TWI721495B - Substrate processing apparatus, processing liquid and substrate processing method - Google Patents

Abstract

The substrate processing apparatus 1 includes a substrate holding part 2, a processing liquid supply part, a heating part 5, and a liquid removing part. The substrate holding part 2 holds the substrate 9 in a horizontal state. The processing liquid supply part supplies the processing liquid having a surface tension higher than that of IPA to the upper surface 91 of the substrate 9 to form a liquid film of the processing liquid which covers the entire upper surface 91 of the substrate 9. The heating part 5 heats the substrate 9 from the lower surface side to vaporize a part of the liquid film, thereby forming a gas phase layer between the upper surface 91 of the substrate 9 and the liquid film. The liquid removing part removes the liquid film on the gas phase layer. Thereby, damage to the liquid film which is not intended can be suppressed.

Description

Substrate processing device, processing liquid, and substrate processing method

The present invention relates to a substrate processing device for processing a substrate, a processing liquid used in the substrate processing device, and a substrate processing method for processing a substrate.

Conventionally, various processes have been applied to the substrate in the manufacturing process of a semiconductor substrate (hereinafter referred to as a "substrate"). For example, a chemical liquid is sprayed from a substrate on which a resist pattern (that is, a plurality of fine structures) is formed on the surface of the nozzle to perform chemical liquid treatment such as etching on the surface of the substrate.

In addition, after the substrate is treated with a chemical solution, a rinse process and a drying process are further performed. The cleaning process is a process of supplying pure water to the substrate and removing the chemical solution, and the drying process is a process of rotating the substrate at a high speed and removing the liquid on the substrate.的处理。 The treatment. When a fine pattern is formed on the substrate, when the cleaning process and the drying process are sequentially performed, a liquid surface of pure water is formed between two adjacent pattern elements during the drying process. In this case, there is a risk that the pattern elements may collapse due to the surface tension of pure water acting on the pattern elements.

Therefore, in the substrate processing apparatuses of Japanese Patent Application Publication No. 2014-112652 (Document 1), Japanese Patent Application Publication No. 2016-136599 (Document 2), and Japanese Patent Application Publication No. 2016-162847 (Document 3), the cleaning is performed After the treatment, IPA (isopropyl alcohol) liquid is supplied to the upper surface of the substrate and replaced with the cleaning liquid to form a liquid film of IPA on the substrate. Next, the substrate is heated to form a vapor film of IPA between the liquid film of IPA and the upper surface of the substrate, thereby floating the liquid film of IPA from the upper surface of the substrate, and then the liquid film is removed from the substrate. When removing the liquid film from the substrate, Nitrogen is sprayed from the nozzle to the center of the liquid film and the liquid film is partially removed to form a small diameter drying area; and while the substrate is rotated, nitrogen is further sprayed to the center to make the drying area Expand and expand to the entire upper surface of the substrate. Thereby, the upper surface of the substrate is dried while suppressing the collapse of the pattern elements.

In addition, in the substrate processing apparatus of Document 3, when the liquid film is removed from the substrate, after a drying area is formed in the center of the liquid film, an inert gas is ejected from a circumferential slit opening provided on the outer peripheral surface of the nozzle . Thereby, a radial airflow is formed obliquely downward from the nozzle, and the airflow promotes the expansion of the drying area.

However, in the substrate processing apparatus, the liquid film may be unexpectedly damaged when the liquid film of IPA is formed and heated (that is, before the liquid film of IPA is started to be removed). Specifically, the IPA may flow down from the periphery of the substrate or the contact portion between the chuck pin and the liquid film. Or, there may be cracks in the liquid film due to the vapor of IPA generated under the liquid film of IPA. In this way, there is a possibility that the time for heating the liquid film of the IPA may be reduced. From the viewpoint of sufficiently floating and removing the liquid film of IPA from the upper surface of the substrate by the vapor film, it is preferable to ensure the heating time of the liquid film of IPA to some extent.

The present invention focuses on a substrate processing apparatus for processing substrates, and aims to suppress unexpected damage of the liquid film.

A substrate processing apparatus of a preferred form of the present invention is provided with: a substrate holding part which holds the substrate in a horizontal state; and a processing liquid supply part which supplies a processing liquid with a higher surface tension than isopropanol onto the substrate Surface, thereby forming a liquid film of the processing liquid covering the entire surface of the upper surface of the substrate; the heating part heats the substrate from the lower surface side and vaporizes a part of the liquid film, thereby forming a liquid film on the substrate A gas phase layer is formed between the upper surface and the liquid film; and a liquid removal part removes the liquid film on the gas phase layer. According to the substrate The treatment device can prevent unexpected breakage of the liquid film.

Preferably, the vapor pressure of the treatment liquid is higher than the vapor pressure of isopropanol.

Preferably, the aforementioned treatment liquid contains cis-1,2-dichloroethylene (cis-1,2-dichloroethylene), trichloromethane (trichloromethane), methyl acetate (methyl acetate), 1,3-dioxide Pentane (1,3-dioxolane), tetrahydrofuran (tetrahydrofuran), 1,1,1-trichloroethane (1,1,1-trichloroethane), tetrachloromethane, benzene, cyclohexane (cyclohexane), acetonitrile, trichloroethylene, tetrahydropyran, nitric acid, 1,2-dichloroethane, 1,2-dichloropropane ( At least one of 1,2-dichloropropane, fluorotrinitromethane, pyrrolidine, acrylonitrile, and cyclohexene.

Preferably, the heating of the substrate by the heating unit is started after the entire surface of the upper surface of the substrate is covered by the processing liquid supplied from the processing liquid supply unit.

Preferably, in a state where the entire upper surface of the substrate is covered with the isopropyl alcohol, the processing liquid is supplied to the upper surface of the substrate from the processing liquid supply part, and the processing liquid is replaced by the processing liquid. The isopropyl alcohol on the upper surface of the substrate thereby forms the liquid film of the processing liquid.

Preferably, the treatment liquid is a mixture of a substance having a surface tension higher than that of the isopropanol and a vapor pressure lower than that of the isopropanol to the mixed liquid of the isopropanol.

Preferably, the liquid removal section includes: a gas ejection section that ejects gas toward the center of the liquid film; and the gas from the gas ejection section forms radiation from the center of the liquid film toward the surroundings. And move the processing liquid from the center portion of the liquid film toward the outer edge of the substrate and remove it from the substrate.

Preferably, the gas ejection portion includes: a first ejection port for ejecting gas toward the center portion of the liquid film; and a plurality of second ejection ports that are circumferentially arranged around the first ejection port , The gas is ejected radially from the center portion of the liquid film toward the surrounding direction.

Preferably, the substrate processing apparatus is further provided with: a chamber for accommodating the substrate holding part in the internal space; and a gas flow forming part for sending gas from the upper part of the chamber to the internal space, and A downward airflow from the upper side to the lower side of the substrate is formed around the substrate. The downward air flow promotes the movement of the processing liquid in the peripheral edge portion of the upper surface of the substrate toward the outer edge when the processing liquid is removed from the substrate.

Preferably, the substrate processing apparatus is further provided with: a rotating mechanism that rotates the substrate holding portion; a cup is arranged around the substrate holding portion with a gap therebetween to catch the rotating The liquid scattered from the substrate; and a cover moving mechanism that relatively moves the cover with respect to the substrate holding portion. When the processing liquid is removed from the substrate, the cover is moved relatively by the cover moving mechanism, and the gap between the substrate holding portion and the cover is reduced.

Preferably, when the heating section starts to heat the substrate, the air flow forming section stops forming the down flow.

Preferably, at the same time when the processing liquid supply unit stops supplying the processing liquid before the heating unit starts to heat the substrate, the airflow forming unit stops forming the downflow.

Preferably, after the temperature of the peripheral edge portion of the substrate becomes a predetermined temperature or higher, the airflow forming portion starts to form the downward airflow again.

The present invention also focuses on a processing liquid used in substrate processing. Of the invention A preferred form of the processing liquid system has a higher surface tension than isopropanol, and is supplied to the upper surface of the substrate in the substrate processing apparatus.

The present invention also focuses on a substrate processing method for processing substrates. A preferred form of the substrate processing method of the present invention is provided with: step (a) is to hold the substrate in a horizontal state; step (b) is to supply a processing solution with a higher surface tension than isopropanol to the aforementioned substrate The upper surface, thereby forming a liquid film of the treatment liquid covering the entire surface of the upper surface of the substrate; step (c), heating the substrate from the lower surface side and vaporizing a part of the liquid film, thereby A gas phase layer is formed between the upper surface of the substrate and the liquid film; and step (d) is to remove the liquid film on the gas phase layer. According to this substrate processing method, unexpected breakage of the liquid film can be suppressed.

The object of the present invention and other objects, features, aspects, and advantages are made clear by the detailed description of the present invention described below with reference to the accompanying drawings.

