Substrate processing method, substrate processing apparatus, and computer-readable recording medium

Abstract

To provide a substrate processing method, a substrate processing apparatus, and a computer-readable recording medium that are capable of suppressing the occurrence of watermarks while suppressing the cost of substrate processing.SOLUTION: A substrate processing method according to an embodiment includes a first step of supplying a cleaning liquid to a substrate while rotating the substrate to form a liquid film of the cleaning liquid on the substrate, a second step of supplying a rinsing liquid to the substrate while rotating the substrate after the first step to form a liquid film of the rinsing liquid on the substrate, a third step of supplying a first organic solvent to the substrate while rotating the substrate after the second step to form a liquid film of the first organic solvent on the substrate, a fourth step of supplying a second organic solvent to the substrate while rotating the substrate after the third step to form a liquid film of the second organic solvent on the substrate, and a fifth step of drying the substrate after the fourth step. The second organic solvent has a lower solubility in water than the first organic solvent and a higher boiling point than the first organic solvent.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present disclosure relates to a substrate processing method, a substrate processing apparatus, and a computer-readable recording medium. [Background technology]

[0002] Patent Document 1 discloses a substrate processing method including the steps of supplying a processing liquid to a substrate, heating the substrate on which a liquid film of the processing liquid has been formed, supplying a volatile processing liquid to the substrate, and removing the volatile processing liquid to dry the substrate. The heating step includes heating the substrate so that the surface temperature of the substrate becomes higher than the dew point temperature before the surface of the substrate is exposed from the volatile processing liquid. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-146951 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure describes a substrate processing method, a substrate processing apparatus, and a computer-readable recording medium that can suppress the occurrence of watermarks while suppressing the cost of substrate processing. [Means for solving the problem]

[0005] An example of a substrate processing method may include a first step of supplying a cleaning liquid to the substrate while rotating the substrate to form a liquid film of the cleaning liquid on the substrate, a second step of supplying a rinsing liquid to the substrate while rotating the substrate after the first step, thereby draining the cleaning liquid from the substrate and forming a liquid film of the rinsing liquid on the substrate, a third step of supplying a first organic solvent to the substrate while rotating the substrate after the second step, thereby draining the rinsing liquid from the substrate and forming a liquid film of the first organic solvent on the substrate, a fourth step of supplying a second organic solvent to the substrate while rotating the substrate after the third step, thereby draining the first organic solvent from the substrate and forming a liquid film of the second organic solvent on the substrate, and a fifth step of drying the substrate. The second organic solvent may have lower solubility in water than the first organic solvent and a higher boiling point than the first organic solvent. [Effects of the Invention]

[0006] According to the substrate processing method, substrate processing apparatus, and computer-readable recording medium disclosed herein, it is possible to suppress the occurrence of watermarks while suppressing the cost of substrate processing. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a plan view schematically illustrating an example of a substrate processing system. [Figure 2] FIG. 2 is a side view schematically illustrating an example of a processing unit. [Figure 3] FIG. 3 is a block diagram showing an example of a main part of a substrate processing system. [Figure 4] FIG. 4 is a schematic diagram illustrating an example of a hardware configuration of the controller. [Figure 5] FIG. 5 is a flowchart illustrating an example of a substrate processing procedure. [Figure 6] FIG. 6 is a diagram illustrating an example of a substrate processing procedure. [Figure 7] FIG. 7 is a diagram for explaining the procedure subsequent to FIG. [Figure 8]FIG. 8 is a diagram for explaining an example of the flow state of the organic solvent on the substrate. [Figure 9] 9A and 9B are diagrams for explaining another example of the flow state of the organic solvent on the substrate, and are diagrams for explaining an example of a substrate treatment procedure. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the following description, the same elements or elements having the same functions will be designated by the same reference numerals, and redundant explanations will be omitted. Note that in this specification, when referring to the top, bottom, right, and left of the drawings, the directions of the reference numerals will be used as the basis.

[0009] [Substrate processing system] 1, a substrate processing system 1 (substrate processing apparatus) configured to process a substrate W will be described. The substrate processing system 1 includes a loading / unloading station 2, a processing station 3, and a controller Ctr (controller). The loading / unloading station 2 and the processing station 3 may be aligned in a horizontal line, for example.

[0010] The substrate W may be disk-shaped or may be a non-circular plate-shaped shape such as a polygon. The substrate W may have a cutout portion cut out from a portion thereof. The cutout portion may be, for example, a notch (a U-shaped, V-shaped groove, or the like) or a linear portion extending linearly (so-called orientation flat). The substrate W may be, for example, a semiconductor substrate (silicon wafer), a glass substrate, a mask substrate, an FPD (Flat Panel Display) substrate, or any other type of substrate. The diameter of the substrate W may be, for example, approximately 200 mm to 450 mm. As shown in FIG. 2, which will be described later, a predetermined pattern P may be formed on the surface Wa of the substrate W.

[0011] The loading / unloading station 2 includes a mounting section 4, a loading / unloading section 5, and a shelf unit 6. The mounting section 4 includes a plurality of mounting tables (not shown) arranged in the width direction (the vertical direction in FIG. 1). Each mounting table is configured to be able to mount a carrier 7 (storage container). The carrier 7 is configured to store at least one substrate W in a sealed state. The carrier 7 includes an opening / closing door (not shown) for loading and unloading the substrate W.

[0012] The loading / unloading section 5 is disposed adjacent to the mounting section 4 in the direction in which the loading / unloading stations 2 and the processing stations 3 are lined up (the left-right direction in FIG. 1). The loading / unloading section 5 includes an opening / closing door (not shown) provided in correspondence with the mounting section 4. When the carrier 7 is placed on the mounting section 4, the opening / closing door of the carrier 7 and the opening / closing door of the loading / unloading section 5 are both opened, thereby connecting the interior of the carrier 7 to the interior of the loading / unloading section 5.

[0013] The loading / unloading section 5 incorporates a transport arm A1 and a shelf unit 6. The transport arm A1 is configured to be able to move horizontally in the width direction of the loading / unloading section 5 (the vertical direction in FIG. 1), move up and down in the vertical direction, and pivot about a vertical axis. The transport arm A1 is configured to take out a substrate W from a carrier 7 and pass it to the shelf unit 6, and also to receive a substrate W from the shelf unit 6 and return it to the carrier 7. The shelf unit 6 is located near the processing station 3, and is configured to act as an intermediary for the transfer of substrates W between the loading / unloading section 5 and the processing station 3.

[0014] The processing station 3 includes a transport section 8 and a plurality of processing units 10. The transport section 8 extends horizontally, for example, in the direction in which the loading / unloading station 2 and the processing station 3 are lined up (the left-right direction in FIG. 1). The transport section 8 incorporates a transport arm A2. The transport arm A2 is configured to be able to move horizontally in the longitudinal direction of the transport section 8 (the left-right direction in FIG. 1), move up and down in the vertical direction, and pivot about a vertical axis. The transport arm A2 is configured to take out substrates W from the shelf unit 6 and deliver them to each processing unit 10, and to receive substrates W from each processing unit 10 and return them to the shelf unit 6.

