 intersects with the convex portion W1, the convex portion W1 is not subjected to the surface tension of the processing liquid g. Therefore, the liquid film G decreases without exerting a significant force on the convex portion W1. The solvent leaves the substrate W without exerting a significant force on the convex portion W1.

[0157] FIG. 8 is a diagram showing a substrate W in the solidified film formation process. FIG. 8 shows a schematic diagram of the substrate W at the end of the solidified film formation process, for example. At the end of the solidified film formation process, all of the liquid film G has disappeared from the substrate W. The liquid film G is not present on the substrate W. The liquid film G does not remain in the recess A. All of the processing liquid g has disappeared from the substrate W. The processing liquid g is not present on the substrate W. The processing liquid g does not remain in the recess A. All of the solvent has disappeared from the substrate W. The solvent is not present on the substrate W. The solvent also does not remain in the recess A.

[0158] At the end of the solidified film formation process, only the solidified film K exists on the substrate W. The recess A is filled with the solidified film K. The entire recess A is filled with only the solidified film K. The pattern P is in contact with the solidified film K. The solidified film K supports the pattern P. The solidified film K protects the pattern P. For example, the solidified film K prevents the pattern P from collapsing. The protrusion W1 is in contact with the solidified film K. The solidified film K supports the protrusion W1. The solidified film K protects the protrusion W1. For example, the solidified film K prevents the protrusion W1 from collapsing.

[0159] Step S17: Sublimation process In the sublimation step, the solidified film K is sublimated.

[0160] The fifth supply unit 15e supplies dry gas to the substrate W held by the substrate holding unit 13. Specifically, the valve 18e opens. The nozzle 16e ejects dry gas. The nozzle 16e blows the dry gas onto the substrate W. The dry gas is supplied to the upper surface of the substrate W. The dry gas is supplied to the solidified film K. The solidified film K is exposed to the dry gas. This causes the solidified film K to sublime. The solidified film K changes into gas without passing through a liquid state. The sublimation of the solidified film K removes the solidified film K from the substrate W.

[0161] Thereafter, the fifth supply unit 15e stops supplying the dry gas to the solidified film K. Specifically, the valve 18e closes. The nozzle 16e stops blowing out the dry gas.

[0162] 9 is a diagram showing a substrate W in a sublimation process. As the solidified film K sublimes, the solidified film K gradually decreases. As the solidified film K sublimes, the solidified film K gradually becomes thinner. The pattern P starts to be exposed to the gas J. The protruding portion W1 starts to be exposed to the gas J.

[0163] When the solidified film K sublimes, the solidified film K does not apply a significant force to the pattern P. The solidified film K leaves the substrate W without applying a significant force to the pattern P. When the solidified film K sublimes, the solidified film K does not apply a significant force to the protrusion W1. The solidified film K leaves the substrate W without applying a significant force to the protrusion W1.

[0164] When the solidified film K sublimes, the solidified film K does not change into the processing liquid g. Therefore, in the sublimation process, the processing liquid g is not generated on the substrate W. Therefore, in the sublimation process, the processing liquid g does not exist on the substrate W. In the sublimation process, the processing liquid g does not exist in the recess A. Therefore, in the sublimation process, a gas-liquid interface between the processing liquid g and the gas does not occur in the vicinity of the pattern P. In the sublimation process, a gas-liquid interface between the processing liquid g and the gas does not occur in the vicinity of the protrusion W1.

[0165] When the solidified film K sublimes, the solidified film K does not change into liquid. Therefore, in the sublimation process, no liquid is generated on the substrate W. Therefore, in the sublimation process, no liquid is present on the substrate W. In the sublimation process, no liquid is present in the recess A. Therefore, in the sublimation process, a gas-liquid interface between the liquid and the gas is not generated in the vicinity of the pattern P. In the sublimation process, a gas-liquid interface between the liquid and the gas is not generated in the vicinity of the protrusion W1.

[0166] Therefore, in the sublimation process, the pattern P does not intersect with the gas-liquid interface. In the sublimation process, the convex portion W1 does not intersect with the gas-liquid interface. Therefore, in the sublimation process, the pattern P is not subjected to the surface tension of the treatment liquid g. In the sublimation process, the pattern P is not subjected to the surface tension of the liquid. In the sublimation process, the convex portion W1 is not subjected to the surface tension of the treatment liquid g. In the sublimation process, the convex portion W1 is not subjected to the surface tension of the liquid.