1: Substrate processing equipment

2: Board holding part

3: Rotating mechanism

4: Hood

5: Heating part

6: Liquid supply part

7: Gas supply department

9: Substrate (semiconductor substrate)

11: Chamber

21: Base

22: Keep the shaft

23: Fixture pin

24: Lid

41: Hood

42: Hood moving mechanism

43: hood side wall

44: Cover top cover

45: discharge port

51: heating plate

52: Heating shaft

53: Plate lifting mechanism

61: The first nozzle

62: second nozzle

63: The third nozzle

64: Treatment liquid supply source

65: liquid medicine supply source

66: Cleaning fluid supply source

71: Airflow forming part

72: fan unit

74: Gas supply source

91: (of the substrate) upper surface

92: (of the substrate) lower surface

93: Liquid film

94: Gas phase layer

95: interface

96: well

610: The first nozzle moving mechanism

611: Nozzle body

612: Treatment liquid flow path

613: The first gas flow path

614: second gas flow path

615: Ejector

616: first outlet

617: second outlet

620: Second nozzle moving mechanism

616: first outlet

617: second outlet

641, 651, 661, 741, 743: Piping

642, 652, 662, 742, 744: valve

911: Structure

J1: Central axis

Fig. 1 is a side view of a substrate processing apparatus according to one embodiment.

Fig. 2 is a block diagram showing the liquid supply part and the gas supply part.

Figure 3 is an enlarged side view showing the first nozzle.

Fig. 4 is a diagram showing the flow of substrate processing.

Fig. 5 is a diagram showing a substrate in the middle of processing and a part of the substrate processing apparatus.

Fig. 6 is a diagram showing a substrate in the middle of processing and a part of the substrate processing apparatus.

Fig. 7 is an enlarged longitudinal sectional view showing the vicinity of the upper surface of the substrate.

Fig. 8 is an enlarged longitudinal sectional view showing the vicinity of the upper surface of the substrate.

Fig. 9 is a diagram of a flow of substrate processing.

Fig. 10 is a diagram showing a substrate in the middle of processing and a part of the substrate processing apparatus.

FIG. 11 is a diagram showing a substrate in the middle of processing and a part of the substrate processing apparatus.

Fig. 12 is a diagram showing a substrate in the middle of processing and a part of the substrate processing apparatus.

Fig. 1 is a side view showing the structure of a substrate processing apparatus 1 according to one embodiment of the present invention. The substrate processing apparatus 1 is a blade-type apparatus for processing semiconductor substrates 9 (hereinafter referred to as "substrate 9") one by one. The substrate processing apparatus 1 supplies a chemical liquid to the substrate 9 on which a fine pattern is formed on the upper surface 91 and performs liquid processing. In FIG. 1, a part of the configuration of the substrate processing apparatus 1 is shown in cross section.

The substrate processing apparatus 1 includes a substrate holding section 2, a rotating mechanism 3, a cover section 4, a heating section 5, a liquid supply section 6, a gas supply section 7, and a chamber 11. The substrate holding part 2, the rotating mechanism 3, the cover part 4, the heating part 5, a part of the liquid supply part 6, and a part of the gas supply part 7 are housed in the internal space of the chamber 11.

The substrate holding portion 2 is a mechanical chuck for directly contacting the peripheral edge of the substrate 9 and fixing the position of the substrate 9. The substrate 9 is held by the substrate holding portion 2 in a horizontal state. The rotation mechanism 3 rotates the substrate 9 and the substrate holding portion 2 with a central axis J1 oriented in the vertical direction as a center. The rotating mechanism 3 is, for example, an electric motor. The substrate holding portion 2 and the rotating mechanism 3 constitute a spin chuck for holding and rotating the substrate 9.

The substrate holding portion 2 includes a base portion 21, a holding shaft portion 22 and a plurality of chuck pins 23. The base portion 21 is a substantially disc-shaped portion with the center axis J1 as the center. The holding shaft portion 22 is a substantially cylindrical portion extending downward from the center portion of the base portion 21. The holding shaft portion 22 is housed in a cover portion 24 having a substantially cylindrical shape, and the cover portion 24 is provided below the base portion 21. A rotating mechanism 3 for rotating and holding the shaft 22 is also contained in the cover 24. The diameter of the cover portion 24 is, for example, approximately the same as the diameter of the base portion 21.

The plurality of clamp pins 23 protrude upward from the upper surface of the base portion 21. A plurality of clamp pins 23 are arranged at slightly equal angular intervals in the circumferential direction with the center axis J1 as the center (hereinafter also abbreviated as Called "circumferential direction"). The number of the plurality of clamp pins 23 is, for example, three or four. The substrate 9 is arranged at a position separated from the upper surface of the base portion 21 by supporting the peripheral edge portion by a plurality of clamp pins 23.

The cover 4 is provided with a cover 41 and a cover moving mechanism 42. The cover 41 is arranged around the substrate 9 and the substrate holding portion 2 with a gap therebetween. The cover 41 catches liquids such as chemical liquid, cleaning liquid, and processing liquid scattered from the rotating substrate 9. The cover 41 includes a cover side wall portion 43 and a cover top cover portion 44. The cover side wall portion 43 is a substantially cylindrical portion with the center axis J1 as the center. The top cover part 44 is a roughly annular part centered on the central axis J1. The cover top cover portion 44 extends from the upper end portion of the cover side wall portion 43 toward the inner side in the radial direction. In the example shown in FIG. 1, the inner side surface of the top cover part 44 is an inclined surface which faces upwards as it faces radially inward. The liquid system scattered outward in the radial direction from the peripheral edge portion of the rotating substrate 9 for example, after colliding with the inner surface of the cover 41, drops toward the bottom of the cover 41, and then enters the chamber through a discharge port 45 provided at the bottom. 11 is discharged from the outside.

The cover moving mechanism 42 moves the cover 41 relative to the substrate holding portion 2. In the example shown in FIG. 1, the cover moving mechanism 42 is an elevating mechanism for moving the cover 41 in the vertical direction. The cover moving mechanism 42 is provided with, for example, an air cylinder, which faces the up-down direction, and a connecting member, which connects the movable part of the cylinder and the cover 41. In addition, the cover moving mechanism 42 does not necessarily need to be a mechanism for moving the cover 41, and may be a mechanism for moving the substrate holding portion 2 in the vertical direction.

The heating unit 5 includes a heating plate 51, a heating shaft 52 and a plate lifting mechanism 53. The heating plate 51 is a substantially disc-shaped portion with the center axis J1 as the center. The heating plate 51 is located between the base portion 21 of the substrate holding portion 2 and the substrate 9 and faces the lower surface 92 of the substrate 9 in the vertical direction. The upper surface of the heating plate 51 is slightly parallel to the lower surface 92 of the substrate 9. The diameter of the upper surface of the heating plate 51 is slightly smaller than the diameter of the substrate 9. For example, in the case where the diameter of the substrate 9 is 300 mm, the diameter of the upper surface of the heating plate 51 is 294 mm. A heater (not shown) is provided inside the heating plate 51.

The heating shaft portion 52 is a substantially cylindrical portion, and is connected to the central portion of the heating plate 51. The heating shaft portion 52 extends downward from the heating plate 51 through the inside of the holding shaft portion 22. A plate lifting mechanism 53 is connected to the heating shaft portion 52. The plate lifting mechanism 53 is, for example, an electric motor. The heating shaft portion 52 is raised and lowered by the plate lifting mechanism 53, whereby the heating plate 51 is moved in the vertical direction between the base portion 21 and the substrate 9. Specifically, the heating plate 51 is at the position shown by the solid line in FIG. 1 (hereinafter referred to as the "standby position") and the position shown by the two-dot chain line in FIG. 1 (hereinafter referred to as the "heating position") Move in the up and down direction between.

The upper surface of the heating plate 51 at the heating position directly contacts the lower surface 92 of the substrate 9. Alternatively, the upper surface of the heating plate 51 at the heating position and the lower surface 92 of the substrate 9 are separated from the lower surface 92 of the substrate 9 with a very small gap (for example, a gap having a height of about 0.1 mm) and separated downward from the lower surface 92 of the substrate 9. In the heating plate 51 located at the heating position, electric power is supplied to the built-in heater, thereby substantially uniformly heating a substantially entire surface of the upper surface of the heating plate 51 and also substantially uniformly heating a substantially entire surface of the substrate 9. The standby position described above is a position below the heating position. Since the heating plate 51 in the standby position is largely separated from the lower surface 92 of the substrate 9 to the lower side, the substrate 9 is not heated. In addition, the heating plate 51 and the heating shaft portion 52 do not rotate.

FIG. 2 is a block diagram showing the liquid supply part 6 and the gas supply part 7 of the substrate processing apparatus 1. In FIG. 2, structures other than the liquid supply part 6 and the gas supply part 7 are also shown together. The liquid supply unit 6 supplies a plurality of types of liquids to the substrate 9 individually. The plural types of liquid systems include, for example, chemical liquids, cleaning liquids, and treatment liquids. As shown in FIGS. 1 and 2, the liquid supply unit 6 includes a first nozzle 61, a second nozzle 62, and a third nozzle 63. The first nozzle 61, the second nozzle 62, and the third nozzle 63 supply liquid from above the substrate 9 to the upper surface 91 of the substrate 9, respectively. The gas supply part 7 is provided with a gas flow forming part 71. The first nozzle 61 described above is also included in the gas supply unit 7.