[0015] The processing units 10 are arranged on both sides of the transport section 8 so as to be aligned in a row along the longitudinal direction of the transport section 8 (the left-right direction in FIG. 1). The processing units 10 are configured to perform a predetermined process (e.g., a cleaning process) on the substrate W. Details of the processing units 10 will be described later.

[0016] The controller Ctr is configured to partially or entirely control the substrate processing system 1. The controller Ctr will be described in detail later.

[0017] [Processing unit] Next, the processing unit 10 will be described in detail with reference to Fig. 2. The processing unit 10 includes a spin holder 20, a cleaning liquid supply unit 30, a rinsing liquid supply unit 40, a solvent supply unit 50 (first solvent supply unit), a solvent supply unit 60 (second solvent supply unit), and a solvent supply unit 70 (third solvent supply unit).

[0018] The rotation holding unit 20 includes a rotating unit 21, a shaft 22, and a holding unit 23. The rotating unit 21 is configured to operate based on an operation signal from the controller Ctr and rotate the shaft 22. The rotating unit 21 may be a power source such as an electric motor.

[0019] The holder 23 is provided at the tip of the shaft 22. The holder 23 may be configured to hold the entire back surface of the substrate W by suction, for example, by suction. In this case, even if the substrate W is warped, the substrate W is corrected so that it is approximately horizontal along the surface of the holder 23. In other words, the spin holder 20 may be configured to rotate the substrate W around a central axis (rotation axis) perpendicular to the surface of the substrate W while the substrate W is in an approximately horizontal position. As illustrated in FIG. 2, the spin holder 20 may rotate the substrate W counterclockwise when viewed from above.

[0020] The cleaning liquid supply unit 30 is configured to supply a cleaning liquid L1 to the substrate W. The cleaning liquid L1 includes, for example, an acidic chemical liquid for removing a thin film (e.g., a natural oxide film such as a silicon oxide film) from the surface Wa of the substrate W, and an alkaline chemical liquid for removing foreign matter (e.g., particles, organic matter, etc.) adhering to the surface Wa of the substrate W. Examples of acidic chemical liquids include SC-2 liquid (a mixture of hydrochloric acid, hydrogen peroxide, and pure water), HF liquid (hydrofluoric acid), DHF liquid (dilute hydrofluoric acid), and HNO3 + HF liquid (a mixture of nitric acid and hydrofluoric acid). Examples of alkaline chemical liquids include SC-1 liquid (a mixture of ammonia, hydrogen peroxide, and pure water), hydrogen peroxide solution, etc.

[0021] The cleaning liquid supply unit 30 includes a liquid source 31, a pump 32, a valve 33, a nozzle 34, and a pipe 35. The liquid source 31 is a supply source of the cleaning liquid L1. The pump 32 operates based on an operation signal from the controller Ctr, and is configured to pump the cleaning liquid L1 sucked from the liquid source 31 to the nozzle 34 via the pipe 35 and the valve 33.

[0022] The valve 33 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the fluid to flow through the pipe 35 and a closed state that prevents the fluid from flowing through the pipe 35. The nozzle 34 is disposed above the substrate W so that the outlet faces the front surface Wa of the substrate W. The nozzle 34 is configured to discharge the cleaning liquid L1 fed from the pump 32 from the outlet.

[0023] The nozzle 34 may be directly or indirectly connected to a driving source (not shown). The driving source may be configured to operate based on an operation signal from the controller Ctr and move the nozzle 34 horizontally or vertically above the substrate W. The pipe 35 connects the liquid source 31, the pump 32, the valve 33, and the nozzle 34 in this order from the upstream side.

[0024] The rinse liquid supply unit 40 is configured to supply a rinse liquid L2 to the substrate W. The rinse liquid L2 is, for example, a liquid for removing (rinsing away) the cleaning liquid L1 supplied to the surface Wa of the substrate W and dissolved components of a film formed by the cleaning liquid L1 from the surface Wa. The rinse liquid L2 includes, for example, deionized water (DIW), ozone water, carbonated water (CO2 water), ammonia water, etc.

[0025] The rinse liquid supply unit 40 includes a liquid source 41, a pump 42, a valve 43, a nozzle 44, and a pipe 45. The liquid source 41 is a supply source of the rinse liquid L2. The pump 42 operates based on an operation signal from the controller Ctr, and is configured to suck in the rinse liquid L2 from the liquid source 41 and send it to the nozzle 44 via the pipe 45 and the valve 43.

[0026] The valve 43 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the fluid to flow through the pipe 45 and a closed state that prevents the fluid from flowing through the pipe 45. The nozzle 44 is disposed above the substrate W so that its outlet faces the front surface Wa of the substrate W. The nozzle 44 is configured to discharge the rinsing liquid L2 fed from the pump 42 from the outlet.

[0027] The nozzle 44 may be directly or indirectly connected to a driving source (not shown). The driving source may be configured to operate based on an operation signal from the controller Ctr and move the nozzle 44 horizontally or vertically above the substrate W. The pipe 45 connects the liquid source 41, the pump 42, the valve 43, and the nozzle 44 in this order from the upstream side.

[0028] The solvent supply unit 50 is configured to supply an organic solvent L3 (first organic solvent) to the substrate W. The organic solvent L3 is, for example, a liquid for removing (rinsing away) the rinse liquid L2 supplied to the surface Wa of the substrate W from the surface Wa. The organic solvent L3 includes, for example, IPA (isopropyl alcohol).

[0029] The solvent supply unit 50 includes a liquid source 51, a pump 52, a valve 53, a nozzle 54, and a pipe 55. The liquid source 51 is a supply source of the organic solvent L3. The pump 52 operates based on an operation signal from the controller Ctr, and is configured to pump the organic solvent L3 sucked from the liquid source 51 to the nozzle 54 via the pipe 55 and the valve 53.

[0030] The valve 53 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the fluid to flow through the pipe 55 and a closed state that prevents the fluid from flowing through the pipe 55. The nozzle 54 is disposed above the substrate W so that the discharge outlet faces the front surface Wa of the substrate W. The nozzle 54 is configured to discharge the organic solvent L3 delivered from the pump 52 from the discharge outlet.

[0031] The nozzle 54 may be directly or indirectly connected to a driving source (not shown). The driving source may be configured to operate based on an operation signal from the controller Ctr and move the nozzle 54 horizontally or vertically above the substrate W. The piping 55 connects the liquid source 51, the pump 52, the valve 53, and the nozzle 54 in this order from the upstream side.

[0032] The solvent supply unit 60 is configured to supply an organic solvent L4 (second organic solvent) to the substrate W. The organic solvent L4 is, for example, a liquid for removing (washing away) the organic solvent L3 supplied to the surface Wa of the substrate W from the surface Wa. Details of the organic solvent L4 will be described later.

