SUBSTRATE PROCESSING METHOD AND SUBSTRATE PROCESSING APPARATUS

Abstract

To suppress pattern collapse during dry processing.SOLUTION: A substrate processing method comprises: a step S11 of supplying chemicals to an upper surface of a substrate; a step S12 of supplying a rinse liquid to the upper surface of the substrate; a step S14 of forming a liquid film of a dry process liquid on the upper surface of the substrate by supplying the dry process liquid to the upper surface of the substrate; a step S15 of heating the substrate in which the liquid film of the dry process liquid is formed on the upper surface from the lower surface side; and a step S16 of drying the substrate by removing the liquid film of the dry process liquid from the upper surface of the substrate. Surface tension of the dry process liquid is lower than surface tension of the rinse liquid. A boiling point of the dry process liquid is higher than a boiling point of the rinse liquid. A heating temperature of the substrate at the step S15 is higher than or equal to the boiling point of the rinse liquid and less than the boiling point of the dry process liquid. This makes it possible to suppress pattern collapse during the dry processing of the step S16.SELECTED DRAWING: Figure 5

Description

[Technical field]

[0001] The present invention relates to techniques for processing substrates. [Background technology]

[0002] Conventionally, in the manufacturing process of semiconductor substrates (hereinafter simply referred to as "substrates"), various processes are performed on the substrate. For example, a chemical solution such as an etching solution is supplied to the surface of the substrate held in a horizontal state to perform a chemical process. After the chemical process is completed, a rinse solution is supplied onto the substrate to perform a rinse process, and then the substrate is rotated and dried.

[0003] When a fine pattern is formed on the surface of a substrate, the surface tension of the liquid acts at the contact position between the pattern and the liquid surface (i.e., the interface between the liquid and air). Water, which is typically used as the above-mentioned rinsing liquid, has a high surface tension, so there is a risk that the pattern will collapse during the drying process after the rinsing process.

[0004] Therefore, in order to prevent the collapse of the pattern, Patent Document 1 discloses a technique in which IPA (isopropyl alcohol), which has a surface tension and boiling point lower than water, is supplied onto the substrate after the rinsing process to replace the water, and then the IPA is removed from the substrate to perform a drying process for the substrate. Patent Document 1 lists HFE (hydrofluoroether), methanol, ethanol, and the like, which have surface tension and boiling point lower than water, as liquids that can be used in place of IPA.

[0005] Patent Document 2 also discloses a technique in which, in order to prevent collapse of a pattern, IPA is supplied onto a substrate after a rinsing process to replace water, a hydrophobizing agent is supplied onto the substrate to hydrophobize the upper surface of the substrate, and IPA is further supplied onto the substrate to replace the hydrophobizing agent, and then the IPA is removed from the substrate to perform a drying process for the substrate. Patent Document 2 lists HFE, HFC (hydrofluorocarbon), methanol, ethanol, and the like, which have lower surface tensions and boiling points than water, as liquids that can be used in place of IPA. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2017-117954 A [Patent Document 2] JP 2013-157625 A Summary of the Invention [Problem to be solved by the invention]

[0007] In recent years, as the aspect ratio of patterns on a substrate increases, the patterns become more susceptible to collapse, and there is a demand for further suppression of pattern collapse during drying treatment.

[0008] The present invention has been made in consideration of the above problems, and has an object to suppress collapse of patterns during drying processing. [Means for solving the problem]

[0009] The invention described in claim 1 is a substrate processing method for processing a substrate having a pattern including a recess formed on an upper surface thereof, the method comprising the steps of: a) supplying a chemical liquid to the upper surface of the substrate; b) supplying a rinsing liquid to the upper surface of the substrate after the step a); c) supplying a drying processing liquid to the upper surface of the substrate after the step b) to form a liquid film of the drying processing liquid on the upper surface of the substrate; d) heating the substrate from below with the liquid film of the drying processing liquid formed on the upper surface; and e) drying the substrate by removing the liquid film of the drying processing liquid from the upper surface of the substrate after the step d), wherein the surface tension of the drying processing liquid is lower than the surface tension of the rinsing liquid, the boiling point of the drying processing liquid is higher than the boiling point of the rinsing liquid, and the heating temperature of the substrate in the step d) is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying processing liquid. The substrate processing method further includes, between the step b) and the step c), a step of supplying a replacement liquid to the upper surface of the substrate to replace the rinsing liquid on the upper surface of the substrate with the replacement liquid. In the step c), the replacement liquid on the upper surface of the substrate is replaced with the drying processing liquid. The invention described in claim 2 is a substrate processing method for processing a substrate having a pattern including a recess formed on an upper surface thereof, the method comprising the steps of: a) supplying a chemical liquid to the upper surface of the substrate; b) supplying a rinsing liquid to the upper surface of the substrate after the step a); c) supplying a drying liquid to the upper surface of the substrate after the step b) to form a liquid film of the drying liquid on the upper surface of the substrate; d) heating the substrate from below with the liquid film of the drying liquid formed on the upper surface; and e) removing the liquid film of the drying liquid from the upper surface of the substrate after the step d), thereby drying the substrate, wherein the drying liquid contains a fluorine-containing alcohol having a surface tension lower than that of the rinsing liquid and a boiling point higher than that of the rinsing liquid, and the heating temperature of the substrate in the step d) is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying liquid.

[0010] Claim 3 The invention described in claim 1 OR 2 The substrate processing method according to claim 1, further comprising the step of: f) removing molecules of the drying processing liquid adsorbed on the upper surface of the substrate by heating the substrate after the step e).

[0012] A fourth aspect of the present invention provides the substrate processing method according to any one of the first to third aspects, wherein in the step c), the drying processing liquid that has been preheated is supplied to the upper surface of the substrate.

[0013] A fifth aspect of the present invention provides the substrate processing method according to any one of the first to fourth aspects, wherein the substrate is heated from the lower surface side even during the step e).

[0014] The invention described in claim 6 is a substrate processing method described in any one of claims 1 to 5, wherein heating of the substrate in the d) step is performed by an electric heater arranged opposite the lower surface of the substrate.

[0016] The invention as set forth in claim 7 is a substrate processing apparatus for processing a substrate having a pattern including recesses formed on an upper surface thereof, the substrate processing apparatus including: a chemical liquid supply unit that supplies a chemical liquid to an upper surface of the substrate; a rinsing liquid supply unit that supplies a rinsing liquid to the upper surface of the substrate; a replacement liquid supply unit that supplies a replacement liquid to the upper surface of the substrate with a liquid film of the rinsing liquid formed on the upper surface and replaces the rinsing liquid on the upper surface with the replacement liquid; and a drying processing liquid that supplies a drying processing liquid to the upper surface of the substrate with a liquid film of the replacement liquid formed on the upper surface and replaces the replacement liquid on the upper surface with the replacement liquid. the substrate heating unit for heating the substrate from below while the substrate has a liquid film of the drying treatment liquid formed on the upper surface thereof; and a drying treatment unit for drying the substrate by removing the liquid film of the drying treatment liquid from the upper surface of the substrate, wherein the surface tension of the drying treatment liquid is lower than the surface tension of the rinsing liquid, the boiling point of the drying treatment liquid is higher than the boiling point of the rinsing liquid, and the heating temperature of the substrate by the substrate heating unit is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying treatment liquid. The invention according to claim 8 is a substrate processing apparatus for processing a substrate having a pattern including a recess formed on an upper surface thereof, the substrate processing apparatus comprising: a chemical liquid supply unit for supplying a chemical liquid to the upper surface of the substrate; a rinsing liquid supply unit for supplying a rinsing liquid to the upper surface of the substrate; a drying processing liquid supply unit for supplying a drying processing liquid to the upper surface of the substrate; a substrate heating unit for heating the substrate from a lower surface side in a state in which a liquid film of the drying processing liquid is formed on the upper surface; and a drying processing unit for drying the substrate by removing the liquid film of the drying processing liquid from the upper surface of the substrate, Is that surface tension but Lower than the surface tension of the rinse liquid, the boiling point but The boiling point of the rinse solution is higher than that of the rinse solution. Contains fluorine-containing alcohol, The heating temperature of the substrate by the substrate heating unit is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying processing liquid.

[0017] The invention described in claim 9 is7 or 9. The substrate processing apparatus according to claim 8, wherein the substrate heating section is an electric heater disposed opposite the lower surface of the substrate. Effect of the Invention

[0019] In the present invention, it is possible to suppress the collapse of the pattern during the drying process. [Brief description of the drawings]

[0020] [Figure 1] 1 is a plan view showing a substrate processing system according to an embodiment; [Diagram 2] FIG. 2 is a side view showing a configuration of the substrate processing apparatus. [Diagram 3] FIG. 2 is a diagram illustrating a configuration of a control unit. [Figure 4] FIG. 4 is a block diagram showing a gas / liquid supply unit. [Diagram 5] FIG. 2 is a diagram showing a flow of substrate processing. [Figure 6A] FIG. 4 is a diagram illustrating molecules of a first drying treatment liquid adsorbed onto a substrate. [Figure 6B] FIG. 13 is a diagram illustrating molecules of a second drying treatment liquid adsorbed onto a substrate. [Figure 6C] FIG. 13 is a diagram illustrating molecules of a third drying treatment liquid adsorbed onto a substrate. [Figure 7] FIG. 13 is a diagram showing a pattern collapse rate. [Figure 8] FIG. 13 is a diagram showing a pattern collapse rate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] 1 is a schematic plan view showing a layout of a substrate processing system 10 including a substrate processing apparatus according to one embodiment of the present invention. The substrate processing system 10 is a system for processing semiconductor substrates 9 (hereinafter simply referred to as "substrates 9"). The substrate processing system 10 includes an indexer block 101 and a processing block 102 coupled to the indexer block 101.

[0022] The indexer block 101 includes a carrier holding unit 104, an indexer robot 105 (i.e., substrate transport means), and an IR moving mechanism 106. The carrier holding unit 104 holds a plurality of carriers 107 capable of accommodating a plurality of substrates 9. The plurality of carriers 107 (e.g., FOUPs) are held by the carrier holding unit 104 in a state arranged in a horizontal carrier arrangement direction (i.e., the up-down direction in FIG. 1). The IR moving mechanism 106 moves the indexer robot 105 in the carrier arrangement direction. The indexer robot 105 performs an unloading operation to unload the substrate 9 from the carrier 107, and a loading operation to load the substrate 9 into the carrier 107 held by the carrier holding unit 104. The substrate 9 is transported in a horizontal position by the indexer robot 105.