In the example shown in FIG. 1, the first nozzle 61 is movable between a processing position above the substrate 9 (for example, above the center of the substrate 9) and a retracted position radially outside the outer edge of the substrate 9. The movement of the first nozzle 61 is performed by the first nozzle moving mechanism 610. The first nozzle moving mechanism 610 is provided with, for example, an arm portion that supports the first nozzle 61; and an electric motor that is driven from The arm part extending to the side of the first nozzle 61 swings and moves up and down.

Like the first nozzle 61, the second nozzle 62 may be moved between a processing position above the substrate 9 (for example, above the center of the substrate 9) and a retracted position radially outside the outer edge of the substrate 9. The movement of the second nozzle 62 is performed by the second nozzle moving mechanism 620. The second nozzle moving mechanism 620 is provided with, for example, an arm that supports the second nozzle 62 and an electric motor that swings and raises and lowers the arm that extends from the second nozzle 62 to the side.

The third nozzle 63 directs the ejection port of the liquid toward the center of the upper surface 91 of the substrate 9 and is fixed above the substrate 9. In addition, similarly to the first nozzle 61 and the second nozzle 62, the third nozzle 63 may also move between the processing position and the retreat position.

FIG. 3 is an enlarged side view showing the first nozzle 61. The first nozzle 61 includes a nozzle body 611, a processing liquid flow path 612, a first gas flow path 613, and a second gas flow path 614. The nozzle body 611 is a substantially cylindrical member. The processing liquid flow path 612, the first gas flow path 613, and the second gas flow path 614 are formed inside the nozzle body 611.

The ejection port 615 of the processing liquid flow path 612 is provided at the center of the lower end surface of the nozzle body 611. The first ejection port 616 of the first gas flow path 613 is also provided at the center of the lower end surface of the nozzle body 611. With the first nozzle 61 at the processing position, the ejection port 615 of the processing liquid flow path 612 and the first ejection port 616 of the first gas flow path 613 are opposed to the center of the upper surface 91 of the substrate 9 in the vertical direction. .

The second gas flow path 614 is connected to a plurality of small second ejection ports 617, and the plurality of second ejection ports 617 are circumferentially arranged around the first ejection port 616. In the example shown in FIG. 3, a plurality of second ejection ports 617 are circumferentially arranged at substantially the same position in the vertical direction at approximately equal angular intervals on the outer surface of the first nozzle 61. The shapes and sizes of the plurality of second ejection ports 617 are slightly the same. The shape of each second ejection port 617 when viewed from the side is, for example, a slightly circular shape. The diameter of each second ejection port 617 is, for example, smaller than the diameter of the first ejection port 616, and is about 1 mm.

The processing liquid flow path 612 of the first nozzle 61 is connected to the processing liquid supply source 64 via the pipe 641 and the valve 642 shown in FIG. 2. When the first nozzle 61 is at the processing position, the valve 642 is opened, thereby supplying the processing liquid from the processing liquid supply source 64 to the processing liquid flow path 612 via the pipe 641 and from the ejection port 615 toward the center of the upper surface 91 of the substrate 9 Squirting. The valve 642 is closed, whereby the ejection of the processing liquid from the first nozzle 61 is stopped. The first nozzle 61 is a processing liquid supply unit for supplying the processing liquid to the upper surface 91 of the substrate 9. The pipe 641 and the valve 642 may be included in the processing liquid supply part.

The surface tension of the processing liquid supplied from the first nozzle 61 to the substrate 9 is higher than the surface tension of isopropyl alcohol (molecular formula: C ₃ H ₈ O, hereinafter referred to as "IPA") at the same temperature. In addition, it is preferable that the vapor pressure of the treatment liquid is higher than the vapor pressure of IPA at the same temperature. In other words, the boiling point of the treatment liquid is lower than the boiling point of IPA under the same pressure. In the following description of the relationship between the surface tension, vapor pressure, and boiling point of a plurality of liquids, the surface tension, vapor pressure, and boiling point of the plurality of liquids are set to be at the same temperature and the same pressure. In addition, the surface tension at room temperature (25°C) and atmospheric pressure (100kPa) of IPA is 20.8mN/m, the vapor pressure at room temperature (25°C) and atmospheric pressure (100kPa) of IPA is 5.87kPa, and the room temperature of IPA ( The boiling point at 25°C) and normal pressure (100kPa) is 82.4°C. The surface tension of the treatment liquid is lower than that of pure water, for example. In addition, the vapor pressure of the treatment liquid is higher than that of pure water, for example.

Preferably, the treatment liquid contains cis-1,2-dichloroethylene (molecular formula: C ₂ H ₂ Cl ₂ ), chloroform (molecular formula: CHCl ₃ ), and methyl acetate (molecular formula: C ₃ H ₆ O ₂ ), 1,3-dioxolane (molecular formula: C ₃ H ₆ O ₂ ), tetrahydrofuran (molecular formula: C ₄ H ₈ O), 1,1,1-trichloroethane (molecular formula: C ₂ H ₃ Cl ₃ ), tetrachloromethane (molecular formula: CCl ₄ ), benzene (molecular formula: C ₆ H ₆ ), cyclohexane (molecular formula: C ₆ H ₁₂ ), acetonitrile (molecular formula: C ₂ H ₃ N), trichloro Ethylene (molecular formula: C ₂ HCl ₃ ), tetrahydropiperan (molecular formula: C ₅ H ₁₀ O), nitric acid (molecular formula: HNO ₃ ), 1,2-dichloroethane (molecular formula: C ₂ H ₄ Cl ₂ ) , 1,2-Dichloropropane (molecular formula: C ₃ H ₆ Cl ₂ ), fluorotrinitromethane (molecular formula: CFN ₃ O ₆ ), pyrrolidine (molecular formula: C ₄ H ₉ N), acrylonitrile (molecular formula: A liquid of at least one of C ₃ H ₃ N) and cyclohexene (molecular formula: C ₆ H _{10 ).}

The surface tension and vapor pressure of each liquid contained in the liquid group described above are higher than the surface tension and vapor pressure of IPA. In addition, the processing liquid may be a mixture of two or more liquids in the liquid group described above. In addition, the processing liquid may be a processing liquid in which one or two or more liquids in the liquid group described above are diluted with a solvent.

The first gas flow path 613 (see FIG. 3) is connected to a gas supply source 74 via a pipe 741 and a valve 742. The second gas flow path 614 (refer to FIG. 3) is connected to a gas supply source 74 via a pipe 743 and a valve 744. When the first nozzle 61 is at the processing position, the valve 742 is opened, thereby supplying gas from the gas supply source 74 to the first gas flow path 613 via the pipe 741, and from the first ejection port 616 (refer to FIG. 3) toward the substrate 9 The center part of the upper surface 91 is ejected. The valve 742 is closed, thereby stopping the gas ejection from the first ejection port 616. In addition, the valve 744 is opened, thereby supplying gas from the gas supply source 74 to the second gas flow path 614 via the pipe 743, and facing the center of the upper surface 91 of the substrate 9 from the plurality of second ejection ports 617 (see FIG. 3). The portion is ejected radially in a direction inclined to the periphery (that is, inclined downward toward the outside in the radial direction). The valve 744 is closed, thereby stopping the gas ejection from the second ejection port 617.

As described above, the first nozzle 61 is a gas ejection portion, and includes a first ejection port 616 and a plurality of second ejection ports 617. The gas ejection portion may include pipes 741 and 743 and valves 742 and 744. In the first nozzle 61, the ejection of gas from the first ejection port 616 and the stopping of the ejection of gas from the first ejection port 616 and the ejection of gas from the second ejection port 617 and the stop of the ejection of gas from the second ejection port 617 can be individually controlled. In addition, the flow rate of the gas ejected from the first ejection port 616 and the flow rate of the gas ejected from the second ejection port 617 can be individually controlled. The gas sent from the gas supply source 74 to the first nozzle 61 is preferably an inert gas (for example, nitrogen (N ₂ ), argon (Ar), or clean dry gas). In the example shown in FIG. 1, nitrogen is ejected from the first ejection port 616 and the second ejection port 617 of the first nozzle 61. The gas ejected from the first nozzle 61 may be a gas other than an inert gas.

The second nozzle 62 is connected to a chemical liquid supply source 65 via a pipe 651 and a valve 652. When the second nozzle 62 is at the processing position, the valve 652 is opened, whereby the chemical solution supply source 65 passes through the piping 651 supplies the processing liquid to the second nozzle 62 and ejects it toward the center of the upper surface 91 of the substrate 9. The valve 652 is closed, whereby the spraying of the chemical liquid from the second nozzle 62 is stopped. The liquid medicine is acid, alkali and other liquids. The chemical liquid system is, for example, an etching liquid or a cleaning liquid. Specifically, use hydrofluoric acid, SC1 (standard clean-1; the first standard cleaning solution; that is, a mixture of ammonia and hydrogen peroxide), SC2 (standard clean-2; the second standard cleaning solution; that is A mixture of hydrochloric acid and hydrogen peroxide water), or buffered hydrofluoric acid (buffered HF; that is, a mixture of hydrofluoric acid and ammonium fluoride) is used as the chemical solution.