[0033] The solvent supply unit 60 includes a liquid source 61, a pump 62, a valve 63, a nozzle 64, and a pipe 65. The liquid source 61 is a supply source of the organic solvent L4. The pump 62 operates based on an operation signal from the controller Ctr, and is configured to pump the organic solvent L4 sucked from the liquid source 61 to the nozzle 64 via the pipe 65 and the valve 63.

[0034] The valve 63 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the fluid to flow through the pipe 65 and a closed state that prevents the fluid from flowing through the pipe 65. The nozzle 64 is disposed above the substrate W so that the discharge outlet faces the front surface Wa of the substrate W. The nozzle 64 is configured to discharge the organic solvent L4 delivered from the pump 62 from the discharge outlet.

[0035] The nozzle 64 may be directly or indirectly connected to a driving source (not shown). The driving source may be configured to operate based on an operation signal from the controller Ctr and move the nozzle 64 horizontally or vertically above the substrate W. The piping 65 connects the liquid source 61, the pump 62, the valve 63, and the nozzle 64 in this order from the upstream side.

[0036] The solvent supply unit 70 is configured to supply an organic solvent L5 (third organic solvent) to the substrate W. The organic solvent L5 is, for example, a liquid for removing (washing away) the organic solvent L4 supplied to the front surface Wa of the substrate W from the front surface Wa. Details of the organic solvent L5 will be described later.

[0037] The solvent supply unit 70 includes a liquid source 71, a pump 72, a valve 73, a nozzle 74, and a pipe 75. The liquid source 71 is a supply source of the organic solvent L5. The pump 72 operates based on an operation signal from the controller Ctr, and is configured to pump the organic solvent L5 sucked from the liquid source 71 to the nozzle 74 via the pipe 75 and the valve 73.

[0038] The valve 73 operates based on an operation signal from the controller Ctr, and is configured to transition between an open state that allows the fluid to flow through the pipe 75 and a closed state that prevents the fluid from flowing through the pipe 75. The nozzle 74 is disposed above the substrate W so that the discharge outlet faces the front surface Wa of the substrate W. The nozzle 74 is configured to discharge the organic solvent L5 delivered from the pump 72 from the discharge outlet.

[0039] The nozzle 74 may be directly or indirectly connected to a driving source (not shown). The driving source may be configured to operate based on an operation signal from the controller Ctr and move the nozzle 74 horizontally or vertically above the substrate W. The piping 75 connects the liquid source 71, the pump 72, the valve 73, and the nozzle 74 in this order from the upstream side.

[0040] [Liquid for substrate processing] The liquids used in this specification for substrate processing will now be described in more detail.

[0041] Organic solvent L4 has lower solubility in water than organic solvent L3. or the same as organic solvent L3and a solvent having a boiling point higher than that of organic solvent L3. Organic solvent L5 has a lower solubility in water than organic solvent L3 and a boiling point higher than that of organic solvent L4. Organic solvents L4 and L5 may be, for example, at least one solvent selected from the group consisting of esters mainly based on propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), butyl acetate (nBA) or ethyl lactate, cyclohexanone, higher alcohols (e.g., 1-pentanol), fluorocarbon solvents (e.g., "NOVEC (registered trademark) 7300" manufactured by 3M), chlorinated solvents, long-chain alkanes (e.g., octane), and aromatic hydrocarbons (e.g., toluene).

[0042] The organic solvents L4 and L5 may be a mixture of multiple organic solvents. The organic solvents L4 and L5 may be a mixture of two or more solvents selected from the above group. In this case, for example, by mixing multiple organic solvents with different solubilities in water, it becomes possible to easily adjust parameters such as boiling point. The organic solvents L4 and L5 may be, for example, a mixture of 10% to 90% by mass of PGME and 90% to 10% by mass of PGMEA, or a mixture of 10% to 90% by mass of PGME and 90% to 10% by mass of butyl acetate. The organic solvents L4 and L5 may be, for example, a mixture of 70% by mass of PGME and 30% by mass of PGMEA (OK73 thinner, manufactured by Tokyo Ohka Kogyo Co., Ltd.).

[0043] The solubility parameter (hereinafter also referred to as "SP value") of organic solvent L3 may be smaller than that of rinse liquid L2. The SP value of organic solvent L4 may be smaller than that of organic solvent L3. The SP value of organic solvent L5 may be smaller than that of organic solvent L4. The SP value is a parameter that indicates a measure of affinity between substances, and it is empirically known that the smaller the difference in SP values between two components, the greater the solubility. Known methods for estimating the SP value include the Hansen method [CM Hansen: J. Paint Tech., 39

[0505] , 104-117 (1967)], the Hoy method [HL Hoy: J. Paint Tech., 42

[0540] , 76-118 (1970)], and the Fedors method [RF Fedors: Polym. Eng. Sci., 14 [2], 147-154 (1974)].

[0044] Table 1 shows data on boiling points, water solubility, and SP values for some of the liquids exemplified in this specification (Source: Toshikatsu Kobayashi and 20 others, "Solubility Parameter Application Cases," Johokki Co., Ltd., March 2007). The SP values in Table 1 were calculated using the Fedors method. [Table 1]

[0045] [Controller Details] 3, the controller Ctr has a reading unit M1, a memory unit M2, a processing unit M3, and an instruction unit M4 as functional modules. These functional modules are merely a division of the functions of the controller Ctr into a plurality of modules for convenience, and do not necessarily mean that the hardware constituting the controller Ctr is divided into such modules. Each functional module is not limited to being realized by the execution of a program, but may also be realized by a dedicated electric circuit (for example, a logic circuit) or an integrated circuit (ASIC: Application Specific Integrated Circuit) that integrates such circuits.

[0046] The reading unit M1 is configured to read a program from a computer-readable recording medium RM. The recording medium RM stores a program for operating each part of the substrate processing system 1, including the processing unit 10. The recording medium RM may be, for example, a semiconductor memory, an optical recording disk, a magnetic recording disk, or a magneto-optical recording disk. Note that, hereinafter, each part of the substrate processing system 1 may include the rotating unit 21, the holding unit 23, the pumps 32, 42, 52, 62, and 72, and the valves 33, 43, 53, 63, and 73.

[0047] The memory unit M2 is configured to store various data. For example, the memory unit M2 may store a program read from the recording medium RM by the reading unit M1, setting data input by an operator via an external input device (not shown), etc. The memory unit M2 may store, for example, processing conditions for processing the substrate W, etc.

[0048] The processing unit M3 is configured to process various data, and may generate signals for operating each unit of the substrate processing system 1 based on the various data stored in the storage unit M2, for example.

[0049] The instruction unit M4 is configured to transmit the operation signal generated in the processing unit M3 to each unit of the substrate processing system 1.

[0050] The hardware of the controller Ctr may be configured, for example, by one or more control computers. As shown in Fig. 4, the controller Ctr may include a circuit C1 as a hardware configuration. The circuit C1 may be configured by electric circuit elements. The circuit C1 may include, for example, a processor C2, a memory C3, a storage C4, a driver C5, and an input / output port C6.