[0167] FIG. 10 is a diagram showing a substrate W in a sublimation process. FIG. 10 shows a substrate W, for example, at the end of the sublimation process. At the end of the sublimation process, the solidified film K has disappeared from the substrate W. The solidified film K is not present on the substrate W. The processing liquid g is not present on the substrate W. No liquid is present on the substrate W. The pattern P is entirely exposed to the gas J. The protruding portion W1 is entirely exposed to the gas J. The recessed portion A is entirely filled with only the gas J. The substrate W is dried.

[0168] The above-mentioned processes in the processing liquid supplying process, solidified film forming process, and sublimation process are examples of drying processes. The above-mentioned processes in the processing liquid supplying process, solidified film forming process, and sublimation process correspond to examples of using the processing liquid g. Examples of using the processing liquid g are summarized below. The processing liquid g is supplied to the substrate W, the solvent evaporates from the processing liquid g on the substrate W, a solidified film K containing a sublimable substance is formed on the substrate W, and then the solidified film K is sublimated.

[0169] The processing solution g is used in an environment at room temperature and at normal pressure.

[0170] Step S18: Rotation stop process The rotation driver 14 stops the rotation of the substrate holder 13. The substrate W held by the substrate holder 13 stops rotating. The substrate W comes to rest. The processing unit 11 finishes the processing of the substrate W.

[0171] <7. Technical significance of processing solution g> The technical significance of the processing solution g will be explained using Example 1-3.

[0172] The conditions of Example 1 will be described below. In Example 1, the substrate W is subjected to a series of processes including a chemical liquid supplying step, a rinsing liquid supplying step, a replacement liquid supplying step, a processing liquid supplying step, a solidified film forming step, and a sublimation step.

[0173] The chemical used in the chemical supplying step is hydrofluoric acid. Hydrofluoric acid is a mixture of hydrogen fluoride and water. The volume ratio of hydrogen fluoride to water is as follows: Hydrogen fluoride:water = 1:10 (volume ratio)

[0174] The rinse liquid used in the rinse liquid supplying step is deionized water.

[0175] The replacement liquid used in the replacement liquid supplying step is isopropyl alcohol.

[0176] The processing solution g used in the processing solution supplying step is composed of a sublimable substance and a solvent. The sublimable substance is a compound a. Specifically, the sublimable substance is N-methyl-p-toluenesulfonamide. The solvent is isopropyl alcohol. The concentration CON of the sublimable substance in the processing solution g is 1.96 [Vol%]. In other words, the volume ratio of the compound a to isopropyl alcohol is as follows: Compound a: isopropyl = 1:50 (volume ratio)

[0177] In the solidified film forming step, the substrate W is rotated at a rotation speed of 1500 rpm The duration of the solidified film forming step is 10 seconds.

[0178] In the sublimation step, the substrate W is rotated at a rotation speed of 1500 rpm while a dry gas is supplied to the substrate W. The sublimation step lasts for 105 seconds.

[0179] The conditions of Example 2 will be described. In Example 2, the sublimable substance is compound b. Specifically, in Example 2, the sublimable substance is 2-methyl-8-quinolinol. The concentration CON of the sublimable substance in the treatment liquid g is 5.88 [Vol%]. In other words, the volume ratio of compound b to isopropyl alcohol is as follows. Compound B: isopropyl = 1:16 (volume ratio) Other than this, the second embodiment is the same as the first embodiment.

[0180] The conditions of Example 3 will be described. In Example 3, the sublimable substance is compound c. Specifically, in Example 3, the sublimable substance is N-tert-butylacrylamide. The concentration CON of the sublimable substance in the treatment liquid g is 1.96 [Vol%]. In other words, the volume ratio of compound c to isopropyl alcohol is as follows. Compound c: isopropyl = 1:50 (volume ratio) Other than this, the conditions of the third embodiment are the same as those of the first embodiment.

[0181] Each of the substrates W processed in Examples 1-3 was evaluated by the average collapse rate Ea. The average collapse rate Ea is an index indicating the quality of the processing performed on the substrates W in Examples 1-3.