The third nozzle 63 is connected to a cleaning liquid supply source 66 via a pipe 661 and a valve 662. When the valve 662 is opened, the cleaning liquid is supplied from the cleaning liquid supply source 66 to the third nozzle 63 via the pipe 661 and is ejected toward the center of the upper surface 91 of the substrate 9. The valve 662 is closed, whereby the spraying of the cleaning liquid from the third nozzle 63 is stopped. Use, for example, DIW (De-ionized Water), carbonated water, ozone water, or hydrogen water as the cleaning fluid. In the example shown in Figure 1, DIW is used as a cleaning fluid.

As shown in FIG. 1, the air flow forming portion 71 is provided with a fan unit 72 provided in the upper portion of the chamber 11 (that is, a position above the substrate holding portion 2 and the cover portion 4). In the example shown in FIG. 1, the fan unit 72 is provided on the top cover of the chamber 11. The fan unit 72 is connected to a gas supply source 75 different from the gas supply source 74 via a pipe 751 and a valve 752 shown in FIG. 2. When the valve 752 is opened, the gas is supplied from the gas supply source 75 to the fan unit 72 via the pipe 751 and is sent downward in the internal space of the chamber 11. The valve 752 is closed, whereby the blowing of gas from the fan unit 72 is stopped. The air system sent from the air supply source 75 to the fan unit 72 is, for example, clean air (that is, air filtered by a filter). The gas may also be an inert gas such as nitrogen or argon. In the example shown in FIG. 1, clean gas is sent from the fan unit 72.

The air system sent from the fan unit 72 passes through the upper opening of the cover 41 and faces downward in the cover 41, and forms a downward flow from the upper side to the lower side of the substrate 9 around the substrate 9 (so-called down flow) ). The air system that has reached the bottom of the cover 41 is discharged to the outside of the chamber 11 through the discharge port 45. The discharge port 45 is, for example, connected to a suction mechanism (not shown) arranged outside the chamber 11 Show). In the substrate processing apparatus 1, the suction mechanism and the discharge port 45 are also included in the air flow forming part 71 for forming the down air flow.

Next, an example of the processing flow of the substrate 9 by the substrate processing apparatus 1 will be described with reference to FIG. 4. When the substrate 9 is processed in the substrate processing apparatus 1, first, the substrate 9 carried into the chamber 11 is held in a horizontal state by the substrate holding portion 2 (step S11). The fan unit 72 sends clean air into the chamber 11, thereby forming the downward airflow described above around the substrate 9. The supply of the clean air system from the fan unit 72 continues until the supply of the processing liquid is stopped in step S15 described later to maintain the downward air flow.

Next, the rotating mechanism 3 starts to rotate the substrate 9, and the substrate 9 is rotated at a predetermined rotation speed. In addition, by the second nozzle moving mechanism 620, the second nozzle 62 is moved toward the processing position. In addition, the first nozzle 61 is located at the retracted position. Next, the supply of the chemical solution from the second nozzle 62 to the rotating substrate 9 is started. The medicinal solution supplied to the center of the upper surface 91 of the substrate 9 moves radially outward by centrifugal force and spreads to the entire upper surface 91 of the substrate 9. The medicinal solution that has reached the peripheral edge of the substrate 9 scatters radially outward from the peripheral edge, is caught by the cover 41 surrounding the periphery of the substrate 9 as shown in FIG. 1, and is discharged out of the chamber 11 through the discharge port 45. The chemical solution is supplied to the substrate 9 for a predetermined time, thereby ending the chemical solution processing on the substrate 9 (step S12).

When the chemical solution processing is completed, the supply of chemical solution to the substrate 9 is stopped, and the second nozzle 62 moves from the processing position to the retracted position. In addition, the supply of the cleaning liquid from the third nozzle 63 to the rotating substrate 9 is started. The cleaning liquid supplied to the center of the upper surface 91 of the substrate 9 moves radially outward by centrifugal force and spreads to the entire upper surface 91 of the substrate 9. Thereby, the chemical liquid on the upper surface 91 of the substrate 9 is washed and removed from the substrate 9. The cleaning liquid that has reached the peripheral edge portion of the substrate 9 is scattered outward in the radial direction from the peripheral edge portion, is caught by the cover 41 surrounding the periphery of the substrate 9 and is discharged out of the chamber 11 through the discharge port 45. The cleaning liquid is supplied to the substrate 9 for a predetermined time, thereby ending the cleaning process for the substrate 9 (step S13).

When the cleaning process is finished, the supply of the cleaning liquid to the substrate 9 is stopped. In addition, the first nozzle 61 moves from the retracted position to the processing position, and the supply of the processing liquid from the first nozzle 61 to the rotating substrate 9 is started. The processing liquid supplied to the center of the upper surface 91 of the substrate 9 moves radially outward by centrifugal force and spreads to the entire upper surface 91 of the substrate 9. Thereby, the cleaning liquid on the upper surface 91 of the substrate 9 is rinsed and replaced by the processing liquid. That is, the processing liquid is a replacement liquid that replaces the cleaning liquid on the substrate 9. The processing liquid that has reached the peripheral edge of the substrate 9 scatters radially outward from the peripheral edge, is caught by the cover 41 surrounding the substrate 9 and is discharged out of the chamber 11 through the discharge port 45. The processing liquid is supplied to the substrate 9 for a predetermined time, thereby ending the replacement process from the cleaning liquid to the processing liquid.

When the replacement process is finished, the rotation mechanism 3 reduces the rotation speed of the substrate 9 and stops rotating the substrate 9 in a state where the processing liquid is continuously supplied from the first nozzle 61. Thereby, as shown in FIG. 5, a thick liquid film 93 of the treatment liquid covering the entire upper surface 91 of the substrate 9 in a static state is formed (step S14). In other words, the upper surface 91 of the substrate 9 is in a state of being paddle with the processing liquid. In addition, it is not necessary to stop the rotation of the substrate 9, and it is also possible to appropriately maintain the rotation of the liquid film 93 of the processing liquid on the substrate 9 at a low rotation speed.

Next, the supply of the processing liquid from the first nozzle 61 to the substrate 9 is stopped (step S15). In addition, at the same time as the supply of the processing liquid is stopped, the fan unit 72 stops forming the downflow of the clean gas (step S16). Thereby, it is possible to prevent the liquid film 93 of the processing liquid on the substrate 9 from being messy due to the downward air flow. In addition, the supply of the processing liquid may be stopped just before the heating plate 51 described below starts to heat the substrate 9. Thereby, the liquid film 93 of the processing liquid is appropriately maintained on the substrate 9.

Next, the heating plate 51, which has been heated in advance, is raised from the standby position to the heating position by the plate lifting mechanism 53 of the heating unit 5, and the heating plate 51 starts heating the substrate 9 (step S17). The heating by the heating plate 15 is performed on the substrate 9 in a static state. In addition, the heating by the heating plate 51 can also be performed on the substrate 9 that is rotating at a low number of rotations. In this case, the heating plate 51 is separated from the substrate 9 by a slight distance downward. As described above, when the substrate 9 starts to be heated, the fan unit 72 stops forming the downward airflow. In addition, as will be described later, the formation system of the downflow is maintained in a stopped state until the substrate 9 is heated to a predetermined condition.

Then, the heating plate 51 heats the substrate 9 from the side of the lower surface 92, and the upper surface 91 of the substrate 9 becomes higher than the boiling point of the processing liquid, thereby making it contact with the upper surface 91 of the substrate 9 in the liquid film 93 of the processing liquid. The treatment liquid is vaporized in the contacting part. In other words, a part of the liquid film 93 of the processing liquid is vaporized on the upper surface 91 of the substrate 9. Thereby, as shown in FIG. 6, a gas phase layer 94 of the processing liquid is formed between the upper surface 91 of the substrate 9 and the liquid film 93 of the processing liquid (step S18). In FIG. 6, the thickness of the gas phase layer 94 is depicted as being thicker than the actual thickness. The gas phase layer 94 is formed on the entire upper surface 91 of the substrate 9. Thereby, the liquid film 93 of the processing liquid is separated upward from the upper surface 91 of the substrate 9 and is supported by the gas phase layer 94 from below. In other words, the liquid film 93 of the processing liquid is held in a state of floating on the upper surface 91 of the substrate 9 via the gas phase layer 94. In addition, the gas phase layer 94 of the treatment liquid is also referred to as the gas phase film, vapor film, or vapor layer of the treatment liquid.

FIG. 7 is an enlarged longitudinal sectional view showing the vicinity of the upper surface 91 of the substrate 9 in a state where the liquid film 93 is formed in step S14. FIG. 8 is an enlarged longitudinal sectional view showing the vicinity of the upper surface 91 of the substrate 9 in a state where the gas phase layer 94 is formed in step S18. In the state shown in FIG. 7, the space between the convex structures 911 for forming the fine pattern provided on the substrate 9 is filled with the liquid film 93 of the processing liquid. In addition, the liquid film 93 of the treatment liquid is present above the upper end of the structure 911 (that is, the upper surface 91 of the substrate 9). In other words, the upper surface of the liquid film 93 of the treatment liquid is located above the upper end of the structure 911.