[0051] The processor C2 may be configured to execute a program in cooperation with at least one of the memory C3 and the storage C4 and to implement each of the above-mentioned functional modules by inputting and outputting signals via the input / output port C6. The memory C3 and the storage C4 may function as the storage unit M2. The driver C5 may be a circuit configured to drive each component of the substrate processing system 1. The input / output port C6 may be configured to mediate the input and output of signals between the driver C5 and each component of the substrate processing system 1.

[0052] The substrate processing system 1 may include one controller Ctr, or may include a controller group (controller) composed of multiple controllers Ctr. When the substrate processing system 1 includes a controller group, each of the above-mentioned functional modules may be realized by one controller Ctr, or may be realized by a combination of two or more controllers Ctr. When the controller Ctr is composed of multiple computers (circuits C1), each of the above-mentioned functional modules may be realized by one computer (circuit C1), or may be realized by a combination of two or more computers (circuits C1). The controller Ctr may include multiple processors C2. In this case, each of the above-mentioned functional modules may be realized by one processor C2, or may be realized by a combination of two or more processors C2.

[0053] [Substrate processing method] Next, a method for processing a substrate W will be described with reference to Figures 5 to 7. Before the method is started, a carrier 7 is placed in advance on the mounting table of the mounting unit 4. The carrier 7 contains at least one substrate W having a pattern P formed on its surface Wa.

[0054] First, the controller Ctr controls the transport arms A1 and A2 to take out one substrate W from the carrier 7 and transport it into one of the processing units 10. The substrate W transported into the processing unit 10 is placed on the holder .

[0055] Next, the controller Ctr controls the rotation unit 21 and the holder 23 (spin holder 20) to suck and hold the back surface of the substrate W with the holder 23, and rotate the substrate W. In this state, the controller Ctr controls the pump 32 and the valve 33 (cleaning liquid supply unit 30) to supply the cleaning liquid L1 from the nozzle 34 to the vicinity of the center of the front surface Wa of the substrate W (see step S10 in FIG. 5 and FIG. 6(a)). The cleaning liquid L1 supplied to the front surface Wa of the substrate W flows over the entire front surface Wa from the center toward the outer periphery of the substrate W due to the rotation of the substrate W, and is then spun outward from the outer periphery of the substrate W. Therefore, while the supply of the cleaning liquid L1 from the nozzle 34 continues, a liquid film of the cleaning liquid L1 is formed on the front surface Wa of the substrate W. At this time, the substrate W is cleaned by the cleaning liquid L1.

[0056] In step S10, for example, the cleaning liquid L1 may be supplied to the substrate W under the following processing condition 1. <Processing condition 1> Rotation speed of substrate W: Approximately 1000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Cleaning liquid L1 supply time: Approximately 30 seconds Discharge flow rate of cleaning solution L1: Approximately 1000 ml / min

[0057] Next, the controller Ctr controls the rotation unit 21 and the holder 23 (spin holder 20) to suction-hold the back surface of the substrate W with the holder 23 and rotate the substrate W. In this state, the controller Ctr controls the pump 42 and the valve 43 (rinse liquid supply unit 40) to supply a rinse liquid L2 from the nozzle 44 to the vicinity of the center of the front surface Wa of the substrate W (see step S11 of FIG. 5 and FIG. 6(b)). As the substrate W rotates, the rinse liquid L2 supplied to the front surface Wa of the substrate W flows over the entire front surface Wa from the center toward the outer periphery of the substrate W, replacing the cleaning liquid L1, and is then spun outward from the outer periphery of the substrate W. Therefore, the cleaning liquid L1 is discharged from the front surface Wa of the substrate W, and a liquid film of the rinse liquid L2 is formed on the front surface Wa of the substrate W while the rinse liquid L2 continues to be supplied from the nozzle 44.

[0058] In step S11, for example, the rinse liquid L2 may be supplied to the substrate W under the following processing condition 2. <Processing condition 2> Rotation speed of substrate W: Approximately 1000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Rinse liquid L2 supply time: Approximately 30 seconds Rinse liquid L2 discharge flow rate: Approximately 1000 ml / min

[0059] Next, the controller Ctr controls the rotation unit 21 and the holder 23 (spin holder 20) to suction-hold the back surface of the substrate W with the holder 23 and rotate the substrate W. In this state, the controller Ctr controls the pump 52 and the valve 53 (solvent supply unit 50) to supply the organic solvent L3 from the nozzle 54 to the vicinity of the center of the front surface Wa of the substrate W (see step S12 of FIG. 5 and FIG. 6(c)). The organic solvent L3 supplied to the front surface Wa of the substrate W flows over the entire front surface Wa from the center toward the outer periphery of the substrate W while being replaced by the rinsing liquid L2 due to the rotation of the substrate W, and is then spun outward from the outer periphery of the substrate W. Therefore, the rinsing liquid L2 is discharged from the front surface Wa of the substrate W, and a liquid film of the organic solvent L3 is formed on the front surface Wa of the substrate W while the organic solvent L3 continues to be supplied from the nozzle 54.

[0060] In step S12, for example, an organic solvent L3 may be supplied to the substrate W under the following processing condition 3. <Processing condition 3> Rotation speed of substrate W: Approximately 1000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Supply time of organic solvent L3: about 30 seconds Discharge flow rate of organic solvent L3: Approximately 100 ml / min

[0061] Next, the controller Ctr controls the rotation unit 21 and the holder 23 (spin holder 20) to suction-hold the back surface of the substrate W with the holder 23 and rotate the substrate W. In this state, the controller Ctr controls the pump 62 and the valve 63 (solvent supply unit 60) to supply organic solvent L4 from the nozzle 64 to the vicinity of the center of the front surface Wa of the substrate W (see step S13 of FIG. 5 and FIG. 7(a)). As the substrate W rotates, the organic solvent L4 supplied to the front surface Wa of the substrate W flows over the entire front surface Wa from the center toward the outer periphery of the substrate W, replacing the organic solvent L3, and then is thrown outward from the outer periphery of the substrate W. Therefore, the organic solvent L3 is discharged from the front surface Wa of the substrate W, and a liquid film of the organic solvent L4 is formed on the front surface Wa of the substrate W while the organic solvent L4 is continuously supplied from the nozzle 64.

[0062] In step S13, for example, the organic solvent L4 may be supplied to the substrate W under the following processing condition 4. <Processing condition 4> Rotation speed of substrate W: Approximately 1000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Supply time of organic solvent L4: about 10 seconds Discharge flow rate of organic solvent L4: Approximately 100 ml / min

[0063] Next, the controller Ctr controls the rotation unit 21 and the holder 23 (spin holder 20) to suction-hold the back surface of the substrate W with the holder 23 and rotate the substrate W. In this state, the controller Ctr controls the pump 72 and the valve 73 (solvent supply unit 70) to supply organic solvent L5 from the nozzle 74 to the vicinity of the center of the front surface Wa of the substrate W (see step S14 of FIG. 5 and FIG. 7(b)). As the substrate W rotates, the organic solvent L5 supplied to the front surface Wa of the substrate W flows over the entire front surface Wa from the center toward the outer periphery of the substrate W, replacing the organic solvent L4, and then is thrown outward from the outer periphery of the substrate W. Therefore, the organic solvent L4 is discharged from the front surface Wa of the substrate W, and a liquid film of organic solvent L5 is formed on the front surface Wa of the substrate W while the organic solvent L5 is continuously supplied from the nozzle 74.