[0182] The average collapse rate Ea is obtained as follows. The average collapse rate Ea is the average value of a plurality of local collapse rates Ei. The local collapse rate Ei is the collapse rate in the local area Fi. i is any natural number from 1 to NF. The number NF is the number of the local areas Fi. The number NF is a natural number of 2 or more. Each local area Fi is a minute region of the substrate W. Each local area Fi is magnified 50,000 times by a scanning electron microscope, for example. Then, the pattern P in each local area Fi is observed. Each convex portion W1 in each local area Fi is evaluated. Each convex portion W1 in each local area Fi is judged. Specifically, it is judged for each convex portion W1 whether or not the convex portion W1 has collapsed. Each convex portion W1 is classified into either a collapsed convex portion W1 or a non-collapsed convex portion W1. Here, the number of convex portions W1 observed in the local area Fi is NAi. The number of collapsed convex parts W1 in the local area Fi is NBi. The number NBi is equal to or smaller than the number NAi. The local collapse rate Ei is the ratio of the number NBi to the number NAi. The local collapse rate Ei is defined, for example, by the following formula. Ei=NBi / NAi*100 (%) The average collapse rate Ea is the sum of each local collapse rate Ei divided by the number NF.

[0183] Fig. 11 is a table showing the quality of the processing performed on the substrate W in Examples 1-3. Specifically, Fig. 11 shows the average collapse rate Ea in Examples 1-3.

[0184] In Example 1, the average collapse rate Ea was 1.23%. In Example 2, the average collapse rate Ea was 4.66%. In Example 3, the average collapse rate Ea was 3.77%.

[0185] The average collapse rate Ea of Example 1-3 is sufficiently low. Therefore, in Example 1-3, collapse of the pattern P was suitably suppressed. In other words, in Example 1-3, the pattern P was suitably protected. Therefore, in Example 1-3, the substrate W was appropriately dried. Specifically, the substrate W was dried while the pattern P formed on the substrate W was suitably protected.

[0186] 8. Effects of the embodiment The substrate processing method of the embodiment is for processing a substrate W on which a pattern P is formed. The substrate processing method includes a processing liquid supplying step, a solidified film forming step, and a sublimation step. In the processing liquid supplying step, a processing liquid g is supplied to the substrate W. The processing liquid g contains a sublimable substance and a solvent. In the solidified film forming step, the solvent evaporates from the processing liquid g on the substrate W. In the solidified film forming step, a solidified film K is formed on the substrate W. The solidified film K contains a sublimable substance. In the sublimation step, the solidified film K is sublimated. The substrate W is dried by the sublimation of the solidified film K.

[0187] Here, the sublimable substance contains at least one of the compounds ac. Specifically, the sublimable substance contains at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Therefore, the processing liquid g contains at least one of the compounds ac. Therefore, in the solidified film forming step, the solidified film K is suitably formed on the substrate W.

[0188] The solidified film K contains at least one of the compounds ac. Therefore, in the sublimation process, the solidified film K is appropriately sublimated. That is, in the sublimation process, the substrate W is appropriately dried. Specifically, in the sublimation process, the substrate W is dried while the pattern P formed on the substrate W is appropriately protected.

[0189] As described above, according to the present substrate processing method, the substrate W is appropriately dried.

[0190] The solvent is isopropyl alcohol. Isopropyl alcohol dissolves compound a favorably. Isopropyl alcohol dissolves compound b favorably. Isopropyl alcohol dissolves compound c favorably. Therefore, it is easy to use the processing liquid g. It is easy to use a sublimable substance. For example, it is easy to supply the processing liquid g to the substrate W in the processing liquid supplying step. It is easy to supply the sublimable substance to the substrate W in the processing liquid supplying step. Therefore, the processing liquid g is properly supplied to the substrate W. The sublimable substance is properly supplied to the substrate W. Therefore, the substrate W is more properly dried.

[0191] The substrate processing method includes a processing liquid generating step. In the processing liquid generating step, the processing liquid g is generated. Therefore, the processing liquid g is preferably prepared. Therefore, it is easier to use the processing liquid g.