As described above, when the substrate 9 is heated by the heating plate 51 to a temperature higher than the boiling point of the processing liquid (for example, a temperature 10°C to 50°C higher than the boiling point), the processing liquid in contact with the substrate 9 vaporizes (that is, evaporates). ) And generate the gas of the treatment liquid, and a gas phase layer 94 is formed as shown in FIG. 8. The gas phase layer 94 fills the space between the structures 911 and further expands to the upper side of the upper end of the structures 911. In the state shown in FIG. 8, the interface 95 between the gas phase layer 94 of the treatment liquid and the liquid film 93 (that is, the upper surface of the gas phase layer 94) is located above the upper end of the structure 911. Therefore, the liquid film 93 of the treatment liquid (that is, the liquid The treatment fluid) is separated upward from the structure 911 so as not to contact the structure 911.

In the substrate processing apparatus 1, the fan unit 72 stops generating the downward airflow until the temperature of the peripheral portion of the substrate 9 becomes a predetermined temperature (for example, a temperature higher than the boiling point of the processing liquid by 10° C. to 50° C.) or higher. Next, after a predetermined time has elapsed from the start of heating of the substrate 9, after the temperature of the peripheral edge portion of the substrate 9 becomes equal to or higher than the predetermined temperature, the fan unit 72 starts to generate downflow again (step S19). In other words, even in the peripheral edge portion of the substrate 9, after the gas phase layer 94 of the processing liquid is formed and the liquid film 93 moves upward from the structure 911, the downward airflow starts to form around the substrate 9 again. Thereby, it is prevented or suppressed that the temperature of the processing liquid falls due to the downward air flow during the formation of the gas phase layer 94 in the peripheral portion of the substrate 9 and hinders the formation of the gas phase layer 94. In step S19, the temperature of the peripheral portion of the substrate 9 may be measured by the temperature sensor, or the heating time until the temperature of the substrate 9 becomes equal to or higher than the predetermined temperature described above may be measured in advance, and the heating time may elapse On the other hand, it is determined that the temperature of the peripheral portion of the substrate 9 has become higher than the predetermined temperature described above.

When the vapor phase layer 94 of the processing liquid is formed on the entire upper surface 91 of the substrate 9, the liquid film 93 on the vapor phase layer 94 is removed from the substrate 9 (step S20). In step S20, the liquid film 93 of the processing liquid is removed from the substrate 9 while maintaining the state in which it is not in contact with the structure 911 on the substrate 9. Therefore, it is possible to prevent the collapse of the structure 911 due to the surface tension of the treatment liquid, and to remove the treatment liquid from the substrate 9.

The removal of the liquid film 93 of the treatment liquid in step S20 can also be performed by various methods. FIG. 9 is a diagram showing an example of the flow of the removal process of the liquid film 93. In steps S31 to S33 shown in FIG. 9, the substrate 9 is not rotated but is in a stationary state. When removing the liquid film 93, first, after the above-mentioned step S19, an inert gas (for example, nitrogen) is sprayed from the first ejection port 616 of the first nozzle 61 toward the center of the liquid film 93 located on the center of the substrate 9. Thereby, as shown in FIG. 10, a small hole 96 is formed in the center part of the liquid film 93, and a part of the upper surface 91 of the board|substrate 9 is exposed from the hole 96 (step S31). In step S31, the flow rate of the inert gas ejected from the first ejection port 616 is a relatively small first flow rate (for example, 3 liters/minute).

In the substrate processing apparatus 1, the inert gas ejected from the first ejection port 616 forms a radial flow from the center of the liquid film 93 of the processing liquid toward the periphery (that is, toward the radially outer side). Then, the pores 96 of the liquid film 93 of the processing liquid are enlarged by the air flow. As the hole 96 expands, the processing liquid system constituting the liquid film 93 moves radially outward, and the processing liquid system on the peripheral edge of the substrate 9 flows down from the outer edge of the substrate 9 and is removed from the substrate 9. Therefore, the first nozzle 61 is a liquid removal part for removing the liquid film 93 from the substrate 9.

In the substrate processing apparatus 1, in parallel with the ejection of the inert gas from the first ejection port 616, the heating plate 51 of the heating unit 5 also continues to heat the substrate 9. Thereby, the temperature of the substrate 9 rapidly rises in the area overlapping with the hole 96 of the liquid film 93, and a temperature gradient is generated on the substrate 9. Since the liquid film 93 on the gas phase layer 94 moves from the high temperature side to the low temperature side (that is, toward the outside in the radial direction), the pores 96 of the liquid film 93 are also enlarged by the temperature gradient. As described above, since the processing liquid system on the peripheral edge portion of the substrate 9 is removed from the substrate 9 as the hole 96 expands, the heating part 5 is also included in the liquid removal part described above.

As described above, since the downflow of clean gas starts to form around the substrate 9 again, the liquid film 93 supported on the gas phase layer 94 in the peripheral portion of the substrate 9 also moves radially outward by the downflow. mobile. In other words, the downward airflow promotes the processing liquid in the peripheral portion of the upper surface 91 of the substrate 9 to move radially outward (that is, to move toward the outer edge of the substrate 9). Thereby, the removal of the processing liquid on the peripheral edge portion of the substrate 9 is promoted.

In addition, in the substrate processing apparatus 1, in parallel with step S31 or after step S31, the cover 41 is moved downward by the cover moving mechanism 42, and the inner peripheral edge of the cover top cover portion 44 of the cover 41 is set as shown in FIG. The base portion 21 of the substrate holding portion 2 is arranged at the same position in the vertical direction. In other words, the inner periphery of the top cover portion 44 is located between the upper surface and the lower surface of the base portion 21 in the vertical direction. Thereby, the gap between the base portion 21 and the cover 41 is reduced, and the flow path area of the downflow flowing in from the upper side of the cover 41 to the inside of the cover 41 in the periphery of the base portion 21 is reduced (step S32). As a result, the substrate The flow velocity of the descending airflow in the periphery of 9 is increased, and the removal of the processing liquid on the peripheral edge of the substrate 9 is further promoted. In addition, step S32 may be performed before step S31 as long as the rotation of the substrate 9 is stopped in step S14.

After a predetermined time has elapsed since the inert gas is sprayed from the first spray port 616 of the first nozzle 61 shown in FIG. Flow rate (for example, 30 liters/minute). Thereby, the expansion of the pore 96 of the liquid film 93 is promoted. In addition, the heating plate 51 is lowered to the standby position by the plate lifting mechanism 53, and the heating plate 51 stops heating the substrate 9.

As shown in FIG. 12, when the hole 96 of the liquid film 93 of the processing liquid becomes larger to a certain extent, in addition to the inert gas ejected from the first ejection port 616 of the first nozzle 61, the second ejection port is also 617 ejects inert gas (step S33). The inert gas system from the plurality of second ejection ports 617 is ejected radially to the direction from the center of the liquid film 93 (that is, the center of the substrate 9) toward the surroundings. Thereby, the hole 96 of the liquid film 93 of the processing liquid is further enlarged, and the processing liquid on the upper surface 91 of the substrate 9 flows down from the outer edge of the substrate 9 and is removed from the substrate 9. In addition, since the processing liquid on the peripheral edge portion of the substrate 9 can be efficiently moved radially outward by the radial airflow from the plurality of second ejection ports 617, it is possible to appropriately prevent or suppress the processing liquid on the peripheral edge of the substrate 9 Treatment liquid remains in the part.

In addition, in the removal of the liquid film 93 of the processing liquid, step S33 (that is, the inert gas is ejected from the plurality of second ejection ports 617) may be omitted. Even in this case, by steps S31 to S32, the liquid film 93 of the processing liquid on the upper surface 91 of the substrate 9 moves from the center of the substrate 9 toward the outer edge and is removed from the substrate 9.

When the removal of the liquid film 93 of the processing liquid is completed (step S20), the drying process of the substrate 9 is performed (step S21). In step S21, in a state where the cover 41 is raised and located around the substrate 9, the substrate holding portion 31 is rotated at a relatively high rotation speed. Thereby, there is a possibility that the liquid components remaining on the substrate 9 are flung off and removed, and the substrate 9 is dried. In step S21, the idler is continuously ejected from the first nozzle 61 性气。 The gas. Therefore, it is prevented or suppressed that liquid droplets and mist splashed from the cover 41 are reattached to the upper surface 91 of the substrate 9 and the like.

The substrate 9 on which the drying process has been completed is carried out from the substrate processing apparatus 1. In the substrate processing apparatus 1, the above-mentioned steps S11 to S21 are sequentially performed on a plurality of substrates 9.

As described above, the substrate processing apparatus 1 includes the substrate holding section 2, the processing liquid supply section, the heating section 5, and the liquid removal section. The substrate holding portion 2 holds the substrate 9 in a horizontal state. The processing liquid supply unit (the first nozzle 61 in the above example) supplies processing liquid with a surface tension higher than IPA to the upper surface 91 of the substrate 9, thereby forming a processing covering the entire upper surface 91 of the substrate 9液的液膜93。 Liquid liquid film 93. The heating unit 5 heats the substrate 9 from the side of the lower surface 92 and vaporizes a part of the liquid film 93, thereby forming a gas phase layer 94 between the upper surface 91 of the substrate 9 and the liquid film 93. The liquid removal part (the first nozzle 61 in the above example) removes the liquid film 93 on the gas phase layer 94.

