TWI880550B - Substrate processing method and substrate processing apparatus - Google Patents

Abstract

The present invention provides a method for treating a substrate having an anti-corrosion film formed on a main surface. The method includes: a nozzle configuration step, which is to configure a plurality of fluid nozzles toward the main surface of the substrate; a supply step, which is to supply water vapor, ozone gas and sulfuric acid to the plurality of fluid nozzles; and a mixed fluid supply step, which is to supply a mixed fluid of water vapor, ozone gas and sulfuric acid from the plurality of fluid nozzles to the main surface of the above-mentioned substrate, and remove the anti-corrosion film from the main surface of the substrate. The supply step may include a wet ozone gas supply step, and the wet ozone gas supply step is to supply a wet ozone gas formed by a mixture of water vapor and ozone gas to the plurality of fluid nozzles.

Description

Substrate processing method and substrate processing device

The present invention relates to a substrate processing method and a substrate processing device for processing substrates. The substrates to be processed include, for example, semiconductor wafers, liquid crystal display devices and organic EL (Electroluminescence) display devices, FPD (Flat Panel Display) substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, solar cell substrates, etc.

In the manufacturing process of semiconductor devices, an anti-etching agent (photoresist) is used as a mask for forming a pattern on a substrate or injecting ions into an active area. As a wet treatment for removing the anti-etching agent from a substrate after use, a treatment using a sulfuric acid-hydrogen peroxide mixture (SPM) is known. Specifically, as described in Patent Document 1, the anti-etching agent on the substrate is removed by mixing sulfuric acid and hydrogen peroxide to generate SPM and supplying the SPM to the surface of the substrate.

[Prior Art Literature] [Patent Literature]

[Patent document 1] Japanese Patent Publication No. 2009-16497

Since sulfuric acid and hydrogen peroxide are both expensive chemicals, if the amount used can be reduced, the substrate processing cost can be reduced. In addition, since sulfuric acid is a chemical with a high environmental load, it is also required to reduce the amount used from the perspective of reducing environmental load. Research has also been conducted on recycling used SPM to regenerate sulfuric acid and reuse the regenerated sulfuric acid. However, SPM generated by mixing with hydrogen peroxide contains a large amount of water. Therefore, in order to evaporate the water from SPM and obtain sulfuric acid of the target concentration, it is necessary to overcome technical and cost problems.

Therefore, one embodiment of the present invention provides a substrate processing method and a substrate processing device that can efficiently remove the anti-corrosion film on the substrate while reducing the amount of chemical solution used.

One embodiment of the present invention provides a substrate processing method and a substrate processing device having the following exemplary features.

1. A substrate processing method, which is a method for processing a substrate having an anti-corrosion film formed on the main surface, comprising: a nozzle configuration step, which is to configure a plurality of fluid nozzles toward the main surface of the substrate; a supply step, which is to supply water vapor, ozone gas and sulfuric acid to the plurality of fluid nozzles; and a mixed fluid supply step, which is to supply a mixed fluid of water vapor, ozone gas and sulfuric acid from the plurality of fluid nozzles to the main surface of the substrate, and remove the anti-corrosion film from the main surface of the substrate.

According to this method, a mixed fluid of water vapor, ozone gas, and sulfuric acid (typically, sulfuric acid heated to a temperature higher than room temperature) is supplied to the main surface of the substrate, and the anti-corrosion film is removed from the main surface of the substrate by the mixed fluid. The sulfuric acid and water vapor come into contact, generating dilution heat, and the ozone decomposes at the interface of the sulfuric acid heated by the dilution heat, thereby generating persulfuric acid (peroxymonosulfuric acid). The anti-corrosion agent is decomposed by the action of the persulfuric acid (especially active oxygen), thereby being able to efficiently remove (peel off) the anti-corrosion film from the main surface of the substrate.

Since the process does not require (does not use) expensive hydrogen peroxide, a low-cost process with high stripping performance can be achieved. In addition, since the sulfuric acid contained in the mixed fluid flows down from the substrate in the form of liquid, it can be recovered and reused. Since the amount of water in the recovered sulfuric acid is small, the technical and cost barriers for regenerating sulfuric acid of the target concentration from the recovered sulfuric acid are not high. In this way, since the process facilitates the reuse of sulfuric acid, the amount of sulfuric acid used can be reduced. In this way, substrate processing that can efficiently remove the anti-etching film on the substrate while reducing the amount of chemical solution used can be achieved.