[0192] In the treatment liquid generating step, the treatment liquid g is generated by mixing a sublimable substance and a solvent, so that the treatment liquid g can be easily generated.

[0193] In the processing liquid production step, the processing liquid g is stored in the tank 22. Therefore, it is easy to store the processing liquid g, and it is even easier to use the processing liquid g.

[0194] As described above, the solvent is isopropyl alcohol. Therefore, the treatment liquid g is easy to handle. The handling of the treatment liquid includes at least one of preparation of the treatment liquid g, generation of the treatment liquid g, storage of the treatment liquid g, and use of the treatment liquid g. For example, it is easy to prepare the treatment liquid g. For example, it is easy to generate the treatment liquid g. For example, it is easy to store the treatment liquid g. For example, it is easy to use the treatment liquid g.

[0195] The substrate processing apparatus 1 includes a substrate holding unit 13 and a first supply unit 15a. The substrate holding unit 13 holds a substrate W. The first supply unit 15a supplies a processing liquid g to the substrate W held by the substrate holding unit 13. The processing liquid g contains a sublimable substance and a solvent.

[0196] Here, the sublimable substance contains at least one of the compounds ac. Therefore, the processing solution g contains at least one of the compounds ac. Therefore, the solidified film K is suitably formed on the substrate W.

[0197] The solidified film K contains at least one of the compounds ac. Therefore, the solidified film K is appropriately sublimated. That is, the substrate W is appropriately dried. Specifically, the substrate W is dried while the pattern P formed on the substrate W is appropriately protected.

[0198] As described above, according to the substrate processing apparatus 1, the substrate W is appropriately dried.

[0199] The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves the compound ac favorably. Therefore, it is easy to use the processing liquid g. It is easy to use a sublimable substance. For example, it is easy for the first supply unit 15a to supply the processing liquid g to the substrate W held by the substrate holding unit 13. It is easy for the first supply unit 15a to supply the sublimable substance to the substrate W held by the substrate holding unit 13. Therefore, the processing liquid g is appropriately supplied to the substrate W. The sublimable substance is appropriately supplied to the substrate W. Therefore, the substrate W is more appropriately dried.

[0200] The processing liquid g is used to dry the substrate W on which the pattern P is formed. Specifically, the processing liquid g is a drying assistant liquid. The processing liquid g contains a sublimable substance and a solvent.

[0201] Here, the sublimable substance contains at least one of the compounds ac. Therefore, the processing liquid g contains at least one of the compounds ac. Therefore, by supplying the processing liquid g to the substrate W, the solidified film K is suitably formed on the substrate W.

[0202] The solidified film K contains at least one of the compounds ac. Therefore, the solidified film K is appropriately sublimated. That is, the substrate W is appropriately dried. Specifically, the substrate W is dried while the pattern P formed on the substrate W is appropriately protected.

[0203] As described above, the substrate W is appropriately dried using the processing liquid g. In order to dry the substrate W, the processing liquid g is useful.

[0204] The solvent is isopropyl alcohol. As described above, isopropyl alcohol dissolves the compound ac favorably. Therefore, it is easy to use the treatment liquid g. It is easy to use a sublimable substance. Therefore, the substrate W is more appropriately dried using the treatment liquid g. The treatment liquid g is more useful for drying the substrate W.

[0205] As described above, the solvent is isopropyl alcohol, so that the treatment liquid g is easy to handle.

[0206] The processing liquid g is supplied to the substrate W. The solvent evaporates from the processing liquid g on the substrate W. A solidified film K containing a sublimable substance is formed on the substrate W. The solidified film K is then sublimated. When the processing liquid g is used in this manner, the substrate W is more appropriately dried. When the processing liquid g is used in these procedures, the processing liquid g is more useful for drying the substrate W.

[0207] <9. Modified embodiment> The present invention is not limited to the embodiments, and can be modified as follows.

[0208] (1) In the embodiment, the processing liquid g is generated before the processing liquid g is supplied to the first supply unit 15a. In the embodiment, the first supply source 19a generates the processing liquid in the tank 22. However, this is not limited to this. For example, the processing liquid g may be generated when the processing liquid g is supplied to the first supply unit 15a. For example, the first supply source 19a may generate the processing liquid g in a flow path that supplies the processing liquid g to the first supply unit 15a.