[0023] On the other hand, the processing block 102 includes a plurality of (for example, four or more) processing units 108 for processing the substrate 9, and a center robot 109 (i.e., substrate transport means). The plurality of processing units 108 are arranged to surround the center robot 109 in a plan view. The plurality of processing units 108 perform various processes on the substrate 9. A substrate processing apparatus described below is one of the plurality of processing units 108. The center robot 109 performs a loading operation for loading the substrate 9 into the processing unit 108, and an unloading operation for unloading the substrate 9 from the processing unit 108. Furthermore, the center robot 109 transports the substrate 9 between the plurality of processing units 108. The substrate 9 is transported by the center robot 109 in a horizontal position. The center robot 109 receives the substrate 9 from the indexer robot 105 and passes the substrate 9 to the indexer robot 105.

[0024] Fig. 2 is a side view showing the configuration of the substrate processing apparatus 1. The substrate processing apparatus 1 is a single-wafer type apparatus that processes substrates 9 one by one. The substrate processing apparatus 1 performs liquid processing by supplying a processing liquid to the substrate 9. Fig. 2 shows a part of the configuration of the substrate processing apparatus 1 in cross section.

[0025] The substrate processing apparatus 1 includes a substrate holding unit 31, a substrate rotating mechanism 33, a gas / liquid supply unit 5, a blocking unit 6, a substrate heating unit 7, a control unit 8, and a chamber 11. The substrate holding unit 31, the substrate rotating mechanism 33, the blocking unit 6, the substrate heating unit 7, etc. are housed in the internal space of the chamber 11. An airflow forming unit 12 is provided in the canopy of the chamber 11 to supply gas to the internal space and form an airflow flowing downward (so-called downflow). For example, an FFU (fan filter unit) is used as the airflow forming unit 12.

[0026] The control unit 8 is disposed outside the chamber 11 and controls the substrate holder 31, the substrate rotating mechanism 33, the gas / liquid supply unit 5, the interrupter unit 6, the substrate heater 7, and the like. As shown in FIG. 3, the control unit 8 is, for example, a normal computer system including a processor 81, a memory 82, an input / output unit 83, and a bus 84. The bus 84 is a signal circuit that connects the processor 81, the memory 82, and the input / output unit 83. The memory 82 stores programs and various information. The processor 81 executes various processes (for example, numerical calculations) while using the memory 82, etc., according to the programs, etc. stored in the memory 82. The input / output unit 83 includes a keyboard 85 and a mouse 86 that receive input from an operator, a display 87 that displays the output, etc., from the processor 81, and a transmission unit that transmits the output, etc., from the processor 81. The control unit 8 may be a programmable logic controller (PLC), a circuit board, or the like. The control unit 8 may include any of a plurality of components among a computer system, a PLC, a circuit board, and the like.

[0027] The substrate holding unit 31 and the substrate rotation mechanism 33 shown in FIG. 2 are each a part of a spin chuck that holds and rotates the substrate 9. The substrate holding unit 31 holds the substrate 9 in a horizontal state from below. The substrate holding unit 31 is, for example, a mechanical chuck that mechanically supports the substrate 9. The substrate holding unit 31 includes a base unit 311 and a plurality of chucks 312. The base unit 311 is a substantially disk-shaped member centered on a central axis J1 that faces the up-down direction. The substrate 9 is disposed above the base unit 311 and spaced apart from the base unit 311. In other words, the base unit 311 of the substrate holding unit 31 is located at a position spaced downward from the lower main surface of the substrate 9 (hereinafter also referred to as the "lower surface 92"). The diameter of the base unit 311 is slightly larger than the diameter of the substrate 9.

[0028] The multiple chucks 312 are arranged on the outer periphery of the upper surface of the base portion 311 in a circumferential direction (hereinafter simply referred to as the "circumferential direction") centered on the central axis J1. The multiple chucks 312 are arranged, for example, at approximately equal angular intervals in the circumferential direction. In the substrate holding portion 31, the multiple chucks 312 hold the outer edge of the substrate 9. Note that the substrate holding portion 31 may be a chuck having another structure.

[0029] The substrate rotating mechanism 33 is disposed below the substrate holding part 31. The substrate rotating mechanism 33 rotates the substrate 9 together with the substrate holding part 31 about the central axis J1. The substrate rotating mechanism 33 includes a shaft 331 and a motor 332. The shaft 331 is a substantially cylindrical member centered on the central axis J1. The shaft 331 extends in the vertical direction, and is connected to the center of the lower surface of the base part 311 of the substrate holding part 31. The motor 332 is an electric rotary motor that rotates the shaft 331. The substrate rotating mechanism 33 may be a motor having another structure (for example, a hollow motor, etc.).

[0030] The gas / liquid supply unit 5 individually supplies a plurality of types of processing liquids to the substrate 9, and performs liquid processing on the substrate 9. The gas / liquid supply unit 5 also supplies an inert gas toward the substrate 9. The plurality of types of processing liquids include a chemical liquid, a rinsing liquid, a replacement liquid, and a drying processing liquid, which will be described later.

[0031] The gas / liquid supply unit 5 includes a first nozzle 51, a second nozzle 52, a third nozzle 53, and a fourth nozzle 54. The first nozzle 51, the second nozzle 52, the third nozzle 53, and the fourth nozzle 54 each eject different types of processing liquid from above the substrate 9 toward the upper main surface of the substrate 9 (hereinafter, also referred to as "upper surface 91"). A fine pattern including recesses is formed in advance on the upper surface 91 of the substrate 9. The pattern is, for example, a pattern having a high aspect ratio. The first nozzle 51, the second nozzle 52, the third nozzle 53, and the fourth nozzle 54 are formed of, for example, a resin having high chemical resistance, such as Teflon (registered trademark).

[0032] In the gas / liquid supply unit 5, two or more of the first nozzle 51, the second nozzle 52, the third nozzle 53, and the fourth nozzle 54 may be combined into one shared nozzle. In this case, the shared nozzle functions as each of the two or more nozzles. Inside the shared nozzle, an individual flow path may be provided for each type of treatment liquid, or a shared flow path through which multiple types of treatment liquid flow may be provided. Also, each of the first nozzle 51, the second nozzle 52, the third nozzle 53, and the fourth nozzle 54 may be composed of two or more nozzles.

[0033] The gas / liquid supply unit 5 further includes a first nozzle movement mechanism 511, a second nozzle movement mechanism 521, a third nozzle movement mechanism 531, and a fourth nozzle movement mechanism 541. The first nozzle movement mechanism 511 moves the first nozzle 51 approximately horizontally between a supply position above the substrate 9 and a retreat position outside the outer edge of the substrate 9 in a radial direction (hereinafter, simply referred to as the "radial direction") centered on the central axis J1. The second nozzle movement mechanism 521 moves the second nozzle 52 approximately horizontally between a supply position above the substrate 9 and a retreat position outside the outer edge of the substrate 9 in the radial direction. The third nozzle movement mechanism 531 moves the third nozzle 53 approximately horizontally between a supply position above the substrate 9 and a retreat position outside the outer edge of the substrate 9 in the radial direction. The fourth nozzle movement mechanism 541 moves the fourth nozzle 54 approximately horizontally between a supply position above the substrate 9 and a retreat position outside the outer edge of the substrate 9 in the radial direction. The first nozzle moving mechanism 511 includes, for example, an electric linear motor, an air cylinder, or a ball screw and an electric rotary motor connected to the first nozzle 51. The same is true for the second nozzle moving mechanism 521, the third nozzle moving mechanism 531, and the fourth nozzle moving mechanism 541.

[0034] The blocking unit 6 includes a top plate 61, a top plate rotating mechanism 62, and a top plate moving mechanism 63. The top plate 61 is a substantially disk-shaped member centered on a central axis J1, and is disposed above the substrate holding unit 31. The diameter of the top plate 61 is slightly larger than the diameter of the substrate 9. The top plate 61 is a member facing the upper surface 91 of the substrate 9, and is a shielding plate that shields the space above the substrate 9.

[0035] The top plate rotation mechanism 62 is disposed above the top plate 61. The top plate rotation mechanism 62 rotates the top plate 61 about the central axis J1. The top plate rotation mechanism 62 includes a shaft 621 and a motor 622. The shaft 621 is a substantially cylindrical member centered on the central axis J1. The shaft 621 extends in the vertical direction and is connected to the center of the upper surface of the top plate 61. The motor 622 is an electric rotary motor that rotates the shaft 621. The top plate rotation mechanism 62 may be a motor having another structure (for example, a hollow motor, etc.).

[0036] The top plate moving mechanism 63 moves the top plate 61 in the vertical direction above the substrate 9. The top plate moving mechanism 63 includes, for example, an electric linear motor connected to the shaft 621, an air cylinder, or a ball screw and an electric rotary motor.

[0037] The gas / liquid supply unit 5 further includes an upper nozzle 55. The upper nozzle 55 is disposed inside the shaft 621 of the top plate rotation mechanism 62. A lower end of the upper nozzle 55 protrudes downward from an opening provided in the center of the top plate 61, and faces the center of the upper surface 91 of the substrate 9 in the vertical direction. The upper nozzle 55 supplies an inert gas toward the upper surface 91 of the substrate 9.

[0038] The substrate heating unit 7 heats the substrate 9 from the lower surface 92 side. In the example shown in FIG. 2, the substrate heating unit 7 includes a hot plate 71 and a hot plate moving mechanism 72. The hot plate 71 is a substantially disk-shaped member centered on a central axis J1, and is disposed below the substrate 9. Specifically, the hot plate 71 is disposed in a space between the lower surface 92 of the substrate 9 and the upper surface of the base portion 311 of the substrate holding unit 31. The diameter of the hot plate 71 is slightly smaller than the diameter of the substrate 9. The hot plate 71 directly faces the lower surface 92 of the substrate 9 in the up-down direction (i.e., without any other member being sandwiched therebetween). The hot plate 71 is an electric heater including a substantially disk-shaped plate body 711 and a heating wire (not shown) embedded inside the plate body 711. When power is supplied to the heating wire, the plate body 711 formed of ceramics or the like is heated.