2. The substrate processing method as described in item 1, wherein the supply process includes a wet ozone gas supply process, and the wet ozone gas supply process is to supply wet ozone gas mixed with water vapor and ozone gas to the above-mentioned multiple fluid nozzles.

By bringing the humidified ozone gas into contact with sulfuric acid in multiple fluid nozzles, the water (water vapor) in the humidified ozone gas generates dilution heat, which allows the ozone to come into contact with the interface of the sulfuric acid heated by the dilution heat. In this way, persulfuric acid can be efficiently generated, and the newly generated persulfuric acid can be supplied to the main surface of the substrate to react with the anti-etching film. In this way, an efficient anti-etching agent removal process can be achieved.

3. The substrate processing method as described in item 2, wherein the above-mentioned wet ozone gas supply process includes a wet ozone gas generation process, and the wet ozone gas generation process is to generate wet ozone gas by bubbling ozone gas in water.

Wet ozone gas can be generated in a simple manner by bubbling ozone gas in water (typically, in deionized water).

In addition, moist ozone gas can be generated by mixing water vapor and ozone gas. However, since ozone gas decomposes at about 130. ℃, it is better to mix with water vapor at a temperature that can avoid decomposition. When moist ozone gas is generated by bubbling in water, since the boiling point of water is lower than the decomposition temperature of ozone gas, temperature management is not required to avoid decomposition of ozone gas.

The water in which the ozone gas is to be bubbled may also be heated. The bubbling in the heated water can promote the generation of water vapor, thereby generating moist ozone gas containing a moderate amount of water vapor and pressurizing it toward multiple fluid nozzles.

4. The substrate processing method as described in item 2, wherein the above-mentioned wet ozone gas supply process includes the following process: bubbling the ozone gas supplied by the ozone gas supply source in the water in the closed space to generate wet ozone gas in the closed space, and pressurizing the above-mentioned wet ozone gas from the closed space to the above-mentioned multiple fluid nozzles.

By supplying ozone gas to water contained in a closed space and bubbling it, wet ozone gas can be generated and pumped, thereby mixing fluids in multiple fluid nozzles with a simple structure.

5. The substrate processing method as described in any one of items 1 to 4, wherein the mixed fluid supplying step is to supply the mixed fluid containing persulfuric acid generated by mixing the ozone gas and the sulfuric acid to the main surface of the substrate.

By supplying a mixed fluid containing persulfuric acid to the main surface of the substrate, the anti-etching agent on the substrate can be decomposed and removed efficiently.

6. The substrate processing method as described in item 5, wherein the mixed fluid supply step is to supply the mixed fluid containing the persulfuric acid having a higher temperature than the sulfuric acid to the main surface of the substrate by using the dilution heat generated by the contact between the water vapor and the sulfuric acid.

Since dilution heat is generated by mixing water vapor and sulfuric acid, the temperature of the persulfuric acid supplied to the main surface of the substrate is higher than that of sulfuric acid. This can promote the decomposition of the anti-etching agent on the substrate, so that the anti-etching film can be removed efficiently.

7. A substrate processing method as described in any one of items 1 to 6, wherein the water vapor supplied to the above-mentioned multiple fluid nozzles is below 100°C.

By keeping the temperature of water vapor below 100°C, which is lower than the decomposition temperature of ozone, the decomposition of ozone can be suppressed before it comes into contact with sulfuric acid. In this way, persulfuric acid can be efficiently generated when ozone gas comes into contact with sulfuric acid, thus achieving high anti-corrosive agent removal performance.

8. A substrate processing method as described in any one of items 1 to 7, wherein the main surface of the substrate before supplying the mixed fluid in the mixed fluid supplying step presents a dry surface without a liquid film.

By supplying the mixed fluid to the main surface in a dry state without a liquid film, the persulfuric acid in the mixed fluid acts on the anti-corrosion film without being diluted. Therefore, the decomposition reaction of the anti-corrosion agent caused by the persulfuric acid occurs efficiently, so the anti-corrosion agent can be removed efficiently.