[0064] In step S14, for example, an organic solvent L5 may be supplied to the substrate W under the following processing condition 5. <Processing condition 5> Rotation speed of substrate W: Approximately 1000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Supply time of organic solvent L5: about 10 seconds Organic solvent L5 discharge flow rate: approx. 100 ml / min

[0065] Next, the controller Ctr controls the rotation unit 21 and the holder 23 (spin holder 20) to suction-hold the back surface of the substrate W with the holder 23 and rotate the substrate W. As a result, the organic solvent L5 on the front surface Wa of the substrate W is shaken outward from the outer periphery of the substrate W, and the substrate W is dried (see step S15 in FIG. 5 and FIG. 7(c)). This completes the processing of the substrate W.

[0066] In step S15, the substrate W may be dried under the following processing condition 6, for example. <Processing condition 6> Rotation speed of substrate W: Approximately 1500 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Drying time for substrate W: about 30 seconds

[0067] [Effect] According to the above example, the organic solvent L3, the organic solvent L4, and the organic solvent L5 are supplied to the substrate W in this order. Agent L Organic solvent L5 has lower solubility in water than organic solvent L3, and therefore is relatively resistant to absorbing moisture from the atmosphere. Therefore, when organic solvent L3 is replaced with organic solvent L4, and then organic solvent L4 is replaced with organic solvent L5, and then the substrate W is dried, moisture is extremely unlikely to remain on the substrate W. Furthermore, organic solvent L4 has a higher boiling point than organic solvent L3, and therefore is relatively resistant to vaporization. In addition, organic solvent L5 has a higher boiling point than organic solvent L4, and therefore is even more resistant to vaporization. Therefore, a decrease in the temperature of the substrate W is extremely unlikely to occur. Therefore, condensation and absorption of moisture in the atmosphere are suppressed without the need for an additional heating source or moisture absorption device. As a result, it is possible to suppress the occurrence of watermarks while reducing substrate processing costs.

[0068] According to the above example, the SP values can be set to decrease in the order of the rinse liquid L2, the organic solvent L3, the organic solvent L4, and the organic solvent L5. In this case, the organic solvent L3 dissolves more easily in the rinse liquid L2, the organic solvent L4 dissolves more easily in the organic solvent L3, and the organic solvent L5 dissolves more easily in the organic solvent L4. Therefore, when the organic solvent L3 is supplied to the substrate W, the rinse liquid L2 mixes with the organic solvent L3 and is discharged from the substrate W, making it difficult for the rinse liquid L2 to remain on the substrate W. Similarly, when the organic solvent L4 is supplied to the substrate W, the organic solvent L3 mixes with the organic solvent L4 and is discharged from the substrate W, making it difficult for the organic solvent L3 to remain on the substrate W. Similarly, when the organic solvent L5 is supplied to the substrate W, the organic solvent L4 mixes with the organic solvent L5 and is discharged from the substrate W, making it difficult for the organic solvent L4 to remain on the substrate W. As a result, the rinse liquid L2, organic solvent L3, and organic solvent L4 are successively replaced by the subsequent liquids, which makes it possible to further suppress the occurrence of watermarks, particularly when DIW (pure water) is used as the rinse liquid.

[0069] [Variations] The disclosure in this specification should be considered to be illustrative in all respects and not restrictive. Various omissions, substitutions, modifications, etc. may be made to the above examples without departing from the scope and spirit of the claims.

[0070] (1) In step S13, the organic solvent L4 may be supplied to the substrate W while repeatedly accelerating and decelerating the rotation of the substrate W. For example, in step S13, after the organic solvent L4 is supplied to the substrate W under the above-described processing condition 4, the supply of the organic solvent L4 may be continued under the following processing condition 4A. That is, under processing condition 4A, the rotation of the substrate W may be accelerated and decelerated while varying the rotation speed of the substrate W between approximately 100 rpm and approximately 1000 rpm. <Processing condition 4A> Rotation speed of substrate W: Approximately 100 rpm to 1000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Supply time of organic solvent L4: about 30 seconds Discharge flow rate of organic solvent L4: Approximately 100 ml / min

[0071] Similarly, in step S14, the organic solvent L5 may be supplied to the substrate W while repeatedly accelerating and decelerating the rotation of the substrate W. For example, in step S14, after the organic solvent L5 is supplied to the substrate W under the above-mentioned processing condition 5, the supply of the organic solvent L5 may be continued under the following processing condition 5A. That is, under processing condition 5A, the rotation of the substrate W may be accelerated and decelerated while varying the rotation speed of the substrate W between approximately 100 rpm and approximately 2000 rpm. <Processing condition 5A> Rotation speed of substrate W: Approximately 100 rpm to 2000 rpm Acceleration of substrate W rotation: Approximately 500 rpm / s Supply time of organic solvent L4: about 30 seconds Discharge flow rate of organic solvent L4: Approximately 100 ml / min

[0072] In the above case, when the rotation of the substrate W is accelerated, the liquid on the substrate W moves toward the outer periphery of the substrate W in the radial direction of the substrate W (see FIG. 8(a)). Therefore, if a pattern P is formed on the substrate W, a rotational flow is generated in the gaps between the patterns P, which moves from top to bottom and then moves toward the center of rotation of the substrate W (see FIG. 8(a)). On the other hand, when the rotation of the substrate W is decelerated, the liquid on the substrate W moves toward the center of rotation of the substrate W in the radial direction of the substrate W (see FIG. 8(b)). Therefore, if a pattern P is formed on the substrate W, a flow is generated in the gaps between the patterns P, which moves toward the center of rotation of the substrate W and obliquely downward (see FIG. 8(b)). Therefore, when the rotation of the substrate W is repeatedly accelerated and decelerated, the liquid on the substrate W oscillates in the radial direction of the substrate W. Therefore, in step S13, organic solvent L4 is more likely to be replaced by organic solvent L3, and in step S14, organic solvent L5 is more likely to be replaced by organic solvent L4. In particular, when patterns P are formed on the substrate W, as illustrated in Fig. 8(c), the organic solvent that has entered the gaps between the patterns P is mixed with the subsequent organic solvent in the gaps, and the organic solvent supplied in the previous step is easily discharged from the gaps. Therefore, the organic solvent supplied in the previous step can be effectively discharged from the substrate W.

[0073] As exemplified by process conditions 4A and 5A, the maximum rotation speed of the substrate W in step S14 (e.g., about 2000 rpm) may be greater than the maximum rotation speed of the substrate W in step S13 (e.g., about 1000 rpm). In this case, a greater centrifugal force acts on the organic solvent L5, which can promote the replacement of the organic solvent L4 with the organic solvent L5.