[0039] The hot plate moving mechanism 72 moves the hot plate 71 in the vertical direction below the substrate 9. The hot plate moving mechanism 72 includes a shaft 721 extending downward from the lower surface of the hot plate 71, and a drive unit (not shown) connected to the shaft 721. The shaft 721 is disposed inside the shaft 331 of the substrate rotating mechanism 33. The drive unit moves the shaft 721 in the vertical direction, thereby moving the hot plate 71 in the vertical direction below the substrate 9. The drive unit of the hot plate moving mechanism 72 is, for example, an electric linear motor, an air cylinder, or a ball screw and an electric rotary motor.

[0040] In the substrate heating section 7, the heated hot plate 71 is raised by the hot plate moving mechanism 72 and brought into contact with or close to the lower surface 92 of the substrate 9, thereby heating the substrate 9 from the lower surface 92 side. When the hot plate 71 comes into contact with the lower surface 92 of the substrate 9, the upper surface of the plate body 711 comes into contact with the lower surface 92 of the substrate 9 over substantially the entire surface. In the example shown in FIG. 2, since no mechanism is provided for rotating the hot plate 71, when the hot plate 71 comes into contact with the lower surface 92 of the substrate 9, the substrate 9 and the substrate holding section 72 move in a rotating manner. 31The rotation of the hot plate 71 is stopped. 31 may be rotated together with

[0041] FIG. 4 is a block diagram showing the gas / liquid supply unit 5 of the substrate processing apparatus 1. The first nozzle 51 is connected to a chemical supply source 512 via a pipe 513 and a valve 514. The valve 514 is opened under the control of the control unit 8 (see FIG. 2), and the chemical used for chemical processing of the substrate 9 is discharged from the tip of the first nozzle 51 to the upper surface 91 of the substrate 9. That is, the first nozzle 51 is a chemical supply unit that supplies the chemical to the substrate 9. The chemical is, for example, hydrofluoric acid. The chemical may be a liquid other than hydrofluoric acid. The chemical may be, for example, a liquid containing at least one of sulfuric acid, acetic acid, nitric acid, hydrochloric acid, hydrofluoric acid, ammonia water, hydrogen peroxide water, organic acid (for example, citric acid, oxalic acid, etc.), organic alkali (for example, TMAH: tetramethylammonium hydroxide, etc.), surfactant, and corrosion inhibitor.

[0042] The second nozzle 52 is connected to a rinse liquid supply source 522 via a pipe 523 and a valve 524. When the valve 524 is opened under the control of the control unit 8, the rinse liquid used for rinsing the substrate 9 is discharged from the tip of the second nozzle 52 onto the upper surface 91 of the substrate 9. That is, the second nozzle 52 is a rinse liquid supply unit that supplies the rinse liquid to the substrate 9. The rinse liquid is, for example, DIW (De-ionized Water). The rinse liquid may be a liquid other than DIW. The rinse liquid may be, for example, any one of carbonated water, electrolytic ionized water, hydrogen water, ozone water, and hydrochloric acid water having a dilution concentration of about 10 ppm to 100 ppm.

[0043] The third nozzle 53 is connected to a replacement liquid supply source 532 via a pipe 533 and a valve 534. The valve 534 is opened under the control of the control unit 8, and the replacement liquid used in the replacement process of the rinsing liquid is discharged from the tip of the third nozzle 53 to the upper surface 91 of the substrate 9. That is, the third nozzle 53 is a replacement liquid supply unit that supplies the replacement liquid to the substrate 9. The replacement process is a process in which the replacement liquid is supplied to the substrate 9 to replace the rinsing liquid on the substrate 9 with the replacement liquid. As the replacement liquid, a liquid that has a relatively high affinity with the above-mentioned rinsing liquid and also has a relatively high affinity with a drying process liquid described later is used. The replacement liquid is, for example, IPA (isopropyl alcohol). The replacement liquid may be a liquid other than IPA. The replacement liquid may be, for example, methanol or ethanol.

[0044] The fourth nozzle 54 is connected to the drying treatment liquid supply source 542 via a pipe 543, a valve 544, and a liquid heating unit 545. The liquid heating unit 545 preheats the drying treatment liquid used for drying the substrate 9 (specifically, applied to the substrate 9 to perform the drying treatment of the substrate 9) as necessary. The liquid heating unit 545 is, for example, an electric heater that is heated by supplying power to a built-in heating wire. The valve 544 is opened under the control of the control unit 8, so that the drying treatment liquid is discharged from the tip of the fourth nozzle 54 onto the upper surface 91 of the substrate 9. In other words, the fourth nozzle 54 is a drying treatment liquid supply unit that supplies the drying treatment liquid to the substrate 9 and brings it into contact with the substrate 9.

[0045] The drying treatment liquid preferably contains a fluorine-containing alcohol. The fluorine-containing alcohol may have, for example, a group having "-CF 2 H (difluoromethyl group)" or "-CF 3(trifluoromethyl group)". The term "terminal" refers to the terminal of the fluorinated alkyl chain opposite to "-OH (hydroxy group)" in the molecule of the fluorinated alcohol. When the fluorinated alkyl chain is branched, the terminal may be the terminal of the main chain or the terminal of the branched chain. The surface tension of the drying treatment liquid is lower than that of the above-mentioned rinse liquid. The boiling point of the drying treatment liquid is higher than that of the rinse liquid. The drying treatment liquid is a liquid that does not chemically react with the surface of the substrate 9 and the above-mentioned pattern formed on the substrate 9. The number of C included in the molecular formula of the fluorinated alcohol is preferably 3 or more, more preferably 4 or more. The number of C included in the molecular formula of the fluorinated alcohol is preferably 8 or less, more preferably 7 or less. By setting the number of C to 7 or less, it is possible to avoid being subject to PFOA (perfluorooctanoic acid) regulations.

[0046] The drying treatment liquid is, for example, 1H,1H,7H-Dodecafluoroheptanol (rational formula: H(CF 2 ) 6 CH 2 The drying treatment liquid is a liquid containing 1H,1H,3H-Tetrafluoropropanol (rational formula: CHF 2 CF 2 CH 2 Alternatively, the drying treatment liquid may be a liquid containing 2-(perfluorohexyl)ethanol (rational formula: F(CF 2 ) 6 CH 2 CH 2 The first drying treatment liquid and the second drying treatment liquid may be a liquid containing -CF 2 The third drying treatment liquid contains a fluorine-containing alcohol having -CF 3 The fluorine-containing alcohol includes a fluorine-containing alcohol having the formula:

[0047] The above-mentioned drying treatment liquid may be a liquid other than the first drying treatment liquid, the second drying treatment liquid, and the third drying treatment liquid. The drying treatment liquid may be one type of liquid or a mixed liquid containing two or more types of liquid. Preferably, the drying treatment liquid contains at least one liquid selected from the group consisting of the first drying treatment liquid, the second drying treatment liquid, and the third drying treatment liquid.

[0048] In this embodiment, the first drying treatment liquid is substantially composed of 1H,1H,7H-Dodecafluoroheptanol only. The second drying treatment liquid is substantially composed of 1H,1H,3H-Tetrafluoropropanol only. The third drying treatment liquid is substantially composed of 2-(Perfluorohexyl)ethanol only. The molecular weight of the first drying treatment liquid is 332.1 (g / mol) and the specific gravity (d20) is 1.76 (g / cm 3 ) and the boiling point is 169°C to 170°C. The molecular weight of the second drying treatment liquid is 132.1 (g / mol), and the specific gravity (d20) is 1.49 (g / cm 3 ) and the boiling point is 109°C to 110°C. The molecular weight of the third drying treatment liquid is 364.1 (g / mol), and the specific gravity (d20) is 1.68 (g / cm 3 ) and has a boiling point of 190° C. to 200° C. The first drying treatment liquid, the second drying treatment liquid, and the third drying treatment liquid are all available from Daikin Industries, Ltd.

[0049] In the substrate processing apparatus 1, when a chemical liquid is supplied from the first nozzle 51 to the substrate 9, the first nozzle 51 is located at a supply position, and the second nozzle 52, the third nozzle 53, and the fourth nozzle 54 are located at retracted positions. When a rinsing liquid is supplied from the second nozzle 52 to the substrate 9, the second nozzle 52 is located at a supply position, and the first nozzle 51, the third nozzle 53, and the fourth nozzle 54 are located at retracted positions. When a replacement liquid is supplied from the third nozzle 53 to the substrate 9, the third nozzle 53 is located at a supply position, and the first nozzle 51, the second nozzle 52, and the fourth nozzle 54 are located at retracted positions. When a drying processing liquid is supplied from the fourth nozzle 54 to the substrate 9, the fourth nozzle 54 is located at a supply position, and the first nozzle 51, the second nozzle 52, and the third nozzle 53 are located at retracted positions.

[0050] The upper nozzle 55 is connected to a gas supply source 552 via a pipe 553 and a valve 554. The valve 554 is opened under the control of the control unit 8, and nitrogen (N 2 An inert gas such as nitrogen (Ni) gas is supplied from the tip of the upper nozzle 55 to the space between the upper surface 91 of the substrate 9 and the lower surface of the top plate 61 (see FIG. 2). The inert gas may be a gas other than nitrogen (e.g., argon (Ar) gas).

[0051] Next, a flow of processing the substrate 9 in the substrate processing apparatus 1 of FIG. 2 will be described with reference to FIG. 5. In the substrate processing apparatus 1, first, the substrate 9 having a fine pattern formed on its upper surface 91 is held in a horizontal state by the substrate holder 31. Then, the upper nozzle 55 starts to supply an inert gas (e.g., nitrogen gas). The flow rate of the inert gas supplied from the upper nozzle 55 is, for example, 10 liters / min. The substrate rotation mechanism 33 starts to rotate the substrate 9. The rotation speed of the substrate 9 is, for example, 800 rpm to 1000 rpm. The top plate rotation mechanism 62 starts to rotate the top plate 61. The rotation direction and rotation speed of the top plate 61 are, for example, the same as those of the substrate 9. The top plate 61 is positioned in the up-down direction at which the first nozzle 51 and the like can be arranged between the top plate 61 and the substrate 9 (hereinafter, also referred to as the "first processing position").