9. The substrate processing method as described in any one of items 1 to 8, further comprising a substrate rotating step, wherein the substrate is rotated around a rotation axis passing through the main surface, and the mixed fluid supply step comprises a sweeping step, wherein the sweeping step is performed in parallel with the substrate rotating step, wherein the mixed fluid is sprayed from the plurality of fluid nozzles while the landing point of the mixed fluid on the main surface is moved from the outer periphery of the substrate to the rotation axis.

As the substrate rotates, the liquid on the main surface of the substrate flows toward the periphery due to centrifugal force. Therefore, by sweeping the main surface of the substrate with a mixed fluid ejected from multiple fluid nozzles from the periphery of the substrate, the mixed fluid is supplied to the surface substantially free of liquid film. In this way, the persulfuric acid in the mixed fluid is not diluted and acts on the anti-etching film on the main surface of the substrate, so that highly efficient anti-etching agent removal can be achieved.

10. A substrate processing method as described in any one of items 1 to 9, wherein the anti-corrosion film on the main surface of the substrate is removed without bringing hydrogen peroxide into contact with the sulfuric acid.

Since hydrogen peroxide and sulfuric acid do not come into contact, a large amount of water can be prevented from mixing in sulfuric acid. This can reduce the amount of water required to remove sulfuric acid, making it easier to regenerate sulfuric acid and reuse it, which in turn reduces the amount of sulfuric acid used.

11. A substrate processing device, comprising: a substrate holding unit that holds a substrate; a plurality of fluid nozzles that are arranged toward the main surface of the substrate held by the substrate holding unit; a water vapor/ozone supply unit that supplies water vapor and ozone gas to the plurality of fluid nozzles; and a sulfuric acid supply unit that supplies sulfuric acid (typically, sulfuric acid heated to a temperature higher than room temperature) to the plurality of fluid nozzles; and the substrate processing device is configured to supply a mixed fluid of water vapor, ozone gas and sulfuric acid from the plurality of fluid nozzles to the main surface of the substrate held by the substrate holding unit.

12. The substrate processing device as described in item 11, wherein the water vapor/ozone supply unit supplies a mixed gas of water vapor and ozone gas, i.e., wet ozone gas.

13. The substrate processing device as described in item 12, wherein the water vapor/ozone supply unit includes a humidified ozone gas generating unit, and the humidified ozone gas generating unit generates the humidified ozone gas by bubbling ozone gas in water.

14. The substrate processing device as described in item 13, wherein the above-mentioned wet ozone gas generating unit includes a sealed container forming a closed space, and an ozone gas supply unit that supplies ozone gas to water stored in the above-mentioned sealed container, and pressurizes the above-mentioned wet ozone gas to the above-mentioned multiple fluid nozzles.

15. One or more of the features described for the above substrate processing method may be combined with the features described in items 11 to 14.

The above or other purposes, features and effects of the present invention will be clarified by referring to the attached drawings and the description of the implementation methods described below.