[0074] (2) As described above, when the rotation of the substrate W is repeatedly accelerated and decelerated in steps S13 and S14, the supply rates of the organic solvents L4 and L5 to the substrate W may be temporarily increased when the substrate W is rotating at a low speed (for example, at approximately 100 rpm to 300 rpm). In this case, when the substrate W is rotating at a low speed, puddles PU of the organic solvents L4 and L5 are formed on the surface Wa of the substrate W (see FIG. 9(a)). Therefore, when the rotation speed of the substrate W is subsequently accelerated, the puddles PU, which have a relatively large mass, move toward the outer periphery of the substrate W in a clumped state (see FIG. 9(b)). At this time, the liquid on the substrate W is also attracted by the movement of the clumped liquid puddles PU and moves toward the outer periphery of the substrate W. In particular, when a pattern P is formed on the substrate W, the liquid (organic solvent supplied in the previous step) that has entered the gaps between the patterns P is drawn outward from the gaps by the movement of the clumped liquid puddles PU. This makes it possible to effectively remove the organic solvent supplied in the previous step from the substrate W.

[0075] (3) In the above example, organic solvent L5 is supplied to substrate W after organic solvent L4 is supplied, but organic solvent L5 does not have to be supplied. That is, step S14 in Fig. 5 may be omitted. Alternatively, after organic solvent L5 is supplied, another organic solvent may be supplied to substrate W.

[0076] In a configuration in which multiple organic solvents are supplied after organic solvent L3, these multiple organic solvents will be referred to as the second organic solvent, the third organic solvent, ..., the Nth organic solvent (N is a natural number of 2 or greater). In this case, the nth organic solvent (n is a natural number from 3 to N) may have lower solubility in water than the first organic solvent and a higher boiling point than the (n-1)th organic solvent. In addition, the SP value of the nth organic solvent may be set to be smaller than the SP value of the (n-1)th organic solvent.

[0077] (4) In the above examples, various liquids are supplied to the front surface Wa of the substrate W, but the various liquids may be supplied to the rear surface of the substrate W. In this case, too, it is possible to suppress the occurrence of watermarks while suppressing the cost of substrate processing.

[0078] (5) The technology of this specification may be applied to a substrate W on which no pattern P is formed. In this case, too, it is possible to suppress the occurrence of watermarks while suppressing the cost of substrate processing.

[0079] [Other examples] Example 1. An example of a substrate processing method may include a first step of supplying a cleaning liquid to the substrate while rotating the substrate to form a liquid film of the cleaning liquid on the substrate; a second step of supplying a rinsing liquid to the substrate while rotating the substrate after the first step, thereby draining the cleaning liquid from the substrate and forming a liquid film of the rinsing liquid on the substrate; a third step of supplying a first organic solvent to the substrate while rotating the substrate after the second step, thereby draining the rinsing liquid from the substrate and forming a liquid film of the first organic solvent on the substrate; a fourth step of supplying a second organic solvent to the substrate while rotating the substrate after the third step, thereby draining the first organic solvent from the substrate and forming a liquid film of the second organic solvent on the substrate; and a fifth step of drying the substrate after the fourth step. The second organic solvent may have lower solubility in water than the first organic solvent and a higher boiling point than the first organic solvent.

[0080] However, when a substrate is dried after being supplied with a rinse liquid, if a pattern is formed on the substrate, there is a concern that the pattern may be damaged or collapsed due to the surface tension of the rinse liquid. Furthermore, particularly when the substrate surface is hydrophobic, the centrifugal force acting on the liquid near the outer periphery of the substrate increases, making it more likely that the liquid film will be interrupted. In this case, there is a concern that watermarks will occur in the areas of the substrate where the liquid film is interrupted, and that minute particles will adhere to the substrate. Therefore, a known method is to supply a volatile organic solvent (e.g., IPA (isopropyl alcohol)) to the substrate after the rinse liquid has been applied, replace the rinse liquid with the organic solvent, and then dry the substrate.

[0081] However, in this case, the substrate is cooled by the heat of vaporization of the organic solvent, and moisture in the atmosphere condenses on the substrate, raising concerns that watermarks may form on the substrate. Furthermore, particularly when IPA is used, the high hygroscopicity of IPA increases the risk of watermarks forming on the substrate. For this reason, known methods include processing the substrate while heating it (see Patent Document 1) and processing the substrate in a dry atmosphere. These methods require the addition of a heating source or moisture absorption device, which can increase the cost of the device and running costs.

[0082] On the other hand, in Example 1, the second organic solvent is supplied after the first organic solvent is supplied. The second organic solvent has lower solubility in water than the first organic solvent, so it is relatively less likely to absorb moisture from the atmosphere. Therefore, when the substrate is dried after the first organic solvent is replaced with the second organic solvent, moisture is less likely to remain on the substrate. Furthermore, the second organic solvent has a higher boiling point than the first organic solvent, so it is relatively less likely to evaporate. Therefore, a decrease in the temperature of the substrate is less likely to occur. Therefore, condensation and moisture absorption of moisture in the atmosphere are suppressed without adding a heating source or moisture absorption device. As a result, it is possible to suppress the occurrence of watermarks while reducing substrate processing costs.

[0083] Example 2: In the method of Example 1, the solubility parameter (SP value) of the first organic solvent may be smaller than that of the rinse solution, and the solubility parameter (SP value) of the second organic solvent may be smaller than that of the first organic solvent. It is known that solutions with similar solubility parameters (SP values) tend to dissolve more readily. Therefore, according to Example 2, the first organic solvent dissolves more readily in the rinse solution, and the second organic solvent dissolves more readily in the first organic solvent. Therefore, when the first organic solvent is supplied to the substrate, the rinse solution mixes with the first organic solvent and is discharged from the substrate, making it difficult for the rinse solution to remain on the substrate. Similarly, when the second organic solvent is supplied to the substrate, the first organic solvent mixes with the second organic solvent and is discharged from the substrate, making it difficult for the first organic solvent to remain on the substrate. As a result, the occurrence of watermarks can be further suppressed, particularly when pure water is used as the rinse solution.

[0084] Example 3: In the method of Example 1 or Example 2, the second organic solvent may be a mixture of multiple organic solvents. In this case, for example, by mixing multiple organic solvents with different solubilities in water, it becomes possible to easily adjust parameters such as boiling point.

[0085] Example 4: In any of the methods of Examples 1 to 3, the fourth step may include supplying the second organic solvent to the substrate while repeatedly accelerating and decelerating the rotation of the substrate. In this case, the liquid on the substrate moves radially toward the outer edge of the substrate or toward the center of the substrate. That is, the liquid on the substrate oscillates radially toward the substrate. This makes it easier for the second organic solvent to replace the first organic solvent. In particular, when a pattern is formed on the substrate, the first organic solvent that has entered gaps between the patterns mixes with the second organic solvent in the gaps, making it easier for the first organic solvent to be discharged from the gaps. This makes it possible to effectively discharge the first organic solvent from the substrate.