[0052] Then, with the first nozzle 51 located at the supply position, a chemical liquid (e.g., hydrofluoric acid) is supplied from the first nozzle 51 to the center of the upper surface 91 of the substrate 9 (step S11). The chemical liquid supplied to the center of the substrate 9 spreads radially outward from the center of the substrate 9 due to centrifugal force caused by the rotation of the substrate 9, and is applied to the entire upper surface 91 of the substrate 9. The chemical liquid scatters or flows out radially outward from the outer edge of the substrate 9. The chemical liquid that scatters or flows out from the substrate 9 is received and collected by a cup portion or the like (not shown). The same applies to other processing liquids. In the substrate processing apparatus 1, the chemical liquid is applied to the substrate 9 for a predetermined period of time, thereby performing chemical processing of the substrate 9.

[0053] 2, the hot plate 71 is positioned at a position far below the lower surface 92 of the substrate 9, and the substrate 9 is not heated by the hot plate 71. Similarly to step S11, the substrate 9 is not heated by the hot plate 71 during the rinsing process of step S12 and the replacement process of step S13, which will be described below.

[0054] When the chemical liquid processing of the substrate 9 is completed, the first nozzle 51, which has stopped discharging the chemical liquid, is moved from the supply position to the retreat position, and the second nozzle 52 is moved from the retreat position to the supply position. Then, a rinse liquid (e.g., DIW) is supplied from the second nozzle 52 to the center of the upper surface 91 of the substrate 9 (step S12). The rotation speed of the substrate 9 during the supply of the rinse liquid is, for example, 800 rpm to 1200 rpm. The rinse liquid supplied to the center of the substrate 9 spreads radially outward from the center of the substrate 9 due to centrifugal force caused by the rotation of the substrate 9, and is applied to the entire upper surface 91 of the substrate 9. The chemical liquid on the substrate 9 is moved radially outward by the rinse liquid and removed from the substrate 9. In the substrate processing apparatus 1, the rinse liquid is applied to the substrate 9 for a predetermined time, thereby performing a rinse process on the substrate 9.

[0055] When the chemical liquid is removed from substrate 9 (i.e., when the chemical liquid on substrate 9 is entirely replaced with the rinsing liquid), the rotation speed of substrate 9 is reduced. As a result, a liquid film of the rinsing liquid is formed and maintained on upper surface 91 of substrate 9. The rotation speed of substrate 9 is, for example, 10 rpm. The liquid film of the rinsing liquid covers the entire upper surface 91 of substrate 9. When the liquid film of the rinsing liquid is formed, the discharge of the rinsing liquid from second nozzle 52 is stopped, and second nozzle 52 is retracted from the supply position to the retracted position. The rotation speed of substrate 9 may be any speed at which upper surface 91 of substrate 9 does not dry out, and may be, for example, 10 rpm or higher.

[0056] Next, the third nozzle 53 is moved from the retreated position to the supply position, and the replacement liquid is supplied from the third nozzle 53 to the center of the upper surface 91 of the substrate 9 (i.e., the center of the liquid film of the rinsing liquid) (step S13). The replacement liquid is, for example, IPA. The rotation speed of the substrate 9 during the supply of the replacement liquid is, for example, 100 rpm to 300 rpm. The replacement liquid supplied to the center of the substrate 9 spreads radially outward from the center of the substrate 9 due to centrifugal force caused by the rotation of the substrate 9, and is applied to the entire upper surface 91 of the substrate 9. The rinsing liquid on the substrate 9 (i.e., the rinsing liquid in contact with the upper surface 91 of the substrate 9) is moved radially outward by the replacement liquid and removed from the substrate 9. In the substrate processing apparatus 1, the replacement liquid is applied to the substrate 9 for a predetermined time, thereby performing a replacement process for replacing the rinsing liquid with the replacement liquid on the substrate 9.

[0057] When the rinsing liquid is removed from the substrate 9 (i.e., when the rinsing liquid on the substrate 9 is entirely replaced with the replacement liquid), the rotation speed of the substrate 9 is reduced. As a result, a liquid film of the replacement liquid is formed and maintained on the upper surface 91 of the substrate 9. The rotation speed of the substrate 9 is, for example, 10 rpm. The liquid film of the replacement liquid covers the entire upper surface 91 of the substrate 9. When the liquid film of the replacement liquid is formed, the discharge of the replacement liquid from the third nozzle 53 is stopped, and the third nozzle 53 is retracted from the supply position to the retracted position. The rotation speed of the substrate 9 may be any speed at which the upper surface 91 of the substrate 9 does not dry out, and may be, for example, 10 rpm or higher.

[0058] Next, the fourth nozzle 54 is moved from the retreated position to the supply position, and the drying process liquid is supplied from the fourth nozzle 54 to the center of the upper surface 91 of the substrate 9 (i.e., the center of the liquid film of the replacement liquid). The drying process liquid is, for example, the above-mentioned first drying process liquid or second drying process liquid. The rotation speed of the substrate 9 when the drying process liquid is supplied is, for example, 100 rpm to 300 rpm. The drying process liquid supplied to the center of the substrate 9 spreads radially outward from the center of the substrate 9 by centrifugal force due to the rotation of the substrate 9, and is applied to the entire upper surface 91 of the substrate 9. The replacement liquid on the substrate 9 (i.e., the replacement liquid in contact with the upper surface 91 of the substrate 9) is moved radially outward by the drying process liquid and removed from the substrate 9. In the substrate processing apparatus 1, the drying process liquid is applied to the substrate 9 for a predetermined time, so that the replacement liquid on the substrate 9 is entirely replaced with the drying process liquid.

[0059] The drying treatment liquid supplied to the substrate 9 from the fourth nozzle 54 may or may not be preheated by the above-mentioned liquid heating unit 545 (see FIG. 4). When heating is performed by the liquid heating unit 545, the temperature of the drying treatment liquid after heating by the liquid heating unit 545 is higher than room temperature (e.g., 25° C.) and lower than the boiling point of the drying treatment liquid.

[0060] When the replacement liquid on the substrate 9 is entirely replaced with the drying processing liquid, the rotation speed of the substrate 9 is reduced. As a result, a liquid film of the drying processing liquid is formed and maintained on the upper surface 91 of the substrate 9 (step S14). The liquid film of the drying processing liquid covers the entire upper surface 91 of the substrate 9. When the liquid film of the drying processing liquid is formed, the ejection of the drying processing liquid from the fourth nozzle 54 is stopped, and the fourth nozzle 54 is retracted from the supply position to the retracted position. In addition, the substrate holding portion 51 is rotated by the substrate rotation mechanism 33. 31 And the rotation of the substrate 9 is stopped.

[0061] 2 by the hot plate moving mechanism 72, and the hot plate 71 is brought into contact with the lower surface 92 of the substrate 9. The hot plate 71 has been heated to a predetermined temperature in advance, and as the hot plate 71 comes into contact with the lower surface 92 of the substrate 9, the drying treatment liquid in contact with the upper surface 91 of the substrate 9 is heated together with the substrate 9, and is heated to a predetermined contact temperature and maintained at that contact temperature (step S15).

[0062] In step S15, the hot plate 71 may be close to the lower surface 92 of the substrate 9 with a small gap therebetween, without contacting the lower surface 92. In this case, after the liquid film of the drying processing liquid is formed on the substrate 9, the rotation of the substrate 9 may be continued at a low speed (e.g., 10 rpm) without being stopped. In this case, heating of the substrate 9 from the lower surface 92 side by the hot plate 71 may be started in parallel with the supply of the drying processing liquid in step S14.

[0063] In step S15, as described above, the drying treatment liquid supplied onto the substrate 9 may be heated in advance to a temperature higher than room temperature. In this case, the time required for increasing the temperature of the drying treatment liquid on the substrate 9 to the contact temperature by heating with the hot plate 71 can be shortened.

[0064] The above-mentioned contact temperature is a temperature equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying liquid. This suppresses evaporation of the drying liquid on the substrate 9, and even if a component of the rinsing liquid (e.g., moisture) is mixed into the drying liquid, the component of the rinsing liquid is evaporated and removed from the drying liquid. When water is used as the rinsing liquid, the drying liquid is set to have a boiling point equal to or higher than the rinsing liquid, so that moisture in the air is prevented from condensing and being mixed into the drying liquid. Preferably, the difference between the contact temperature and the boiling point of the drying liquid is 65° C. or lower. In other words, it is preferable that the contact temperature is lower than the boiling point of the drying liquid and is equal to or higher than a temperature that is 65° C. lower than the boiling point of the drying liquid.

[0065] In the substrate processing apparatus 1, the drying processing liquid at the contact temperature is brought into contact with the entire upper surface 91 of the substrate 9 for a predetermined contact time (preferably, 10 seconds or more). As a result, molecules of the drying processing liquid are adsorbed onto the upper surface 91 of the substrate 9 and the surface of the pattern on the upper surface 91 of the substrate 9.

[0066] FIG. 6A is a diagram showing a schematic diagram of a molecule of a first drying treatment liquid (i.e., 1H,1H,7H-Dodecafluoroheptanol) adsorbed on the upper surface 91 of the substrate 9. FIG. 6B is a diagram showing a schematic diagram of a molecule of a second drying treatment liquid (i.e., 1H,1H,3H-Tetrafluoropropanol) adsorbed on the upper surface 91 of the substrate 9. FIG. 6C is a diagram showing a schematic diagram of a molecule of a third drying treatment liquid (i.e., 2-(Perfluorohexyl)ethanol) adsorbed on the upper surface 91 of the substrate 9. In FIG. 6A to FIG. 6C, the molecules of the first drying treatment liquid, the second drying treatment liquid, and the third drying treatment liquid are shown by skeletal structural formulas.

[0067] As shown in FIG. 6A, the hydroxyl groups (-OH) of the first drying treatment liquid attract oxygen atoms (O) on the upper surface 91 of the substrate 9, and the molecules of the first drying treatment liquid are adsorbed onto the upper surface 91 of the substrate 9. As a result, the upper surface 91 of the substrate 9 is covered with the molecules of the first drying treatment liquid. In detail, the upper surface 91 of the substrate 9 is covered with -CF 2 Similarly, in the case of the second drying treatment liquid shown in FIG. 6B, the molecules of the second drying treatment liquid are adsorbed to the upper surface 91 of the substrate 9, and the upper surface 91 of the substrate 9 is covered with -CF 2 In the case of the third drying treatment liquid shown in FIG. 6C, the molecules of the third drying treatment liquid are adsorbed to the upper surface 91 of the substrate 9 in a substantially similar manner, and the upper surface 91 of the substrate 9 is covered with -CF 3 6A to 6C are schematic diagrams, and therefore the adsorption direction and adsorption density of the first drying treatment liquid, the second drying treatment liquid, and the third drying treatment liquid to the substrate 9 differ from the actual ones.