1: Substrate processing equipment

2: Processing unit

3: Controller

3A: Input device

3B: Display device

3C: Alarm device

3a: Computer body

3b: Processor

3c: Memory

3d: Peripheral devices

3e: Auxiliary memory device

3f: Reading device

3g: communication device

4: Fluid box

5: Storage box

6: Framework

7: Chamber

7a: Upper wall

7c: Inner space

8: Rotating chuck

9: 1st moving nozzle

10: Second moving nozzle

11: 3rd moving nozzle

13: Water vapor/ozone supply unit

13A: Ozone gas supply unit

13B: Water vapor supply unit

14: Substrate heating component

14a: Heating noodles

15: Handle the cup

16: Sulfuric acid supply unit

20: Holding pin

21: Rotating base

21a: Through hole

22: Rotation axis

23: Rotary drive mechanism

25: No. 1 nozzle drive mechanism

25a: Arm 1

25b: 1st arm drive mechanism

26: Second nozzle drive mechanism

26a: Arm 2

26b: Second arm drive mechanism

27: No. 3 nozzle drive mechanism

27a: Arm 3

27b: Third arm drive mechanism

28: Baffle

29: Accept the cup

30: External wall components

31: Air supply unit

32: Discharge piping

33: Ozone removal device

35: Drain pipe

36: Abandoned piping

37: Valve

38: Valve

40: Sulfuric acid piping

41: Common piping

42: Liquid piping

43: Flushing liquid piping

44: Organic solvent piping

45: Wet ozone gas piping

50A: Sulfuric acid valve

50B: Sulfuric acid flow regulating valve

50C:Filter

50D: Pump

50E: Heater unit

51: Common valve

52A: Liquid valve

52B: Liquid flow regulating valve

53A: Flushing fluid valve

53B: Flushing fluid flow regulating valve

54A: Organic solvent valve

54B: Organic solvent flow regulating valve

55: Sulfuric acid tank

56: Wet ozone gas generation unit

57: Sealed container

58: Ozone gas supply unit

59: Heater unit

60: Plate body

61: Heater

62: Temperature sensor

63: Power supply unit

64: Power supply line

65: Heater lifting shaft

66: Heater drive mechanism

70: Ozone gas piping

70A: Ozone gas valve

70B: Ozone gas flow regulating valve

70C:Filter

71: New liquid piping

71A: New liquid valve

80: Sulfuric acid recovery/regeneration unit

81: Regeneration tank

82: Heater unit

83: Regeneration sulfuric acid piping

83A: Regeneration sulfuric acid valve

83B: Pump

83C:Filter

90: Nozzle housing

91: 1st channel

91a: No. 1 spray outlet

92: Second passage

92a: No. 2 nozzle

100:Mixed fluid

100a: Landing point

A1: Rotation axis

C: Vehicles

IR: The first transport robot

CR: Second transport robot

LP: Loading port

TR: Transport path

TW: Treatment tower

W: Substrate

S1: Steps

S2: Step

S3: Step

S4: Step

S5: Step

S6: Step

S7: Step

S8: Step

S9: Step

S10: Step

S11: Step

S21: Step

S22: Step

S41: Step

S42: Step

S43: Step

S44: Step

S51: Step

S52: Step

S53: Step

S54: Steps

FIG1 is a schematic top view of a configuration example of a substrate processing device for illustrating one embodiment of the present invention.

FIG2 is a schematic diagram for explaining the structure of the processing unit of the above-mentioned substrate processing device.

Figure 3 shows an example of the configuration of a supply system for supplying a mixed fluid of water vapor, ozone gas, and sulfuric acid.

FIG4 is a block diagram for illustrating the electrical structure of the above-mentioned substrate processing device.

Figure 5 is a flow chart for illustrating an example of substrate processing.

FIG6A is a schematic diagram used to illustrate the substrate and its surroundings during substrate processing, showing the nozzle configuration process.

FIG6B is a schematic diagram for explaining the substrate and its surroundings during substrate processing, showing the mixed fluid supply process.

FIG. 6C is a schematic diagram for explaining the state of a substrate and its surroundings during substrate processing, showing the rinsing process.

FIG7 shows an example of the sweeping process (step S52 in FIG5 ).

FIG8 is a diagram for explaining the structure of the mixed fluid supply system in other embodiments of the present invention.

FIG. 1 is a schematic top view of a configuration example of a substrate processing device 1 for illustrating an embodiment of the present invention. The substrate processing device 1 is a single-chip device for processing substrates W one by one. In this embodiment, the substrate W has a circular plate shape. The substrate W is a substrate W such as a silicon wafer, and has a pair of main surfaces.

The substrate processing device 1 includes: a plurality of processing units 2, which process substrates W; a loading port LP (container holding unit) for holding a carrier C (container) for holding a plurality of substrates W processed by the processing unit 2; a transfer robot (a first transfer robot IR and a second transfer robot CR) for transferring substrates W between the loading port LP and the processing unit 2; and a controller 3, which controls the various components of the substrate processing device 1.

The first transport robot IR transports the substrate W between the carrier C and the second transport robot CR. The second transport robot CR transports the substrate W between the first transport robot IR and the processing unit 2. Each transport robot is, for example, a multi-joint arm robot.

A plurality of processing units 2 are arranged on both sides of the transport path TR along which the second transport robot CR transports the substrate W, and are stacked in the vertical direction. The plurality of processing units 2 have, for example, the same structure. The plurality of processing units 2 form four processing towers TW respectively arranged at four horizontally separated positions. Each processing tower TW includes a plurality of processing units 2 stacked in the vertical direction. Two of the four processing towers TW are arranged on both sides of the transport path TR extending from the loading port LP toward the second transport robot CR.