[0086] Example 5: In the method of Example 4, the fourth step may include increasing the amount of the second organic solvent supplied to the substrate while the substrate is rotating at a low speed. In this case, when the substrate is rotating at a low speed, a puddle of the second organic solvent is formed on the surface of the substrate. Therefore, when the rotation speed of the substrate is subsequently accelerated, the puddle with a relatively large mass moves toward the outer edge of the substrate while remaining in a lumpy state. At this time, the liquid on the substrate is also attracted by the movement of the lumpy puddle and moves toward the outer edge of the substrate. In particular, when a pattern is formed on the substrate, the first organic solvent that has entered the gaps between the patterns is drawn outward from the gaps by the movement of the lumpy puddle. This makes it possible to effectively remove the first organic solvent from the substrate.

[0087] Example 6: The methods of Examples 1 to 5 may further include a sixth step, after the fourth step and before the fifth step, of supplying a third organic solvent to the substrate while rotating the substrate, thereby draining the second organic solvent from the substrate and forming a liquid film of the third organic solvent on the substrate. The third organic solvent may have a lower solubility in water than the first organic solvent and a higher boiling point than the second organic solvent. In this case, the third organic solvent is supplied after the second organic solvent is supplied. Because the third organic solvent has a lower solubility in water than the second organic solvent, it is less likely to absorb moisture from the atmosphere. Therefore, when the substrate is dried after replacing the second organic solvent with the third organic solvent, moisture is less likely to remain on the substrate. Furthermore, because the third organic solvent has a higher boiling point than the second organic solvent, it is even more difficult to evaporate. Therefore, a decrease in the temperature of the substrate is significantly reduced. Therefore, condensation and absorption of moisture in the atmosphere can be suppressed without adding a heating source or moisture absorption device, which makes it possible to further suppress the occurrence of watermarks while reducing the cost of substrate processing.

[0088] Example 7: In the method of Example 6, the solubility parameter (SP value) of the third organic solvent may be smaller than the solubility parameter (SP value) of the second organic solvent. In this case, the third organic solvent is easily soluble in the second organic solvent. Therefore, when the third organic solvent is supplied to the substrate, the second organic solvent mixes with the third organic solvent and is discharged from the substrate, making it difficult for the second organic solvent to remain on the substrate. As a result, it is possible to further suppress the occurrence of watermarks, particularly when pure water is used as a rinse liquid.

[0089] Example 8 In the method of Example 6 or Example 7, the third organic solvent may be a mixture of multiple organic solvents. In this case, for example, by mixing multiple organic solvents with different solubilities in water, it becomes possible to easily adjust parameters such as boiling point.

[0090] Example 9: In any of the methods of Examples 6 to 8, the sixth step may include supplying the third organic solvent to the substrate while repeatedly accelerating and decelerating the rotation of the substrate. In this case, as in Example 4, the liquid on the substrate oscillates in the radial direction of the substrate. This makes it easier for the third organic solvent to be replaced by the second organic solvent. In particular, when a pattern is formed on the substrate, the second organic solvent that has entered gaps between the patterns mixes with the third organic solvent in the gaps, making it easier for the second organic solvent to be discharged from the gaps. This makes it possible to effectively discharge the second organic solvent from the substrate.

[0091] Example 10 In the method of Example 9, the maximum rotation speed of the substrate in the sixth step may be higher than the maximum rotation speed of the substrate in the fourth step. In this case, a greater centrifugal force acts on the third organic solvent, which can promote the substitution of the second organic solvent with the third organic solvent.

[0092] Example 11: In the method of Example 9 or Example 10, the sixth step may include increasing the amount of the third organic solvent supplied to the substrate while the substrate is rotating at a low speed. In this case, as in Example 5, the liquid on the substrate is attracted by the movement of the lumpy liquid pools and moves to the outer periphery of the substrate. In particular, when a pattern is formed on the substrate, the second organic solvent that has entered the gaps between the patterns is drawn outward from the gaps by the movement of the lumpy liquid pools. Therefore, the second organic solvent can be effectively discharged from the substrate.

[0093] Example 12. An example of a substrate processing apparatus may include a spin holder configured to hold and rotate a substrate, a cleaning liquid supply unit configured to supply a cleaning liquid to the substrate, a rinsing liquid supply unit configured to supply a rinsing liquid to the substrate, a first solvent supply unit configured to supply a first organic solvent to the substrate, a second solvent supply unit configured to supply a second organic solvent to the substrate, and a control unit. The second organic solvent may have lower solubility in water than the first organic solvent and a higher boiling point than the first organic solvent. The control unit may be configured to control the spin holder and the cleaning liquid supply unit to perform a first process of forming a liquid film of cleaning liquid on the substrate while the spin holder is rotating the substrate; a second process of controlling the spin holder and the rinsing liquid supply unit after the first process to drain the cleaning liquid from the substrate while the spin holder is rotating the substrate; a third process of controlling the spin holder and the first solvent supply unit after the second process to drain the rinsing liquid from the substrate while the spin holder is rotating the substrate; a fourth process of controlling the spin holder and the second solvent supply unit after the third process to drain the first organic solvent from the substrate while the spin holder is rotating the substrate; and a fifth process of controlling the spin holder after the fourth process to dry the substrate. In this case, the same effects as those of the method of Example 1 can be obtained.

[0094] Example 13: In the apparatus of Example 12, the solubility parameter (SP value) of the first organic solvent may be smaller than that of the rinse liquid, and the solubility parameter (SP value) of the second organic solvent may be smaller than that of the first organic solvent. In this case, the same effects as those of the method of Example 2 can be obtained.

[0095] Example 14 In the apparatus of Example 12 or Example 13, the second organic solvent may be a mixture of multiple organic solvents. In this case, the same effects as those of the method of Example 3 can be obtained.

[0096] Example 15: In the apparatus of any one of Examples 12 to 14, the fourth process may include the second solvent supply unit supplying the second organic solvent to the substrate while the rotation holder repeatedly accelerates and decelerates the rotation of the substrate. In this case, the same effects as those of the method of Example 4 can be obtained.

[0097] Example 16 In the apparatus of Example 15, the fourth process may include increasing the supply amount of the second organic solvent from the second solvent supply unit during low-speed rotation of the substrate. In this case, the same effects as those of the method of Example 5 can be obtained.

[0098] Example 17: The apparatus of any of Examples 12 to 16 may further include a third solvent supply unit configured to supply a third organic solvent to the substrate. The third organic solvent may have lower solubility in water than the first organic solvent and a higher boiling point than the second organic solvent. The control unit may be configured to control the spin holder and the third solvent supply unit after the fourth process and before the fifth process to further perform a sixth process in which, while the spin holder is rotating the substrate, a liquid film of the third organic solvent is formed on the substrate while the second organic solvent is being discharged from the substrate. In this case, the same effects as those of the method of Example 6 can be obtained.

[0099] Example 18 In the apparatus of Example 17, the solubility parameter (SP value) of the third organic solvent may be smaller than the solubility parameter (SP value) of the second organic solvent. In this case, the same effects as those of the method of Example 7 can be obtained.