[0068] Similarly, for the pattern on the upper surface 91 of the substrate 9, the molecules of the first drying treatment liquid are adsorbed to the pattern surface, and the pattern surface is formed by -CF 2 H. As a result, the surface free energy of the pattern is reduced compared to when the first drying treatment liquid is not adsorbed on the pattern surface, and the contact angle of the first drying treatment liquid with respect to the pattern surface increases and approaches 90°. Similarly, in the case of the second drying treatment liquid, the molecules of the second drying treatment liquid are adsorbed on the pattern surface, and the pattern surface is covered with -CF 2 H. As a result, the surface free energy of the pattern is reduced compared to when the second drying treatment liquid is not adsorbed on the pattern surface, and the contact angle of the second drying treatment liquid with respect to the pattern surface increases and approaches 90°. In the case of the third drying treatment liquid, the molecules of the third drying treatment liquid are adsorbed on the pattern surface in a substantially similar manner, and the pattern surface is covered with -CF 3 The pattern surface is covered with the third drying treatment liquid. As a result, the surface free energy of the pattern is reduced compared to when the third drying treatment liquid is not adsorbed on the pattern surface, and the contact angle of the third drying treatment liquid with respect to the pattern surface increases and approaches 90°. Regardless of whether any one of the first drying treatment liquid, the second drying treatment liquid, and the third drying treatment liquid is adsorbed on the pattern surface, the surface free energy of the pattern with the drying treatment liquid adsorbed thereon is lower than the surface free energy of silicon (Si) with no drying treatment liquid adsorbed thereon.

[0069] On the pattern surface, the longer the fluorinated alkyl chain of the fluorine-containing alcohol molecule, the closer to perpendicular the adsorption direction of the molecules of the drying treatment liquid to the pattern surface, and the higher the orientation of the molecules of the drying treatment liquid on the pattern surface. The number of Cs contained in the molecules of the first drying treatment liquid shown in FIG. 6A is 7, and the number of Cs contained in the molecules of the second drying treatment liquid shown in FIG. 6B is 3. Thus, since the molecules of the first drying treatment liquid have a longer fluorinated alkyl chain than the molecules of the second drying treatment liquid, the adsorption direction of the molecules of the first drying treatment liquid is closer to perpendicular than the adsorption direction of the molecules of the second drying treatment liquid. Therefore, the molecules of the first drying treatment liquid are more densely adsorbed to the pattern surface than the molecules of the second drying treatment liquid. As a result, when the first drying treatment liquid is used as the drying treatment liquid, the amount of reduction in the surface free energy of the pattern is larger than when the second drying treatment liquid is used, and the contact angle with respect to the pattern surface is closer to 90°.

[0070] After the drying processing liquid at the contact temperature has been brought into contact with the entire upper surface 91 of the substrate 9, and the above-mentioned contact time has elapsed, the top plate 61 descends from the first processing position to a position (hereinafter also referred to as the "second processing position") closer to the upper surface 91 of the substrate 9. As a result, the space between the upper surface 91 of the substrate 9 and the lower surface of the top plate 61 is substantially isolated from the surrounding space (i.e., the space radially outside the substrate 9).

[0071] Also, the hot plate 71 is slightly lowered and separated from the lower surface 92 of the substrate 9, and is brought into a state in which it is close to the lower surface 92 with a small gap therebetween. Even in this state, the temperature of the liquid film of the drying processing liquid on the substrate 9 is maintained at the above-mentioned contact temperature, substantially similar to the state in which the hot plate 71 is in contact with the lower surface 92 of the substrate 9. Note that, as described above, when the hot plate 71 is in contact with the substrate holding portion 31 If configured to rotate with the hot plate 71 , the hot plate 71 may be maintained in contact with the underside 92 of the substrate 9 .

[0072] Then, by spraying the inert gas from the upper nozzle 55 toward the center of the upper surface 91 of the substrate 9, a hole (i.e., a region where the drying processing liquid is pushed aside and the upper surface 91 of the substrate 9 is exposed) is formed in the center of the liquid film of the drying processing liquid. The hole is pushed outward in the circumferential direction by the inert gas supplied from the upper nozzle 55. In other words, the liquid film of the drying processing liquid on the substrate 9 (i.e., the drying processing liquid in contact with the upper surface 91 of the substrate 9) is moved outward in the radial direction by the inert gas and removed from above the substrate 9.

[0073] In the substrate processing apparatus 1, the substrate 9 is further rotated at high speed by the substrate rotating mechanism 33. As a result, the drying processing liquid present on the upper surface 91 of the substrate 9 is moved radially outward by centrifugal force and quickly removed from the substrate 9. In the substrate processing apparatus 1, the high-speed rotation of the substrate 9 by the substrate rotating mechanism 33 is continued for a predetermined time, thereby performing a drying process (so-called spin-drying process) of the substrate 9 (step S16). In the above example, the upper nozzle 55 and the substrate rotating mechanism 33 are a drying processing liquid removal unit that removes the liquid drying processing liquid from the upper surface 91 of the substrate 9, and also a drying processing unit that dries the substrate 9 by removing the drying processing liquid.

[0074] In step S16, the substrate 9 may not be rotated by the substrate rotating mechanism 33, and the drying treatment liquid on the substrate 9 may be removed only by spraying the inert gas from the upper nozzle 55. Alternatively, in step S16, the substrate 9 may not be rotated by the substrate rotating mechanism 33, and the drying treatment liquid on the substrate 9 may be removed only by rotating the substrate 9.

[0075] In the drying process of the substrate 9, when the liquid level of the drying process liquid is lowered to a position between the patterns, a capillary force acts to pull the patterns in the horizontal direction. The capillary force σmax is expressed by the formula (1) using the surface tension γ of the drying process liquid, the contact angle θ between the drying process liquid and the patterns, the distance D between the patterns, the height H of the patterns, and the width W of the patterns. σmax=(6γ cosθ / D) (H / W) 2 ··· Equation (1)

[0076] In the substrate processing apparatus 1, as described above, the surface tension γ of the drying processing liquid is lower than that of the rinsing liquid. Therefore, in the drying processing in step S16, the capillary force σmax acting on the pattern can be made smaller than in the case where the rinsing liquid (e.g., DIW) remaining on the substrate 9 after the rinsing processing is removed by a spin-drying process or the like to dry the substrate 9 (hereinafter, also referred to as a "rinse-drying process"). As a result, in the drying processing in step S16, the collapse of the pattern can be suppressed more effectively than in the rinse-drying process.

[0077] In addition, in the substrate processing apparatus 1, the surface free energy of the pattern is reduced by adsorbing the fluorine-containing alcohol contained in the drying processing liquid to the surface of the pattern. Therefore, compared to the case where the rinsing liquid remaining on the substrate 9 after the rinsing processing is replaced with a replacement liquid (e.g., IPA) and the replacement liquid is removed by a spin-drying process or the like to dry the substrate 9 (hereinafter also referred to as a "replacement drying process"), the contact angle θ on the surface of the pattern can be increased and brought closer to 90°. Therefore, in the drying process of step S16, the capillary force σmax acting on the pattern can be made smaller than in the replacement drying process. As a result, in the drying process of step S16, the collapse of the pattern can be suppressed more than in the replacement drying process.

[0078] In addition, in conventional replacement drying processes, IPA, methanol, ethanol, etc. are used as replacement liquids. Although IPA, methanol, and ethanol can be adsorbed to the pattern surface by -OH, they do not contain fluorine, so they do not contribute much to reducing the surface free energy of the pattern. Therefore, there is a limit to how much they can prevent the pattern from collapsing during drying.

[0079] Moreover, if HFE (hydrofluoroether), HFC (hydrofluorocarbon) or HFO (hydrofluoroolefin) is used instead of the drying liquid in step S14, the molecules of these liquids do not substantially adsorb to the pattern surface because they do not have functional groups such as -OH at their ends that are easily adsorbed to the pattern surface. Therefore, the surface free energy of the pattern is not substantially reduced. For this reason, it is not possible to effectively suppress the collapse of the pattern during the drying process.

[0080] 7 and 8 are diagrams showing experimental comparisons of the collapse rate of the pattern on the substrate 9 after the processing of steps S11 to S16 and the collapse rate of the pattern on the substrate 9 after the above-mentioned replacement drying processing (i.e., processing in which, after steps S11 to S13, steps S14 to S15 are omitted and the replacement liquid on the substrate 9 is removed by spin drying processing and then dried). In Figs. 7 and 8, the experiments were carried out using a test coupon on whose surface a pattern was formed. Fig. 7 shows the results of an experiment in which SiO 2 The results of an experiment using a test coupon with a hydrophilic surface on which a film was formed are shown in FIG. 2 The results of an experiment using a test coupon with an etched hydrophobic surface on the membrane are shown.

[0081] The vertical axis in Figs. 7 and 8 indicates the collapse rate of the pattern on the surface of the test coupon. "Examples 1 and 6" on the horizontal axis in Figs. 7 and 8 indicate the experimental results corresponding to the above-mentioned processing of steps S11 to S16 using the first drying processing liquid as the drying processing liquid. "Example 2" on the horizontal axis indicates the experimental results corresponding to the above-mentioned processing of steps S11 to S16 using the second drying processing liquid as the drying processing liquid. "Examples 3 to 5 and 7" on the horizontal axis indicate the experimental results corresponding to the above-mentioned processing of steps S11 to S16 using the third drying processing liquid as the drying processing liquid. Furthermore, "Comparative Example 1" on the horizontal axis indicates the experimental results corresponding to the replacement drying processing using IPA as the replacement liquid (i.e., processing in which steps S14 to S15 are omitted). "Comparative Example 2" on the horizontal axis indicates the experimental results corresponding to the replacement drying processing using HFE-7100 (rational formula: C 4 F9 OCH 3 4 shows the experimental results corresponding to the processes in steps S11 to S16 described above when a fluorous benzene ring was used (methoxy-nonafluorobutane).