The substrate processing device 1 includes: a plurality of fluid boxes 4, which contain valves or piping, etc.; and a storage box 5, which contains sulfuric acid, chemical solution, rinse solution, organic solvent, or a tank for storing these raw materials. The processing unit 2 and the fluid box 4 are arranged on the inner side of a frame 6 which is roughly quadrilateral in top view.

The processing unit 2 has a chamber 7 for accommodating a substrate W during substrate processing. The chamber 7 includes: an entrance (not shown) for carrying the substrate W into the chamber 7 or carrying the substrate W out of the chamber 7 by the second transfer robot CR; and a gate unit (not shown) for opening and closing the entrance. As the processing liquid supplied to the substrate W in the chamber 7, sulfuric acid, chemical solution, rinse solution, organic solvent, etc. can be cited, and details are described later.

FIG. 2 is a schematic diagram for explaining the structure of the processing unit 2. The processing unit 2 includes: a rotary chuck 8, which holds the substrate W in a specific processing posture while rotating the substrate W around the rotation axis A1; and a plurality of nozzles (a first moving nozzle 9, a second moving nozzle 10, and a third moving nozzle 11), which spray the processing liquid onto the substrate W.

The processing unit 2 further includes: a substrate heating component 14, which heats the substrate W held by the rotary chuck 8; and a processing cup 15, which receives the processing liquid scattered from the substrate W held by the rotary chuck 8.

The rotary chuck 8, a plurality of movable nozzles, a substrate heating component 14, and a processing cup 15 are arranged in the chamber 7.

The rotation axis A1 passes through the center of the substrate W and is orthogonal to each main surface of the substrate W maintained in a processing posture. The processing posture is, for example, the posture of the substrate W shown in FIG. 2, which is a horizontal posture in which the main surface of the substrate W becomes a horizontal plane, but is not limited to a horizontal posture. That is, the processing posture may also be different from FIG. 2, and the main surface of the substrate W may be tilted relative to the horizontal plane. When the processing posture is a horizontal posture, the rotation axis A1 extends vertically.

The rotary chuck 8 is an example of a substrate holding member (substrate holding unit, substrate holder) that holds the substrate W in a processing posture, and is also an example of a rotation holding member that rotates the substrate W around the rotation axis A1 while holding the substrate W in a processing posture.

The rotating chuck 8 includes: a rotating base 21 having a disk shape along the horizontal direction; a plurality of holding pins 20, which hold the substrate W above the rotating base 21 and hold the peripheral portion of the substrate W above the rotating base 21; a rotating shaft 22, which is connected to the rotating base 21 and extends in the vertical direction; and a rotating drive mechanism 23, which rotates the rotating shaft 22 around its central axis (rotation axis A1). The rotating base 21 is an example of a disk-shaped base.

The plurality of holding pins 20 are arranged on the upper surface of the rotating base 21 at intervals in the circumferential direction of the rotating base 21. The rotating drive mechanism 23 includes an actuator such as an electric motor. The rotating drive mechanism 23 rotates the rotating base 21 and the plurality of holding pins 20 around the rotating axis A1 by rotating the rotating shaft 22. Thereby, the substrate W rotates around the rotating axis A1 together with the rotating base 21 and the plurality of holding pins 20.

The plurality of holding pins 20 can move between a closed position where the substrate W is held in contact with the periphery of the substrate W and an open position where the substrate W is released from holding. The plurality of holding pins 20 are moved by an opening and closing mechanism (not shown).

When the plurality of holding pins 20 are in the closed position, they hold the periphery of the substrate W and keep the substrate W horizontal. When the plurality of holding pins 20 are in the open position, they release the holding of the substrate W and support the periphery of the substrate W from below. The opening and closing mechanism includes, for example, a connecting rod mechanism and an actuator that applies a driving force to the connecting rod mechanism.