In this way, the liquid film 93 is formed with a treatment liquid with a higher surface tension than IPA compared to the case where the liquid film is formed by IPA, thereby preventing unintended damage of the liquid film 93 before the liquid film 93 is removed (for example, the treatment liquid is removed from The periphery of the substrate 9 and the clamp pins 23 flow down, or the liquid film 93 is cracked due to the vapor of the processing liquid generated between the liquid film 93 and the substrate 9). As a result, the heating time required to form the gas phase layer 94 of the processing liquid can be ensured, and the liquid film 93 can be appropriately floated above the substrate 9. Therefore, the collapse of the pattern on the substrate 9 (that is, the collapse of the structure 911 described above) can be prevented or suppressed, and the liquid film 93 can be stably removed from the substrate 9.

As described above, it is preferable that the vapor pressure of the treatment liquid is higher than the vapor pressure of IPA. Thereby, the gas phase layer 94 of the treatment liquid can be formed at a lower temperature than in the case where the gas phase layer is formed from the liquid film of IPA. In addition, compared with the case where the gas phase layer is formed from a liquid film of IPA, as long as the heating temperature is the same, the time required to form the gas phase layer 94 of the treatment liquid can be shortened. As a result, the liquid film 93 can be floated above the substrate 9 in a short time. In addition, the time required for the processing of the substrate 9 in the substrate processing apparatus 1 can also be shortened.

Preferably, the treatment liquid contains cis-1,2-dichloroethylene (molecular formula: C ₂ H ₂ Cl ₂ ), chloroform (molecular formula: CHCl ₃ ), methyl acetate (molecular formula: C ₃ H ₆ O ₂ ), 1,3-dioxolane (molecular formula: C ₃ H ₆ O ₂ ), tetrahydrofuran (molecular formula: C ₄ H ₈ O), 1,1,1-trichloroethane (molecular formula: C ₂ H ₃ Cl ₃ ), tetrachloromethane (molecular formula: CCl ₄ ), benzene (molecular formula: C ₆ H ₆ ), cyclohexane (molecular formula: C ₆ H ₁₂ ), acetonitrile (molecular formula: C ₂ H ₃ N), trichloroethylene (Molecular formula: C ₂ HCl ₃ ), tetrahydropiperan (molecular formula: C ₅ H ₁₀ O), nitric acid (molecular formula: HNO ₃ ), 1,2-dichloroethane (molecular formula: C ₂ H ₄ Cl ₂ ), 1,2-Dichloropropane (molecular formula: C ₃ H ₆ Cl ₂ ), fluorotrinitromethane (molecular formula: CFN ₃ O ₆ ), pyrrolidine (molecular formula: C ₄ H ₉ N), acrylonitrile (molecular formula: C At least one of ₃ H ₃ N) and cyclohexene (molecular formula: C ₆ H _{10 ).} Thereby, the surface tension and vapor pressure of the processing liquid can be set higher than the surface tension and vapor pressure of IPA.

As described above, it is preferable that the heating of the substrate 9 by the heating unit 5 (step S17) is restarted after the entire upper surface 91 of the substrate 9 is covered by the processing liquid supplied from the processing liquid supply unit (step S14). . By this, compared with the case where the substrate is heated before the processing liquid is supplied and the case where the substrate is heated before the processing liquid covers the entire upper surface of the substrate, the temperature of the processing liquid supplied to the substrate 9 can be suppressed from rising rapidly and vaporizing rapidly. . As a result, the liquid film 93 of the processing liquid can be stably and appropriately formed on the substrate 9.

In the substrate processing apparatus 1, it is preferable that the liquid removing section includes a gas ejection section (the first nozzle 61 in the above example) for ejecting gas toward the center of the liquid film 93. In this case, the gas from the gas ejection portion forms a radial flow from the center of the liquid film 93 toward the surroundings, so that the processing liquid moves from the center of the liquid film 93 toward the outer edge of the substrate 9 and moves from the substrate 9 On removal. Thereby, the liquid film 93 can be removed from the substrate 9 with a simple structure.

Preferably, the gas ejection portion is provided with a first ejection port 616 and a plurality of second ejection ports 617. The first ejection port 616 ejects gas toward the center of the liquid film 93. The plurality of second ejection ports 617 are circumferentially arranged around the first ejection port 616. The plurality of second ejection ports 617 are aligned with the liquid film The central part of 93 ejects gas radially toward the surrounding direction. Thereby, the hole 96 formed in the center of the liquid film 93 can be rapidly expanded. As a result, the liquid film 93 can be removed from the substrate 9 easily and quickly. In addition, compared with the case where a circular slit-shaped ejection port is provided, by providing a plurality of smaller second ejection ports 617 circumferentially, the flow rate of the gas ejected from the second ejection port 617 can be increased. Increase. As a result, it is possible to appropriately prevent or suppress the remaining processing liquid in the peripheral portion of the substrate 9.

Preferably, the substrate processing apparatus 1 further includes a chamber 11 and an air flow forming part 71. The chamber 11 accommodates the substrate holding portion 2 in the internal space. The gas flow forming part 71 sends gas from the upper part of the chamber 11 to the internal space, and forms a downward flow from the upper side to the lower side of the substrate 9 around the substrate 9. When the processing liquid is removed from the substrate 9, the downward airflow promotes the processing liquid in the peripheral portion of the upper surface 91 of the substrate 9 to move toward the outer edge. Thereby, the liquid film 93 can be quickly removed from the substrate 9.

More preferably, the substrate processing apparatus 1 further includes a rotating mechanism 3, a cover 41, and a cover moving mechanism 42. The rotating mechanism 3 rotates the substrate holding portion 2. The cover 41 is arranged around the substrate holding portion 2 with a gap therebetween. The cover 41 catches the liquid scattered from the rotating substrate 9. The cover moving mechanism 42 relatively moves the cover 41 with respect to the substrate holding portion 2. When removing the processing liquid from the substrate 9, the cover 41 is relatively moved by the cover moving mechanism 42, thereby reducing the gap between the substrate holding portion 2 and the cover 41. Thereby, the flow velocity of the downward airflow described above in the periphery of the substrate 9 can be increased. As a result, the removal of the liquid film 93 from the substrate 9 can be performed more quickly.

As described above, it is preferable that when the heating unit 5 starts to heat the substrate 9 (step S17), the air flow forming unit 71 stops forming the downward air flow. Thereby, it is possible to prevent the peripheral edge portion of the liquid film 93 from being cooled by the downflow. For example, the temperature of the peripheral portion of the substrate 9 that has stopped forming the downflow and has been heated for a predetermined time becomes about 10°C to 20°C higher than that in the case where the downflow is not stopped. As a result, the entire liquid film 93 can be heated substantially uniformly and the gas phase layer 94 can be appropriately formed. In addition, the time required to heat the substrate 9 to a desired temperature can be shortened.

More preferably, it is the same as the process liquid supply before the heating section 5 starts heating the substrate 9 (step S17) At the same time as the supply of the processing liquid is stopped by the supply unit (step S15), the airflow forming unit 71 stops forming the downflow (step S16). Thereby, it is possible to suppress the peripheral edge portion of the liquid film 93 of the processing liquid formed on the substrate 9 from being sloppy due to the downward air flow, and the liquid film 93 can be stably maintained.

In addition, it is more preferable that the air flow forming portion 71 restarts to form a downward air flow after the temperature of the peripheral edge portion of the substrate 9 becomes a predetermined temperature or higher (step S19). Thereby, it is possible to prevent or suppress the temperature of the processing liquid in the process of forming the gas phase layer 94 on the peripheral edge portion of the substrate 9 from being lowered due to the downflow and hindering the formation of the gas phase layer 94.

The above-mentioned substrate processing method includes the following steps: holding the substrate 9 in a horizontal state (step S11); supplying a processing liquid with a surface tension higher than IPA to the upper surface 91 of the substrate 9, thereby forming the upper surface of the covering substrate 9 The liquid film 93 of the treatment liquid on the entire surface of the substrate 91 (step S14); heat the substrate 9 from the side of the lower surface 92 and vaporize a part of the liquid film 93, thereby being between the upper surface 91 of the substrate 9 and the liquid film 93 The gas phase layer 94 is formed (step S18); and the liquid film 93 on the gas phase layer 94 is removed (step S20). As a result, as described above, compared with the case where the liquid film is formed by IPA, the liquid film 93 can be prevented from being damaged unexpectedly before the liquid film 93 is removed. As a result, the heating time required to form the gas phase layer 94 of the processing liquid can be ensured, and the liquid film 93 can be appropriately floated upward of the substrate 9. Therefore, the collapse of the pattern on the substrate 9 can be prevented or suppressed, and the liquid film 93 can be stably removed from the substrate 9.