[0082] The test coupon is a roughly rectangular, flat member measuring 20 mm square. The pattern formed on the surface of the test coupon is composed of a number of rectangles of different sizes that have their centers at the same position when viewed from above. The AR (Aspect Ratio: ratio between the bottom and height of the pattern) of the pattern is 20. The supply of the processing liquids in steps S11 to S14 was performed by immersing the test coupon in a beaker in which each processing liquid was stored.

[0083] In Example 1 in FIG. 7, the test coupon was immersed in the first drying treatment liquid in a beaker at the contact temperature for 1 minute, and then the test coupon was taken out of the beaker and allowed to dry naturally. The contact temperature was 10°C lower than the boiling point of the first drying treatment liquid. Thereafter, the pattern collapse rate on the test coupon was determined. For the substrate 9 having a hydrophilic surface, the pattern collapse rate in Example 1 was about 47%. The pattern collapse rate was determined by performing image analysis of the test coupon. The method for determining the pattern collapse rate is the same in Examples 2 to 7 and Comparative Examples 1 and 2.

[0084] In relation to Example 1, the contact temperature of the first drying treatment liquid was changed in various ways within a range below the boiling point of the first drying treatment liquid to determine the pattern collapse rate, and the collapse rate increased as the difference between the contact temperature and the boiling point increased. Also, in relation to Example 1, the contact angle of the first drying treatment liquid on the test coupon was measured while changing the above-mentioned contact time in various ways. As a result, the contact angle increased as the contact time increased within a range of 15 minutes or less, but the contact angle did not change much when the contact time was 15 minutes or more.

[0085] 7 is similar to Example 1, except that the first drying treatment liquid was changed to the second drying treatment liquid and the contact temperature was set to a temperature 10° C. lower than the boiling point of the second drying treatment liquid. For the substrate 9 having a hydrophilic surface, the pattern collapse rate of Example 2 was about 53%.

[0086] 7 is similar to Example 1, except that the first drying treatment liquid was changed to the third drying treatment liquid and the contact temperature was set to a temperature 40° C. lower than the boiling point of the third drying treatment liquid. For the substrate 9 having a hydrophilic surface, the pattern collapse rate of Example 3 was about 13%.

[0087] 7 is similar to Example 1, except that the first drying treatment liquid was changed to the third drying treatment liquid and the contact temperature was set to a temperature 65° C. lower than the boiling point of the third drying treatment liquid. For the substrate 9 having a hydrophilic surface, the pattern collapse rate in Example 4 was about 17%.

[0088] 7 is the same as Example 1, except that the first drying treatment liquid was changed to the third drying treatment liquid and the contact temperature was set to a temperature 90° C. lower than the boiling point of the third drying treatment liquid. For the substrate 9 having a hydrophilic surface, the pattern collapse rate of Example 5 was about 31%.

[0089] 7 is the same as Example 1, except that the first drying treatment liquid was changed to IPA and the contact temperature was set to a temperature 10° C. lower than the boiling point of IPA. For the substrate 9 having a hydrophilic surface, the pattern collapse rate of Comparative Example 1 was about 86%.

[0090] 7, by carrying out the above-mentioned steps S11 to S16 (Examples 1 to 5) on a substrate 9 having a hydrophilic surface, pattern collapse could be suppressed compared to a replacement drying process (Comparative Example 1) in which steps S14 to S15 were omitted. That is, even for a substrate 9 having a hydrophilic surface in which the rate of pattern collapse is higher than that of a hydrophobic surface in the conventional drying process (Comparative Example 1), pattern collapse can be suppressed by carrying out the steps S11 to S16 (Examples 1 to 5) according to the present invention.

[0091] Comparing Example 1 and Example 2, the -CF 2 Among the first and second drying treatment liquids having H, the use of the first drying treatment liquid (Example 1) whose molecular formula contains 7 C's was able to further suppress pattern collapse compared to the use of the second drying treatment liquid (Example 2) whose molecular formula contains 3 C's. In addition, when Example 1 is compared with Examples 3 to 5, the use of the first drying treatment liquid having -CF 3 By using the third drying treatment liquid (Examples 3 to 5) having 2 Compared to the case where the first drying treatment liquid having H (Example 1) was used, collapse of the pattern could be further suppressed. Comparing Examples 3 and 4 with Example 5, by setting the difference between the contact temperature and the boiling point of the third drying treatment liquid to 65° C. or less (Examples 3 and 4), collapse of the pattern could be further suppressed compared to the case where the difference between the contact temperature and the boiling point of the third drying treatment liquid was greater than 65° C. (Example 5: temperature difference of 90° C.).

[0092] In Example 6 in FIG. 8, a beaker was used to immerse a test coupon in dilute hydrofluoric acid (concentration: about 1% by volume) for 1 minute, then in DIW for 1 minute, and further in IPA for 3 minutes, and then in a first drying treatment liquid at room temperature. The first drying treatment liquid was then heated to a contact temperature 10°C lower than the boiling point of the first drying treatment liquid, and maintained for 1 minute. Thereafter, the test coupon was removed from the beaker and naturally dried, and the pattern collapse rate was determined. For the substrate 9 having a hydrophobic surface, the pattern collapse rate in Example 6 was about 10%.

[0093] Example 7 in FIG. 8 is similar to Example 6, except that the first drying treatment liquid was changed to the third drying treatment liquid and the contact temperature was set to a temperature 40° C. lower than the boiling point of the third drying treatment liquid. Sparse For substrate 9 having an aqueous surface, the pattern collapse rate in Example 7 was about 17%.

[0094] 8 is the same as Example 6, except that the first drying treatment liquid was changed to HFE-7100 and the contact temperature was set to a temperature 10° C. lower than the boiling point of HFE-7100. For the substrate 9 having a hydrophobic surface, the pattern collapse rate of Comparative Example 2 was about 62%.

[0095] As shown in Fig. 8, by carrying out the above-mentioned steps S11 to S16 using a drying treatment liquid for a substrate 9 having a hydrophobic surface (Examples 6 and 7), it was possible to suppress the collapse of the pattern compared to the case where steps S11 to S16 are carried out using HFE (Comparative Example 2). 2 By using the first drying treatment solution (Example 6) having H, 3 In comparison with the case where the third drying treatment liquid having the above structure (Example 7) was used, the collapse of the pattern could be further suppressed.

[0096] Table 1 below shows the relationship between the contact temperature of the drying processing liquid in step S15 (that is, the heating temperature of the drying processing liquid by the hot plate 71) and the collapse rate of the pattern on the substrate 9 after the drying processing in step S16.

[0097] [Table 1]

[0098] In Examples 8 and 9 in Table 1, experiments were performed using a test coupon having a hydrophilic surface on which a pattern different from the above-mentioned test coupon was formed. The pattern of the test coupon was composed of a number of fine pillar-shaped patterns (i.e., pinholder-shaped Si nano pillars). The test coupon was a roughly rectangular flat member with a square of 20 mm. The AR (Aspect Ratio: ratio of the bottom to the height of the pattern) of the pattern formed on the surface of the test coupon was 20. The supply of the treatment liquid in steps S11 to S14 was performed by dropping the treatment liquid onto the upper surface of the test coupon (i.e., the surface on which the above-mentioned pattern was formed) using a pipette. The treatment liquid was removed from the test coupon by sucking the treatment liquid on the test coupon using a pipette.

[0099] In Example 8, the third drying treatment liquid at room temperature was dropped onto the upper surface of the test coupon placed on a hot plate (step S14), and the test coupon was heated to 150°C from the lower surface (i.e., the surface on which the pattern is not formed) by the hot plate (step S15). The temperature of the test coupon in step S15 (i.e., the contact temperature) is lower than the boiling point (190°C to 200°C) of the third drying treatment liquid. Then, the test coupon to which the third drying treatment liquid was applied was maintained at 150°C for 1 minute, and then the third drying treatment liquid on the test coupon was removed, and the collapse rate of the pattern on the test coupon was obtained. The collapse rate of the pattern was obtained by performing image analysis of the test coupon in the same manner as above. The collapse rate of the pattern in Example 8 was 6.8%.

[0100] Example 9 is similar to Example 8, except that the contact temperature in step S15 was 170° C. The pattern collapse rate in Example 9 was 1.7%. Comparing Example 8 and Example 9, the smaller the difference between the contact temperature and the boiling point of the drying treatment liquid, the more the collapse rate was reduced.

[0101] When the above-mentioned step S16 (drying process of the substrate 9) is completed, the substrate 9 is heated by the substrate heating unit 7, thereby removing the molecules of the drying process liquid adsorbed on the surface of the substrate 9 (i.e., the surface of the pattern on the substrate 9, etc.) (step S17). In the adsorbed molecule removal process of step S17, the temperature of the substrate 9 (hereinafter also referred to as the "molecule removal temperature") is set to a temperature higher than the boiling point of the above-mentioned drying process liquid. The molecules of the drying process liquid removed from the substrate 9 in step S17 are not the liquid drying process liquid, but a small number of molecules that remain adsorbed on the substrate 9 even after the liquid drying process liquid is removed from the substrate 9 in the drying process of step S16. When the step S17 is completed, the substrate 9 is unloaded from the substrate processing apparatus 1.

[0102] In the above example, the adsorbed molecule removal process in step S17 is performed on the substrate 9 held by the substrate holder 31 in the same chamber 11 in which steps S11 to S16 are performed, but is not limited to this. For example, after completion of step S16, the substrate 9 may be transferred from the processing unit 108 of the substrate processing apparatus 1 to another processing unit 108 (see FIG. 1), and the adsorbed molecule removal process of the substrate 9 may be performed in the other processing unit 108 by an ashing process using plasma, UV, excimer, or the like. Alternatively, the adsorbed molecule removal process may be performed in the other processing unit 108 by heating with a hot plate.

[0103] In the above example, a replacement process of the rinsing liquid with a replacement liquid in step S13 is performed between the rinsing process in step S12 and the supply of the drying process liquid in step S14, but if the rinsing liquid can be suitably removed from the substrate 9 by directly supplying the drying process liquid to the liquid film of the rinsing liquid on the substrate 9, step S13 may be omitted. For example, if the affinity between the rinsing liquid and the drying process liquid is relatively high, step S13 can be omitted. Also, for example, step S13 can be omitted if the specific gravity of the drying process liquid is somewhat higher than that of the rinsing liquid and the drying process liquid is supplied at a small flow rate to the liquid film of the rinsing liquid so that the drying process liquid settles suitably to the bottom of the liquid film.