[0209] 12 is a diagram showing the configuration of a processing unit 11 and a first supply source 19a according to the modified embodiment. Note that the same components as those in the embodiment are given the same reference numerals and detailed description thereof will be omitted.

[0210] The first supply source 19a includes a first tank 41 and a second tank 42. The first tank 41 stores a sublimable substance. For example, the first tank 41 may store a solvent together with the sublimable substance. The second tank 42 stores a solvent. For example, the second tank 42 stores only a solvent.

[0211] The first supply source 19a includes a mixing section 44. The mixing section 44 is connected to the first tank 41 and the second tank 42. The mixing section 44 communicates with the first tank 41 and the second tank 42. The mixing section 44 produces a processing liquid g. The mixing section 44 is further connected to the first supply section 15a. The mixing section 44 communicates with the first supply section 15a. The mixing section 44 supplies the processing liquid g to the first supply section 15a.

[0212] Specifically, the mixing section 44 includes pipes 45a and 45b and a joint 46. The pipe 45a is connected to the first tank 41. The pipe 45a communicates with the first tank 41. The pipe 45b is connected to the second tank 42. The pipe 45b communicates with the second tank 42. The joint 46 is connected to the pipes 45a and 45b. The joint 46 communicates with the pipes 45a and 45b. The joint 46 is further connected to the pipe 17a. The joint 46 is further connected to the pipe 17a. The pipes 45a and 45b are connected to the pipe 17a via the joint 46. The pipes 45a and 45b communicate with the pipe 17a via the joint 46.

[0213] The mixer 44 includes pumps 47a and 47b. The pumps 47a and 47b are provided on the pipes 45a and 45b, respectively. The pump 47a sends the sublimable substance from the first tank 41 to the joint 46 through the pipe 45a. The pump 47b sends the solvent from the second tank 42 to the joint 46 through the pipe 45b.

[0214] The mixer 44 includes filters 48a and 48b. The filters 48a and 48b are provided on the pipes 45a and 45b, respectively. The sublimable substance passes through the filter 48a. The filter 48a filters the sublimable substance. The solvent passes through the filter 48b. The filter 48b filters the solvent.

[0215] The mixing section 44 includes valves 49a and 49b. The valves 49a and 49b are provided in the pipes 45a and 45b, respectively. The valve 49a adjusts the flow rate of the sublimable material flowing through the pipe 45a. The valve 49b adjusts the flow rate of the solvent flowing through the pipe 45b. Each of the valves 49a and 49b may include, for example, a flow rate control valve. Each of the valves 49a and 49b may include, for example, a flow rate control valve and an on-off valve.

[0216] An example of the operation of the first supply source 19a in the modified embodiment will be described. In the processing liquid supplying step, the first supply source 19a generates the processing liquid g and sends the processing liquid g to the first supply unit 15a. Specifically, the valves 49a and 49b are opened. The pump 47a sends the sublimable substance from the first tank 41 to the joint 46. The pump 47b sends the solvent from the second tank 42 to the joint 46. The sublimable substance and the solvent are mixed in the joint 46. The sublimable substance and the solvent become the processing liquid g in the joint 46. Furthermore, the processing liquid g flows from the joint 46 to the first supply unit 15a. The nozzle 16a ejects the processing liquid g.

[0217] According to this modified embodiment, it is not necessary to store the processing liquid g before the processing liquid g is supplied to the first supply unit 15a. Therefore, the concentration CON of the sublimable substance in the processing liquid g is accurately controlled. Therefore, the substrate W is more appropriately dried.

[0218] Furthermore, the first supply source 19a does not include the tank 22. Therefore, the structure of the first supply source 19a is preferably simplified. The first supply source 19a is preferably miniaturized.

[0219] (2) The substrate processing method of the embodiment includes a chemical liquid supplying step, a rinsing liquid supplying step, and a replacement liquid supplying step. However, the present invention is not limited to this. For example, at least one of the chemical liquid supplying step, the rinsing liquid supplying step, and the replacement liquid supplying step may be omitted. For example, all of the chemical liquid supplying step, the rinsing liquid supplying step, and the replacement liquid supplying step may be omitted.