In the substrate processing apparatus 1, in the case where the cleaning liquid and the processing liquid are not easily approached as described above, the substrate 9 may be IPA between the cleaning process (step S13) and the supply of the processing liquid to the substrate 9 (step S14). Supply processing. Specifically, after the cleaning process of the substrate 9 is completed, the IPA is supplied to the rotating substrate 9 and spread to the entire upper surface 91 of the substrate 9. Thereby, the cleaning liquid on the upper surface 91 of the substrate 9 is rinsed and replaced with IPA. After that, the supply of IPA to the substrate 9 is stopped, and the processing liquid is supplied to the rotating substrate 9 as described above. Next, the processing liquid system spreads from the center of the substrate 9 to the entire upper surface 91, and the IPA system on the upper surface 91 of the substrate 9 is rinsed and replaced with the processing liquid.

In this way, in the substrate processing apparatus 1, the entire upper surface 91 of the substrate 9 may be covered The processing liquid is supplied to the upper surface 91 of the substrate 9 from the processing liquid supply part (the first nozzle 61 in the above-mentioned example) in the state covered with IPA. Next, the IPA on the upper surface 91 of the substrate 9 is replaced by the processing liquid, thereby forming a liquid film 93 of the processing liquid. Since the processing liquid and IPA are relatively easy to get close, the processing liquid can be made close to the substrate 9 and can easily enter between the patterned structures 911. As a result, the liquid film 93 of the processing liquid can be appropriately formed on the substrate 9.

The above-mentioned treatment liquid may be a mixed liquid in which a substance having a surface tension higher than IPA and a vapor pressure lower than IPA is mixed with IPA. In this case as well as the above, it is possible to suppress unexpected breakage of the liquid film 93 before the liquid film 93 is removed, compared to the case where the liquid film is formed by IPA. In addition, since IPA and the cleaning liquid are relatively easy to get close to each other, the replacement of the cleaning liquid and the processing liquid in step S14 can be easily performed, or the replacement of the IPA and the processing liquid can be easily performed when the IPA is supplied as described above. Furthermore, since the vapor pressure of this substance is lower than that of IPA, when the liquid film 93 of the treatment liquid is heated and the gas phase layer 94 is formed, only this substance vaporizes before IPA to prevent the surface tension of the treatment liquid. reduce. As the substance, for example, allyl alcohol (allyl alcohol; molecular formula C ₃ H ₆ O) or 1-propanol (1-propanol; molecular formula C ₃ H ₈ O) can be used.

Various changes can be made in the substrate processing apparatus 1 and the substrate processing method described above.

For example, a circumferential slit-shaped ejection port may be provided instead of a plurality of second ejection ports 617, or in addition to a plurality of second ejection ports 617, a circumferential slit-shaped ejection port may also be provided. The ejection port is a circumferential slit-shaped ejection port that ejects gas radially from the center to the surrounding direction. In addition, it is not necessary to provide an ejection port for ejecting gas on the outer surface of the first nozzle 61.

The processing liquid supplied to the substrate 9 in step S14 is not limited to the liquids described and exemplified above, and various liquids having a surface tension higher than IPA may be used as the processing liquid. For example, a liquid having a surface tension higher than IPA and a vapor pressure of IPA or less can also be used as the above-mentioned treatment liquid.

It is not necessary to stop the formation of downdraft in step S16 with the stop in step S15. While supplying the processing liquid is performed simultaneously, it may be performed before or after step S15. In addition, regardless of the temperature of the peripheral portion of the substrate 9, the formation of the downward airflow may be restarted in step S19. In addition, between step S11 and step S21, the downflow may not be stopped but the downflow may be continuously formed.

As described above, when the heating unit 5 starts to heat the substrate 9, the air flow forming unit 71 stops forming the downward air flow, whereby the entire liquid film 93 can be heated substantially uniformly and the gas phase layer 94 can be appropriately formed. Therefore, from the viewpoint of heating the entire liquid film 93 of the treatment liquid substantially uniformly and appropriately forming the gas phase layer 94, the treatment liquid does not necessarily need to be a liquid with a surface tension higher than IPA, and it may also be a liquid with a surface tension of IPA. The following liquid. For example, the treatment liquid may be IPA.

The heating of the substrate 9 in step S17 does not necessarily need to be started after the formation of the liquid film 93 in step S14, and may be started simultaneously with step S14 or before step S14. In addition, the heating unit 5 for heating the substrate 9 may also be provided with, for example, a heating lamp instead of the heating plate 51, and the heating lamp is used to irradiate the lower surface 92 of the substrate 9 with light and heat the substrate 9.

In the removal of the liquid film 93 in step S20, since it is not necessary to reduce the gap between the substrate holding portion 2 and the cover 41, step S32 may be omitted. In addition, in step S20, it is not necessary to promote the movement of the processing liquid by the downflow.

In step S20, the removal of the liquid film 93 can also be promoted by rotating the substrate 9. In this case, a rotating mechanism 3 for rotating the substrate 9 may also be included in the liquid removing part.

The removal of the liquid film 93 by the liquid removal part may be performed by other various methods. For example, a suction nozzle may also be used as a liquid removal part; the suction nozzle is inserted into the liquid film 93 supported by the gas phase layer 94 and sucks the liquid film 93, thereby removing the liquid film 93 from the substrate 9. Alternatively, a sponge or the like may be used as the liquid removal part, and the sponge contacts the upper surface of the liquid film 93 supported on the gas phase layer 94 and absorbs the liquid film 93. In addition, the inert gas may be sprayed in a strip form toward the upper surface 91 of the substrate 9 from a slit-shaped inert gas ejection port that is longer than the diameter of the substrate 9 while making the inert gas The body ejection port reciprocates above the substrate 9, thereby removing the liquid film 93 from the substrate 9.

The above-mentioned substrate processing apparatus 1 is not only used for processing semiconductor substrates, but also used for glass substrates used in flat panel displays such as liquid crystal display devices or organic EL (Electro Luminescence) display devices. It can also be used in the treatment of glass substrates used in other display devices. In addition, the substrate processing apparatus 1 described above can also be used for processing substrates for optical disks, substrates for magnetic disks, substrates for optical magnetic disks, substrates for photomasks, ceramic substrates, substrates for solar cells, and the like.

As long as the configurations in the above-mentioned embodiment and each modification example do not contradict each other, they may be combined as appropriate.

Although the present invention has been described and explained in detail, the above description is only illustrative and not restrictive. Therefore, as long as it does not deviate from the scope of the present invention, there may be a plurality of changes and aspects.

1: Substrate processing equipment

2: Board holding part

3: Rotating mechanism

5: Heating part

6: Liquid supply part

7: Gas supply department

9: Substrate (semiconductor substrate)

11: Chamber

21: Base

22: Keep the shaft

23: Fixture pin

24: Lid

41: Hood

42: Hood moving mechanism

43: hood side wall

44: Cover top cover

45: discharge port

51: heating plate

52: Heating shaft

53: Plate lifting mechanism

62: second nozzle

63: The third nozzle

71: Airflow forming part

72: fan unit

91: (of the substrate) upper surface

610: The first nozzle moving mechanism

620: Second nozzle moving mechanism

J1: Central axis

Claims (23)