[0104] As described above, the substrate processing method for processing the substrate 9 having a pattern including recesses formed on its upper surface includes a step of supplying a chemical liquid to the upper surface 91 of the substrate 9 (step S11), a step of supplying a rinsing liquid to the upper surface 91 of the substrate 9 after step S11 (step S12), a step of supplying a drying liquid to the upper surface 91 of the substrate 9 after step S12 to form a liquid film of the drying liquid on the upper surface 91 of the substrate 9 (step S14), a step of heating the substrate 9 from the lower surface 92 side in a state in which the liquid film of the drying liquid has been formed on the upper surface 91 (step S15), and a step of drying the substrate 9 by removing the liquid film of the drying liquid from the upper surface 91 of the substrate 9 after step S15 (step S16). The surface tension of the drying liquid is lower than that of the rinsing liquid. The boiling point of the drying liquid is higher than that of the rinsing liquid. The heating temperature of the substrate 9 in step S15 is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying liquid. This makes it possible to prevent the pattern from collapsing during the drying process in step S16.

[0105] The above-mentioned substrate processing method has the following advantages over other heating methods by heating the liquid film of the drying processing liquid from the lower surface 92 side of the substrate 9 in step S15. For example, when the drying processing liquid heated to a temperature higher than the above-mentioned contact temperature is supplied onto the substrate 9 and the temperature of the liquid film of the drying processing liquid on the substrate 9 is controlled to be the contact temperature due to a temperature drop caused by contact with the substrate 9 and the outside air, it is difficult to accurately predict the temperature drop, and the control of the heating temperature of the drying processing liquid may become complicated. In addition, since the temperature of the drying processing liquid needs to be lower than the boiling point in the heating of the drying processing liquid performed in advance, there is a limit to reducing the difference between the boiling point of the drying processing liquid and the liquid film temperature of the drying processing liquid on the substrate 9. Furthermore, in order to maintain the liquid film temperature on the substrate 9, it is necessary to continue supplying the drying processing liquid even after the liquid film is formed, which may increase the cost of processing the substrate 9.

[0106] In contrast, in the above-described substrate processing method, the temperature of the contact portion of the interface between the drying processing liquid on the substrate 9 and the substrate 9 can be easily adjusted to a desired temperature by heating the liquid film of the drying processing liquid from the lower surface 92 side of the substrate 9. In addition, since the difference between the boiling point of the drying processing liquid and the liquid film temperature of the drying processing liquid on the substrate 9 can be reduced, collapse of the pattern during the drying processing in step S16 can be further suppressed as shown in Examples 8 and 9. Furthermore, since the supply of the drying processing liquid can be stopped after the liquid film of the drying processing liquid is formed on the substrate 9, the cost associated with processing the substrate 9 can also be suppressed.

[0107] Furthermore, when the liquid film of the drying processing liquid is heated by irradiating the liquid film with light from above the substrate 9, the light is reflected on the surface of the liquid film of the drying processing liquid, which may reduce the heating efficiency of the liquid film.

[0108] In contrast, in the above-described substrate processing method, the temperature of the portion of the liquid film of the drying processing liquid that contacts the upper surface 91 of the substrate 9 can be made equal to or higher than the surface temperature of the liquid film of the drying processing liquid, so that the occurrence of cracks and the like due to rapid evaporation of the liquid film surface can be suppressed. Also, the liquid film of the drying processing liquid can be efficiently heated.

[0109] As described above, the drying liquid preferably contains a fluorine-containing alcohol. As a result, in steps S14 to S15, -OH of the drying liquid is bonded to oxygen atoms (O) on the pattern surface, and the molecules of the drying liquid are adsorbed to the pattern surface. As a result, the pattern surface is covered with molecules of the drying liquid. Therefore, compared with the case where the drying liquid is not adsorbed on the pattern surface, the surface free energy of the pattern is reduced, and the contact angle of the drying liquid with respect to the pattern surface increases and approaches 90°. As a result, the capillary force acting between the patterns is reduced, and the collapse of the pattern during the drying process in step S16 can be further suppressed.

[0110] The above-mentioned fluorine-containing alcohol has a -CF 2It is preferable that the surface of the pattern has -CF H at the end of the molecule of the drying treatment liquid. 2 The molecule is covered with -CF 2 H has a large effect of reducing the surface free energy, and therefore, the collapse of the pattern during the drying process in step S16 can be further suppressed.

[0111] In addition, fluorine-containing alcohols have a -CF 3 In this way, the pattern surface is free of -CF 3 The molecule is covered with -CF 3 -CF 2 Approximately similar to H, it has a large effect of reducing the surface free energy, and therefore it is possible to further suppress the collapse of the pattern during the drying process in step S16.

[0112] As described above, the number of C's contained in the molecular formula of the fluorine-containing alcohol is preferably 4 or more. As shown in the experimental results of Fig. 7, when the number of C's is 4 or more (Example 1), pattern collapse can be further suppressed compared to when the number of C's is less than 4 (Example 2).

[0113] The above-described substrate processing method preferably further includes, after step S16, a step (step S17) of removing molecules of the drying processing liquid adsorbed on the upper surface 91 of the substrate 9 by heating the substrate 9. In this manner, by removing unnecessary adsorbed matter on the upper surface 91 of the substrate 9, the cleanliness of the substrate 9 can be improved.

[0114] The above-described substrate processing method preferably further includes a step (step S13) of supplying a replacement liquid to the upper surface 91 of the substrate 9 and replacing the rinsing liquid on the upper surface 91 of the substrate 9 with the replacement liquid between step S12 (supply of the rinsing liquid) and step S14 (supply of the drying processing liquid). In this case, in step S14, the replacement liquid on the upper surface 91 of the substrate 9 is replaced with the drying processing liquid. This makes it possible to avoid direct contact between the rinsing liquid and the drying processing liquid on the substrate 9. Therefore, even if the affinity between the rinsing liquid and the drying processing liquid is relatively low, the processing liquid in contact with the upper surface 91 of the substrate 9 can be smoothly changed from the rinsing liquid to the drying processing liquid while preventing liquid splashes and the like caused by the direct contact.

[0115] As described above, preferably, in step S14, a drying treatment liquid that has been heated in advance is supplied to the upper surface 91 of the substrate 9. This makes it possible to shorten the time from when the supply of the drying treatment liquid starts until the substrate 9 comes into contact with the drying treatment liquid at the contact temperature, as compared to a case in which a drying treatment liquid at room temperature is supplied to the upper surface 91 of the substrate 9 and then heated to the contact temperature. As a result, the time required to process the substrate 9 can be shortened.

[0116] As described above, the substrate 9 is preferably heated from the lower surface 92 side even during step S16 (removal of the liquid film of the drying processing liquid). This makes it possible to suppress a decrease in the surface tension of the drying processing liquid even during step S16, thereby further suppressing collapse of the pattern. From the viewpoint of suppressing collapse of the pattern, it is preferable that the heating temperature of the substrate 9 during step S16 is approximately the same as the heating temperature in step S15.

[0117] As described above, the heating of the substrate 9 in step S15 is preferably performed by an electric heater disposed opposite the lower surface 92 of the substrate 9. This allows the substrate 9 to be heated with a simple structure. As described above, the electric heater is preferably a hot plate 71 capable of heating the substrate 9 by contacting or approaching the lower surface 92 of the substrate 9. More preferably, the size of the hot plate 71 is approximately the same as that of the substrate 9. This allows the in-plane uniformity of the temperature of the liquid film of the drying treatment liquid on the upper surface 91 of the substrate 9 to be improved. In other words, the temperature difference of the liquid film due to the difference in position on the upper surface 91 of the substrate 9 can be reduced. As a result, the in-plane uniformity of the adsorption of the molecules of the drying treatment liquid to the pattern surface on the substrate 9 can also be improved. Therefore, the collapse of the pattern can be suppressed approximately uniformly over the entire upper surface 91 of the substrate 9.

[0118] In the above substrate processing method, the difference between the contact temperature and the boiling point of the drying processing liquid is preferably 65° C. or less (for example, Examples 3 and 4 in FIG. 7). This allows efficient adsorption of the molecules of the drying processing liquid to the pattern. As a result, the collapse of the pattern can be further suppressed compared to when the difference between the contact temperature and the boiling point of the drying processing liquid is greater than 65° C. (Example 5).

[0119] As described above, in step S15, the contact time of the drying treatment liquid at the contact temperature with the upper surface 91 of the substrate 9 is preferably 10 seconds or more. This allows the molecules of the drying treatment liquid to be suitably adsorbed onto the pattern surface on the substrate 9. As a result, it is possible to further suppress the collapse of the pattern during the drying treatment in step S16.

[0120] The above-mentioned substrate processing apparatus 1 includes a chemical liquid supplying section (first nozzle 51 in the above example) that supplies a chemical liquid to the upper surface 91 of the substrate 9, a rinsing liquid supplying section (second nozzle 52 in the above example) that supplies a rinsing liquid to the upper surface 91 of the substrate 9, a drying processing liquid supplying section (fourth nozzle 54 in the above example) that supplies a drying processing liquid to the upper surface 91 of the substrate 9, a substrate heating section 7 that heats the substrate 9 from the lower surface 92 side in a state in which a liquid film of the drying processing liquid is formed on the upper surface 91, and a drying processing section (upper nozzle 55 and / or substrate rotating mechanism 33 in the above example) that dries the substrate 9 by removing the liquid film of the drying processing liquid from the upper surface 91 of the substrate 9. The surface tension of the drying processing liquid is lower than that of the rinsing liquid. The boiling point of the drying processing liquid is higher than that of the rinsing liquid. The heating temperature of the substrate 9 by the substrate heating section 7 is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying processing liquid.

[0121] This makes it possible to prevent the pattern from collapsing during the drying process as described above. Also, it is possible to reduce the difference between the boiling point of the drying process liquid and the temperature of the liquid film of the drying process liquid on the substrate 9 while preventing the occurrence of cracks in the liquid film of the drying process liquid.