The plurality of movable nozzles include: a first movable nozzle 9, which sprays a mixed fluid of water vapor, ozone gas and sulfuric acid toward the upper surface (upper main surface) of the substrate W held by the rotating chuck 8; a second movable nozzle 10, which selectively sprays a continuous flow of a liquid and a continuous flow of a rinse solution toward the upper surface of the substrate W held by the rotating chuck 8; and a third movable nozzle 11, which sprays an organic solvent toward the upper surface of the substrate W held by the rotating chuck 8.

The first moving nozzle 9 is an example of a plurality of fluid nozzles that supply a mixed fluid of water vapor, ozone gas, and sulfuric acid toward the main surface (upper surface) of the substrate W held by the rotating chuck 8. The second moving nozzle 10 is an example of a liquid nozzle that sprays a liquid toward the main surface (upper surface) of the substrate W held by the rotating chuck 8, and is an example of a rinse liquid nozzle that sprays a rinse liquid toward the main surface (upper surface) of the substrate W held by the rotating chuck 8. The third moving nozzle 11 is an example of an organic solvent nozzle that sprays an organic solvent toward the main surface (upper surface) of the substrate W held by the rotating chuck 8.

The plurality of movable nozzles are moved in the horizontal direction respectively by the plurality of nozzle driving mechanisms (the first nozzle driving mechanism 25, the second nozzle driving mechanism 26 and the third nozzle driving mechanism 27).

Each nozzle driving mechanism can move the corresponding movable nozzle between the central position and the retreat position. The central position is the position where the movable nozzle is opposite to the central area of the upper surface of the substrate W. The central area of the upper surface of the substrate W refers to the area on the upper surface of the substrate W including the rotation center (central part) and the surrounding part of the rotation center. The retreat position is the position where the movable nozzle is not opposite to the upper surface of the substrate W, and is the position outside the processing cup 15.

Each nozzle driving mechanism includes: an arm (the first arm 25a, the second arm 26a, and the third arm 27a), which supports the corresponding movable nozzle; and an arm driving mechanism (the first arm driving mechanism 25b, the second arm driving mechanism 26b, and the third arm driving mechanism 27b), which moves the corresponding arm in the horizontal direction. Each arm driving mechanism includes an actuator such as an electric motor and a cylinder.

The movable nozzle may be a rotary nozzle that rotates around a specific rotation axis, or a linear motion nozzle that moves linearly along the direction in which the corresponding arm extends. The movable nozzle may be configured to be movable in a vertical direction.

The processing unit 2 further includes: a sulfuric acid supply unit 16, which supplies sulfuric acid to the first movable nozzle 9; and a water vapor/ozone supply unit 13, which supplies water vapor and ozone gas to the first movable nozzle 9. The sulfuric acid supply unit 16 includes a sulfuric acid piping 40, a sulfuric acid valve 50A, and a sulfuric acid flow regulating valve 50B.

The sulfuric acid pipe 40 is connected to the first movable nozzle 9 to guide the sulfuric acid to the first movable nozzle 9. The sulfuric acid valve 50A and the sulfuric acid flow regulating valve 50B are installed in the sulfuric acid pipe 40.

The sulfuric acid valve 50A is installed in the sulfuric acid pipe 40, which means that the sulfuric acid valve 50A is installed in the sulfuric acid pipe 40. The same is true for the other valves described below.

The sulfuric acid valve 50A opens and closes the flow path in the sulfuric acid piping 40. The sulfuric acid flow regulating valve 50B regulates the flow rate of sulfuric acid flowing through the flow path in the sulfuric acid piping 40. When the sulfuric acid valve 50A is opened, sulfuric acid is supplied to the first movable nozzle 9 at the flow rate regulated by the sulfuric acid flow regulating valve 50B.

The sulfuric acid valve 50A includes: a valve body, in which a valve seat is disposed; a valve body, which opens and closes the valve seat; and an actuator, which moves the valve body between an open position and a closed position, but is not shown. Other valves also have the same structure.