A substrate processing device for processing substrates, and is provided with: a substrate holding portion that holds the substrate in a horizontal state; a processing liquid supply portion that supplies a processing liquid with a higher surface tension than isopropanol to the substrate On the upper surface, a liquid film of the processing liquid covering the entire surface of the upper surface of the substrate is formed; the heating part heats the substrate from the lower surface side and vaporizes a part of the liquid film, thereby forming a liquid film on the substrate A gas phase layer is formed between the upper surface of the upper surface and the liquid film; and a liquid removal section for removing the liquid film on the gas phase layer; the vapor pressure of the treatment liquid is higher than the vapor pressure of the isopropanol; The aforementioned treatment liquid system contains cis-1,2-dichloroethylene, chloroform, methyl acetate, 1,3-dioxolane, tetrahydrofuran, 1,1,1-trichloroethane, tetrachloromethane, Benzene, cyclohexane, acetonitrile, trichloroethylene, tetrahydropiperan, nitric acid, 1,2-dichloroethane, 1,2-dichloropropane, fluorotrinitromethane, pyrrolidine, acrylonitrile, cyclohexane At least one of olefins. A substrate processing device for processing substrates, and is provided with: a substrate holding portion that holds the substrate in a horizontal state; a processing liquid supply portion that supplies a processing liquid with a higher surface tension than isopropanol to the substrate On the upper surface, a liquid film of the processing liquid covering the entire surface of the upper surface of the substrate is formed; the heating part heats the substrate from the lower surface side and vaporizes a part of the liquid film, thereby forming a liquid film on the substrate A vapor phase layer is formed between the upper surface and the liquid film; and a liquid removal section for removing the liquid film on the vapor layer; on the entire surface of the upper surface of the substrate covered by the isopropyl alcohol In the state, the processing liquid is supplied from the processing liquid supply part to the upper surface of the substrate, and the isopropyl alcohol on the upper surface of the substrate is replaced by the processing liquid, thereby The aforementioned liquid film of the aforementioned treatment liquid is formed. A substrate processing device for processing substrates, and is provided with: a substrate holding portion that holds the substrate in a horizontal state; a processing liquid supply portion that supplies a processing liquid with a higher surface tension than isopropanol to the substrate On the upper surface, a liquid film of the processing liquid covering the entire surface of the upper surface of the substrate is formed; the heating part heats the substrate from the lower surface side and vaporizes a part of the liquid film, thereby forming a liquid film on the substrate A gas phase layer is formed between the upper surface and the liquid film; and the liquid removal part removes the liquid film on the gas phase layer; the treatment liquid has a surface tension higher than that of the isopropanol and a vapor pressure ratio The above-mentioned isopropanol is still low and mixed into the above-mentioned mixture of isopropanol. The substrate processing apparatus according to any one of claims 1 to 3, wherein the heating of the substrate by the heating section is performed by covering the upper surface of the substrate with the processing liquid supplied from the processing liquid supply section Start after the whole face. The substrate processing apparatus according to any one of claims 1 to 3, wherein the liquid removal section includes: a gas ejection section that ejects gas toward the center of the liquid film; The gas forms a radial flow from the center portion of the liquid film toward the surroundings, and the processing liquid moves from the center portion of the liquid film toward the outer edge of the substrate and is removed from the substrate. The substrate processing apparatus according to claim 5, wherein the gas ejection portion includes: a first ejection port that ejects gas toward the center portion of the liquid film; and a plurality of second ejection ports that are circumferentially arranged Around the first ejection port, gas is ejected radially from the center portion of the liquid film toward the periphery. The substrate processing apparatus described in claim 5, which further includes: The chamber contains the substrate holding part in the internal space; and the air flow forming part sends gas from the upper part of the chamber to the internal space, and forms a drop from the upper side to the lower side of the substrate around the substrate Air flow; The down flow system promotes the processing liquid in the peripheral portion of the upper surface of the substrate to move toward the outer edge when the processing liquid is removed from the substrate. The substrate processing apparatus according to claim 7, further comprising: a rotating mechanism that rotates the substrate holding portion; and a cover is arranged around the substrate holding portion with a gap therebetween to catch the rotating Liquid scattered from the substrate; and a cover moving mechanism that relatively moves the cover relative to the substrate holding portion; when the processing liquid is removed from the substrate, the cover moving mechanism relatively moves the cover, and The gap between the substrate holding portion and the cover is reduced. The substrate processing apparatus according to claim 7, wherein when the heating section starts to heat the substrate, the air flow forming section stops forming the down flow. The substrate processing apparatus according to claim 9, wherein at the same time that the processing liquid supply unit stops supplying the processing liquid before the heating unit starts to heat the substrate, the airflow forming unit stops forming the downflow. The substrate processing apparatus according to claim 9, wherein after the temperature of the peripheral edge portion of the substrate becomes a predetermined temperature or higher, the airflow forming portion starts to form the downflow again. A substrate processing device for processing substrates, and is provided with: a substrate holding portion that holds the substrate in a horizontal state; a processing liquid supply portion that supplies a processing liquid with a higher surface tension than isopropanol to the substrate On the upper surface, a liquid film of the processing liquid covering the entire surface of the upper surface of the substrate is formed; the heating part heats the substrate from the lower surface side and makes a part of the liquid film gas To form a gas phase layer between the upper surface of the substrate and the liquid film; the liquid removal part removes the liquid film on the gas phase layer; the chamber contains the substrate holding part inside Space; and a gas flow forming part, which sends gas from the upper part of the chamber to the internal space, and forms a descending gas flow from the upper side to the lower side of the substrate around the substrate; the liquid removal part is provided with: gas ejection The part is to eject gas toward the center of the liquid film; the gas from the gas ejection section forms a radial gas flow from the center of the liquid film to the surroundings, and causes the processing liquid to flow from the liquid film. The central portion moves toward the outer edge of the substrate and is removed from the substrate; the downward air flow promotes the processing liquid in the peripheral portion of the upper surface of the substrate toward the outer edge when the processing liquid is removed from the substrate mobile. The substrate processing apparatus according to claim 12, wherein the heating of the substrate by the heating section is started after the entire upper surface of the substrate is covered by the processing liquid supplied from the processing liquid supply section. The substrate processing apparatus according to claim 12, wherein the gas ejection portion is provided with: a first ejection port that ejects gas toward the center portion of the liquid film; and a plurality of second ejection ports that are circumferentially arranged Around the first ejection port, gas is ejected radially from the center portion of the liquid film toward the periphery. The substrate processing apparatus according to claim 12, further comprising: a rotating mechanism that rotates the substrate holding portion; and a cover is arranged around the substrate holding portion with a gap therebetween to catch the rotating Liquid scattered from the substrate; and a cover moving mechanism that relatively moves the cover relative to the substrate holding portion; When the processing liquid is removed from the substrate, the cover is moved relatively by the cover moving mechanism, and the gap between the substrate holding portion and the cover is reduced. The substrate processing apparatus according to claim 12, wherein when the heating section starts to heat the substrate, the air flow forming section stops forming the down flow. The substrate processing apparatus according to claim 16, wherein at the same time that the processing liquid supply unit stops supplying the processing liquid before the heating unit starts to heat the substrate, the airflow forming unit stops forming the downflow. The substrate processing apparatus according to claim 16, wherein after the temperature of the peripheral edge portion of the substrate becomes a predetermined temperature or higher, the airflow forming portion starts to form the downflow again. A processing liquid used for the processing of substrates, has a surface tension higher than isopropanol, and is supplied to the upper surface of the substrate in the substrate processing apparatus described in any one of claims 1 to 18. A substrate processing method for processing substrates, and includes: step (a), holding the substrate in a horizontal state; step (b), supplying a processing solution with a higher surface tension than isopropanol to the substrate The upper surface of the substrate, thereby forming a liquid film of the treatment liquid covering the entire surface of the upper surface of the substrate; step (c), heating the substrate from the lower surface side and vaporizing a part of the liquid film, thereby Forming a gas phase layer between the upper surface of the substrate and the liquid film; and step (d) is to remove the liquid film on the gas phase layer; the vapor pressure of the treatment liquid is higher than that of the isopropanol vapor The pressure is still high; the aforementioned treatment liquid system contains cis-1,2-dichloroethylene, chloroform, methyl acetate, 1,3-dioxolane, tetrahydrofuran, 1,1,1-trichloroethane, Tetrachloromethane, benzene, cyclohexane, acetonitrile, trichloroethylene, tetrahydropiperan, nitric acid, 1,2-dichloroethane, 1,2-dichloropropane, fluorotrinitromethane, pyrrolidine, propylene At least one of nitrile and cyclohexene. A substrate processing method for processing substrates, and includes: step (a), holding the substrate in a horizontal state; step (b), supplying a processing solution with a higher surface tension than isopropanol to the substrate The upper surface of the substrate, thereby forming a liquid film of the treatment liquid covering the entire surface of the upper surface of the substrate; step (c), heating the substrate from the lower surface side and vaporizing a part of the liquid film, thereby Forming a vapor phase layer between the upper surface of the substrate and the liquid film; and step (d) is to remove the liquid film on the vapor layer; in the step (b), With propanol covering the entire surface of the upper surface of the substrate, the processing liquid is supplied to the upper surface of the substrate, and the isopropyl alcohol on the upper surface of the substrate is replaced by the processing liquid, thereby The aforementioned liquid film of the aforementioned treatment liquid is formed. A substrate processing method for processing substrates, and includes: step (a), holding the substrate in a horizontal state; step (b), supplying a processing solution with a higher surface tension than isopropanol to the substrate The upper surface of the substrate, thereby forming a liquid film of the treatment liquid covering the entire surface of the upper surface of the substrate; step (c), heating the substrate from the lower surface side and vaporizing a part of the liquid film, thereby A gas phase layer is formed between the upper surface of the substrate and the liquid film; and step (d) is to remove the liquid film on the gas phase layer; the surface tension of the treatment liquid is higher than that of the isopropyl alcohol And a substance with a vapor pressure lower than the aforementioned isopropanol is mixed into the aforementioned mixture of isopropanol. A substrate processing method for processing substrates, and includes: step (a), which is to maintain the aforementioned substrate in a horizontal state in the internal space of the chamber; step (b), to make the surface tension higher than isopropanol The processing liquid is supplied to the aforementioned substrate The upper surface of the substrate, thereby forming a liquid film of the treatment liquid covering the entire surface of the upper surface of the substrate; step (c), heating the substrate from the lower surface side and vaporizing a part of the liquid film, thereby Forming a gas phase layer between the upper surface of the substrate and the liquid film; and step (d) is to remove the liquid film on the gas phase layer; in the step (d), by adding the liquid film to the liquid film The central portion of the liquid film is sprayed with gas to form a radial air flow from the central portion of the liquid film toward the surroundings, and the processing liquid is moved from the central portion of the liquid film toward the outer edge of the substrate and removed from the substrate; When removing the processing liquid from the substrate, by sending the gas from the upper part of the chamber to the internal space, a downward airflow from the upper side to the lower side of the substrate is formed around the substrate, thereby promoting the substrate The processing liquid in the peripheral edge portion of the upper surface moves toward the outer edge.

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