[0122] In the substrate processing apparatus 1, the substrate heating unit 7 is preferably an electric heater disposed facing the lower surface 92 of the substrate 9. This allows the structure of the substrate processing apparatus 1 to be simplified. As described above, the electric heater is preferably a hot plate 71 capable of heating the substrate 9 by contacting or approaching the lower surface 92 of the substrate 9. More preferably, the size of the hot plate 71 is approximately the same as that of the substrate 9. This allows the in-plane uniformity of the liquid film temperature of the drying processing liquid on the upper surface 91 of the substrate 9 to be improved, and also allows the in-plane uniformity of the adsorption of the molecules of the drying processing liquid to the pattern surface on the substrate 9 to be improved. Therefore, the collapse of the pattern can be suppressed approximately uniformly over the entire upper surface 91 of the substrate 9.

[0123] As described above, the drying treatment liquid preferably contains a fluorine-containing alcohol, which can further prevent the pattern from collapsing during the drying treatment of the substrate 9, as described above.

[0124] The above-described substrate processing apparatus 1 and substrate processing method can be modified in various ways.

[0125] For example, the drying treatment liquid is not limited to the first drying treatment liquid and the second drying treatment liquid described above, and may be a liquid having -CF 2 Alternatively, the drying treatment liquid may contain other types of fluorine-containing alcohols having -CF 3 H at the end, as described above. 3 The drying treatment liquid may contain various kinds of fluorine-containing alcohols having a -CF 2 H and -CF 3 The drying treatment liquid may contain various kinds of fluorine-containing alcohols having structures other than those mentioned above. The number of C's contained in the molecular formula of the fluorine-containing alcohol may be 3 or less, or 8 or more. The drying treatment liquid may not contain a fluorine-containing alcohol.

[0126] Heating of the lower surface 92 of the substrate 9 in step S15 does not necessarily have to be performed by the hot plate 71, and the heating may be performed by various methods. For example, a light irradiation unit arranged below the substrate 9 may be provided in the substrate heating unit 7, and the lower surface 92 of the substrate 9 may be heated from the lower surface 92 by irradiating the lower surface 92 of the substrate 9 with light from the light irradiation unit. Alternatively, a nozzle arranged below the substrate 9 may be provided in the substrate heating unit 7, and a fluid such as a heated inert gas may be supplied from the nozzle to the lower surface 92 of the substrate 9, thereby heating the substrate 9 from the lower surface 92.

[0127] In step S15, the contact time of the drying treatment liquid at the contact temperature with the upper surface 91 of the substrate 9 may be less than 10 seconds. In addition, the difference between the contact temperature and the boiling point of the drying treatment liquid may be greater than 65°C.

[0128] In the substrate processing apparatus 1, in the drying process in step S16, the drying process liquid may be removed from the substrate 9 by various methods. For example, the substrate 9 is heated by the hot plate 71 to a temperature equal to or higher than the boiling point of the drying process liquid, whereby the portion of the drying process liquid on the substrate 9 that is in contact with the substrate 9 is vaporized to form a gas layer. layer Nitrogen gas or the like may be sprayed onto the center of the liquid film of the drying treatment liquid supported on the substrate 9 to open a hole in the liquid film, and then the hole may be enlarged radially outward by further spraying of nitrogen gas and rotating the substrate 9, thereby removing the liquid drying treatment liquid from above the substrate 9. Alternatively, the drying treatment liquid on the upper surface 91 of the substrate 9 may be sucked and removed by a suction mechanism having a suction port disposed in the vicinity of the outer periphery of the substrate 9.

[0129] In the substrate processing apparatus 1, while the drying process is being performed in step S16, the drying process liquid on the substrate 9 does not necessarily have to be heated by the substrate heating unit 7. For example, the liquid film of the drying process liquid in step S16 may be heated by irradiating the liquid film with light. Alternatively, the liquid film of the drying process liquid in step S16 may be heated by applying a heated fluid such as an inert gas to the lower surface 92 of the substrate 9. Also, in step S16, the liquid film of the drying process liquid does not necessarily have to be heated, and heating of the liquid film may be omitted.

[0130] If the molecules of the drying processing liquid adsorbed on the pattern surface do not substantially adversely affect the quality of the substrate 9 after step S16 is completed, the adsorbed molecule removal process in step S17 may be omitted.

[0131] The above-mentioned steps S11 to S17 may be performed in an apparatus having a structure other than the substrate processing apparatus 1.

[0132] The above-mentioned substrate processing apparatus 1 may be used to process glass substrates used in flat panel displays such as liquid crystal displays or organic EL (Electro Luminescence) displays, or glass substrates used in other displays, in addition to semiconductor substrates. The above-mentioned substrate processing apparatus 1 may also be used to process substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, and substrates for solar cells.

[0133] The configurations in the above-described embodiment and each of the modified examples may be combined as appropriate as long as they are not mutually inconsistent. [Explanation of symbols]

[0134] 1. Substrate Processing Equipment 7 Substrate heating section 9 Substrate 33 Substrate rotation mechanism 51 No. 1 nozzle 52 No. 2 nozzle 53 3rd nozzle 54 No. 4 nozzle 55 Upper nozzle 71 Hot Plate 91 (Platform) Top 92 (Bottom of board) S11~S17 steps

Claims

1. A substrate processing method for processing a substrate having a pattern including a recess formed on an upper surface thereof, comprising the steps of: a) supplying a chemical solution onto an upper surface of a substrate; b) supplying a rinsing liquid to the top surface of the substrate after the step a); c) supplying a drying treatment liquid onto the upper surface of the substrate after the step b) to form a liquid film of the drying treatment liquid on the upper surface of the substrate; d) heating the substrate from the underside in a state in which the liquid film of the drying treatment liquid is formed on the upper surface; e) drying the substrate by removing the liquid film of the drying treatment liquid from the top surface of the substrate after the step d); and Equipped with the surface tension of the drying processing liquid is lower than the surface tension of the rinsing liquid; the boiling point of the drying treatment liquid is higher than the boiling point of the rinsing liquid, a heating temperature of the substrate in the step d) is equal to or higher than a boiling point of the rinsing liquid and lower than a boiling point of the drying treatment liquid; The substrate processing method further includes, between the step b) and the step c), a step of supplying a replacement liquid to the upper surface of the substrate and replacing the rinsing liquid on the upper surface of the substrate with the replacement liquid; The substrate processing method, wherein in the step c), the replacement liquid on the upper surface of the substrate is replaced with the dry processing liquid.

2. A substrate processing method for processing a substrate having a pattern including a recess formed on an upper surface thereof, comprising the steps of: a) supplying a chemical solution onto an upper surface of a substrate; b) supplying a rinsing liquid to the top surface of the substrate after the step a); c) supplying a drying treatment liquid onto the upper surface of the substrate after the step b) to form a liquid film of the drying treatment liquid on the upper surface of the substrate; d) heating the substrate from the underside in a state in which the liquid film of the drying treatment liquid is formed on the upper surface; e) drying the substrate by removing the liquid film of the drying treatment liquid from the top surface of the substrate after the step d); and Equipped with the drying treatment liquid contains a fluorine-containing alcohol having a surface tension lower than that of the rinse liquid and a boiling point higher than that of the rinse liquid, a heating temperature of the substrate in the step d) being equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying liquid;

3. 3. The substrate processing method according to claim 1, further comprising the steps of: f) after step e), removing molecules of the drying processing liquid adsorbed on the upper surface of the substrate by heating the substrate.

4. 4. A substrate processing method according to claim 1, further comprising the steps of: The substrate processing method, wherein in the step c), the drying processing liquid is supplied to the upper surface of the substrate, the drying processing liquid being preheated.

5. 5. A substrate processing method according to claim 1, further comprising the steps of: The substrate processing method according to claim 1, wherein the substrate is heated from the lower surface side even during the step e).

6. 6. A substrate processing method according to claim 1, further comprising the steps of: The substrate processing method according to claim 1, wherein the heating of the substrate in the step d) is performed by an electric heater disposed opposite to the lower surface of the substrate.

7. A substrate processing apparatus for processing a substrate having a pattern including a recess formed on an upper surface thereof, comprising: a chemical supply unit that supplies a chemical solution to an upper surface of the substrate; a rinse liquid supply unit that supplies a rinse liquid to the upper surface of the substrate; a replacement liquid supply unit that supplies a replacement liquid to the upper surface of the substrate in a state in which a liquid film of the rinsing liquid is formed on the upper surface, thereby replacing the rinsing liquid on the upper surface with the replacement liquid; a drying treatment liquid supply unit that supplies a drying treatment liquid to the upper surface of the substrate in a state in which a liquid film of the replacement liquid is formed on the upper surface, thereby replacing the replacement liquid on the upper surface with the drying treatment liquid; a substrate heating unit that heats the substrate from a lower surface side in a state in which a liquid film of the drying processing liquid is formed on the upper surface; a drying processing unit that dries the substrate by removing the liquid film of the drying processing liquid from the upper surface of the substrate; Equipped with the surface tension of the drying processing liquid is lower than the surface tension of the rinsing liquid; the boiling point of the drying treatment liquid is higher than the boiling point of the rinsing liquid, 2. The substrate processing apparatus according to claim 1, wherein the heating temperature of the substrate by the substrate heating section is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying processing liquid.

8. A substrate processing apparatus for processing a substrate having a pattern including a recess formed on an upper surface thereof, comprising: a chemical supply unit that supplies a chemical solution to an upper surface of the substrate; a rinse liquid supply unit that supplies a rinse liquid to the upper surface of the substrate; a drying treatment liquid supply unit that supplies a drying treatment liquid to the upper surface of the substrate; a substrate heating unit that heats the substrate from a lower surface side in a state in which a liquid film of the drying processing liquid is formed on the upper surface; a drying processing unit that dries the substrate by removing the liquid film of the drying processing liquid from the upper surface of the substrate; Equipped with the drying treatment liquid contains a fluorine-containing alcohol having a surface tension lower than that of the rinse liquid and a boiling point higher than that of the rinse liquid, 2. The substrate processing apparatus according to claim 1, wherein the heating temperature of the substrate by the substrate heating section is equal to or higher than the boiling point of the rinsing liquid and lower than the boiling point of the drying processing liquid.

9. 9. The substrate processing apparatus according to claim 7, 4. The substrate processing apparatus according to claim 1, wherein the substrate heating unit is an electric heater disposed opposite the lower surface of the substrate.

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