[0100] Example 19 In the apparatus of Example 17 or Example 18, the third organic solvent may be a mixture of multiple organic solvents. In this case, the same effects as those of the method of Example 8 can be obtained.

[0101] Example 20: In the apparatus of any one of Examples 17 to 19, the sixth step may include the third solvent supply unit supplying the third organic solvent to the substrate while the rotation holder repeatedly accelerates and decelerates the rotation of the substrate. In this case, the same effects as those of the method of Example 9 can be obtained.

[0102] Example 21 In the apparatus of Example 20, the maximum rotation speed of the substrate in the sixth process may be higher than the maximum rotation speed of the substrate in the fourth process. In this case, the same effects as those of the method of Example 10 can be obtained.

[0103] Example 22 In the apparatus of Example 20 or Example 21, the sixth step may include increasing the supply amount of the third organic solvent from the third solvent supply unit during low-speed rotation of the substrate. In this case, the same effects as those of the method of Example 11 can be obtained.

[0104] Example 23. An example of a computer-readable recording medium may have a program recorded thereon for causing a substrate processing apparatus to execute any one of the methods of Examples 1 to 11. In this case, the same effects as those of the method of Example 1 can be obtained. In this specification, the computer-readable recording medium may include a non-transitory computer recording medium (e.g., various main storage devices or auxiliary storage devices) or a propagated signal (e.g., a data signal that can be provided via a network). [Explanation of symbols]

[0105] 1...substrate processing system (substrate processing apparatus), 10...processing unit, 20...rotational holding section, 30...cleaning liquid supply section, 40...rinsing liquid supply section, 50...solvent supply section (first solvent supply section), 60...solvent supply section (second solvent supply section), 70...solvent supply section (third solvent supply section), Ctr...controller (control section), L1...cleaning liquid, L2...rinsing liquid, L3...organic solvent (first organic solvent), L4...organic solvent (second organic solvent), L5...organic solvent (third organic solvent), P...pattern, RM...recording medium, W...substrate, Wa...surface.

Claims

1. a rotation holder configured to hold and rotate the substrate; a cleaning liquid supply unit configured to supply a cleaning liquid to the substrate; a rinse liquid supply unit configured to supply a rinse liquid to the substrate; a first solvent supply unit configured to supply a first organic solvent to the substrate; a second solvent supply unit configured to supply a second organic solvent to the substrate; a third solvent supply unit configured to supply a third organic solvent to the substrate; a control unit; the second organic solvent has a solubility in water that is lower than or equal to that of the first organic solvent, and a boiling point that is higher than that of the first organic solvent; the third organic solvent has a lower solubility in water than the first organic solvent and a higher boiling point than the second organic solvent; the solubility parameter (SP value) of the first organic solvent is smaller than the solubility parameter (SP value) of the rinse liquid; the solubility parameter (SP value) of the second organic solvent is smaller than the solubility parameter (SP value) of the first organic solvent; The control unit a first process of controlling the spin holder and the cleaning liquid supply unit to form a liquid film of the cleaning liquid on the substrate while the substrate is being rotated by the spin holder; a second process of controlling the spin holder and the rinse liquid supply unit after the first process to discharge the cleaning liquid from the substrate while forming a liquid film of the rinse liquid on the substrate while the substrate is being rotated by the spin holder; a third process of controlling the spin holder and the first solvent supply unit after the second process to discharge the rinse liquid from the substrate while forming a liquid film of the first organic solvent on the substrate while the substrate is being rotated by the spin holder; a fourth process of controlling the spin holding unit and the second solvent supply unit after the third process to discharge the first organic solvent from the substrate while forming a liquid film of the second organic solvent on the substrate while the substrate is being rotated by the spin holding unit; a fifth process of drying the substrate by controlling the rotation holding unit after the fourth process; and a sixth process, which controls the spin holding unit and the third solvent supply unit after the fourth process and before the fifth process, to discharge the second organic solvent from the substrate while forming a liquid film of the third organic solvent on the substrate while the substrate is being rotated by the spin holding unit.

2. The apparatus of claim 1 , wherein the rinse liquid is purified water.

3. the first organic solvent is isopropyl alcohol (IPA); 3. The apparatus of claim 1, wherein the second organic solvent is propylene glycol monomethyl ether (PGME).

4. 4. The apparatus according to claim 1, wherein the second organic solvent is a mixture of a plurality of types of organic solvents.

5. The apparatus according to any one of claims 1 to 4, wherein the fourth process includes the second solvent supply unit supplying a second organic solvent to the substrate while the rotation holding unit repeatedly accelerates and decelerates the rotation of the substrate.

6. The apparatus according to claim 5 , wherein the fourth process includes increasing the supply amount of the second organic solvent from the second solvent supply unit while the substrate is rotating at a low speed.

7. The apparatus according to any one of claims 1 to 6, wherein the sixth process includes the third solvent supply unit supplying a third organic solvent to the substrate while the rotation holding unit repeatedly accelerates and decelerates the rotation of the substrate.

8. The apparatus according to claim 7 , wherein the sixth process includes increasing the supply amount of the third organic solvent from the third solvent supply unit when the substrate is rotating at a low speed.

9. 9. The apparatus according to claim 1, wherein the maximum rotation speed of the substrate in the sixth process is higher than the maximum rotation speed of the substrate in the fourth process.

10. The apparatus according to any one of claims 1 to 9, wherein the third organic solvent is a mixed liquid containing a plurality of types of organic solvents.

11. a first step of supplying a cleaning liquid onto the substrate while rotating the substrate to form a liquid film of the cleaning liquid on the substrate; a second step of supplying a rinse liquid to the substrate while rotating the substrate after the first step, thereby discharging the cleaning liquid from the substrate and forming a liquid film of the rinse liquid on the substrate; a third step of supplying a first organic solvent to the substrate while rotating the substrate after the second step, thereby discharging the rinse liquid from the substrate and forming a liquid film of the first organic solvent on the substrate; a fourth step of supplying a second organic solvent to the substrate while rotating the substrate after the third step, thereby discharging the first organic solvent from the substrate and forming a liquid film of the second organic solvent on the substrate; a fifth step of drying the substrate after the fourth step; a sixth step of supplying a third organic solvent to the substrate while rotating the substrate after the fourth step and before the fifth step, thereby discharging the second organic solvent from the substrate and forming a liquid film of the third organic solvent on the substrate; the second organic solvent has a solubility in water that is lower than or equal to that of the first organic solvent, and a boiling point that is higher than that of the first organic solvent; the third organic solvent has a lower solubility in water than the first organic solvent and a higher boiling point than the second organic solvent; the solubility parameter (SP value) of the first organic solvent is smaller than the solubility parameter (SP value) of the rinse liquid; A substrate processing method, wherein the second organic solvent has a solubility parameter (SP value) smaller than the solubility parameter (SP value) of the first organic solvent.

12. A computer-readable recording medium storing a program for causing a substrate processing apparatus to execute the method according to claim 11.

13. The recording medium according to claim 12, wherein the rinse liquid is pure water.

Images