[0220] (3) In the embodiment, when the processing liquid supplying process was performed, a liquid (e.g., a substitute liquid) was present on the substrate W. In the processing liquid supplying process, the processing liquid g was supplied to the substrate W in a wet state. In other words, in the processing liquid supplying process, the processing liquid g was supplied to the substrate W in a non-dried state. However, this is not limited to this. For example, when the processing liquid supplying process is performed, a liquid (e.g., a substitute liquid) may not be present on the substrate W. For example, in the processing liquid supplying process, the processing liquid g may be supplied to the substrate W in a dry state. In other words, in the processing liquid supplying process, the processing liquid g may be supplied to the substrate W in a non-wet state.

[0221] (4) In the processing liquid supplying step of the embodiment, the processing liquid g removes the replacement liquid from the substrate W. However, this is not limited to this. For example, in the processing liquid supplying step, the processing liquid g may clean the substrate W. For example, in the processing liquid supplying step, the processing liquid g may remove foreign matter adhering to the substrate W. For example, in the processing liquid supplying step, the processing liquid g may dissolve foreign matter adhering to the substrate W. The foreign matter is, for example, resist residue.

[0222] (5) In the solidified film formation process of the embodiment, a dry gas is not supplied to the substrate W. However, this is not limited to this. In the solidified film formation process, a dry gas may be supplied to the substrate W. In the solidified film formation process, a dry gas may be supplied to the processing liquid g on the substrate W. In the solidified film formation process, a dry gas may be supplied to the liquid film G. According to this modified embodiment, in the solidified film formation process, the processing liquid g on the substrate W is exposed to the dry gas. Therefore, in the solidified film formation process, the solvent evaporates efficiently from the processing liquid g on the substrate W. In the solidified film formation process, the solidified film K is efficiently formed on the substrate W.

[0223] (6) In the embodiment, for example, the pattern P on the substrate W may be formed on the substrate W before the processing unit 11 processes the substrate W. Alternatively, the pattern P may be formed on the substrate W when the processing unit 11 processes the substrate W. The pattern P may be formed on the substrate W, for example, in the chemical solution supplying step (step S12).

[0224] (7) The embodiment and each of the modified embodiments described above in (1) to (6) may be modified as appropriate by further replacing or combining each configuration with the configuration of another modified embodiment. [Explanation of symbols]

[0225] 1 ... Substrate processing equipment 10 ... Control section 11 … Processing unit 13... Board holding part 15 … Supply section 15a ... First supply section (processing liquid supply section) 19a … 1st supply source A … Recess g … Processing solution G: Liquid film of processing liquid K: Solidified film P... Pattern W … Substrate W1 … Convex part

Claims

1. A substrate processing method for processing a substrate having a pattern formed thereon, comprising the steps of: a processing liquid supplying step of supplying a processing liquid containing a sublimable material and a solvent to the substrate; a solidified film forming step of evaporating the solvent from the treatment liquid on the substrate to form a solidified film containing the sublimable substance on the substrate; a sublimation step of sublimating the solidified film; Equipped with The sublimable material includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. A method for processing a substrate.

2. 2. The substrate processing method according to claim 1, The solvent is isopropyl alcohol. A method for processing a substrate.

3. A substrate processing apparatus, comprising: A substrate holder for holding a substrate; a processing liquid supply unit that supplies a processing liquid containing a sublimable substance and a solvent to the substrate held by the substrate holding unit; Equipped with The sublimable material includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Substrate processing equipment.

4. 4. The substrate processing apparatus according to claim 3, The solvent is isopropyl alcohol. Substrate processing equipment.

5. A processing liquid used for drying a substrate on which a pattern is formed, comprising: The treatment liquid is A sublimable material; A solvent; Including, The sublimable material includes at least one of N-methyl-p-toluenesulfonamide, 2-methyl-8-quinolinol, and N-tert-butylacrylamide. Processing liquid.

6. The treatment liquid according to claim 5 , The solvent is isopropyl alcohol. Processing liquid.

7. The treatment liquid according to claim 5 , The treatment liquid is supplied to the substrate, the solvent is evaporated from the treatment liquid on the substrate, a solidified film containing the sublimable substance is formed on the substrate, and then the solidified film is sublimated. Processing liquid.

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