In the present embodiment, the water vapor/ozone supply unit 13 is a humidified ozone gas supply unit that supplies a mixed gas of water vapor and ozone gas, i.e., humidified ozone gas, to the first movable nozzle 9. The water vapor/ozone supply unit 13 has a humidified ozone gas pipe 45 coupled to the first movable nozzle 9. In the present embodiment, the first movable nozzle 9 is composed of a two-fluid nozzle. The sulfuric acid supplied by the sulfuric acid supply unit 16 and the humidified ozone gas supplied by the water vapor/ozone supply unit 13 are mixed in the two-fluid nozzle constituting the first movable nozzle 9, thereby generating a mixed fluid. The mixed fluid is ejected toward the upper surface of the substrate W held by the rotary chuck 8. The structure of the water vapor/ozone supply unit 13 will be described later.

The chemical liquid sprayed from the second movable nozzle 10 may be, for example, APM liquid (ammonia-hydrogen peroxide mixture, more specifically, SC1). In addition, chemical liquids containing hydrofluoric acid (HF), dilute hydrofluoric acid (DHF), buffered hydrofluoric acid (BHF), hydrochloric acid (HCl), HPM liquid (hydrochloric acid-hydrogen peroxide mixture), ammonia water, TMAH liquid (Tetramethylammonium hydroxide solution), or hydrogen peroxide (H ₂ O ₂ ) may also be sprayed from the second movable nozzle 10.

The rinse liquid sprayed from the second movable nozzle 10 is, for example, deionized water (DIW) or other water. However, the rinse liquid is not limited to deionized water, and can be deionized water, carbonated water, electrolytic water, hydrochloric acid water with a dilution concentration (for example, 1 ppm or more and 100 ppm or less), ammonia water with a dilution concentration (for example, 1 ppm or more and 100 ppm or less), or reducing water (hydrogen water), or a mixed liquid containing at least two of them.

The second movable nozzle 10 is connected to a common pipe 41 that guides fluid to the second movable nozzle 10. A liquid pipe 42 that supplies liquid to the common pipe 41 and a flushing liquid pipe 43 that supplies flushing liquid to the common pipe 41 are connected to the common pipe 41. The common pipe 41 can be connected to the liquid pipe 42 and the flushing liquid pipe 43 via a mixing valve (not shown).

A common valve 51 for opening and closing the common piping 41 is provided on the common piping 41. A liquid valve 52A for opening and closing the liquid piping 42 and a liquid flow regulating valve 52B for adjusting the flow of the liquid in the liquid piping 42 are provided on the liquid piping 42. A flushing liquid valve 53A for opening and closing the flushing liquid piping 43 and a flushing liquid flow regulating valve 53B for adjusting the flow of the flushing liquid in the flushing liquid piping 43 are provided on the flushing liquid piping 43.

When the liquid medicine valve 52A and the common valve 51 are opened, a continuous flow of liquid medicine is ejected from the second movable nozzle 10. When the flushing liquid valve 53A and the common valve 51 are opened, a continuous flow of flushing liquid is ejected from the second movable nozzle 10.

The organic solvent sprayed from the third movable nozzle 11 contains: alcohols such as ethanol (EtOH) and isopropyl alcohol (IPA), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other ethylene glycol monoalkyl ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and other ethylene glycol monoalkyl ether acetates, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE) and other propylene glycol monoalkyl ethers, lactic acid esters such as methyl lactate and ethyl lactate (EL), aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone, cyclohexanone and other at least one kind.

The third movable nozzle 11 is connected to an organic solvent pipe 44 that guides the organic solvent to the third movable nozzle 11. The organic solvent pipe 44 is provided with an organic solvent valve 54A that opens and closes the organic solvent pipe 44, and an organic solvent flow regulating valve 54B that regulates the flow of the organic solvent in the organic solvent pipe 44.

The processing cup 15 includes: a plurality of (3 in FIG. 2 ) baffles 28 that block the processing liquid that is scattered outward from the substrate W held by the rotating chuck 8; a plurality of (3 in FIG. 2 ) cups 29 that receive the processing liquid guided to the bottom by the plurality of baffles 28; and a cylindrical outer wall member 30 that surrounds the plurality of baffles 28 and the plurality of cups 29.

Each baffle 28 has a cylindrical shape surrounding the rotating chuck 8 in a top view. The upper end of each baffle 28 is inclined inwardly toward the center side of the baffle 28. Each support cup 29 has the shape of an annular groove open upward. A plurality of baffles 28 and a plurality of support cups 29 are arranged on the same axis.

The plurality of baffles 28 are individually raised and lowered by a baffle lifting drive mechanism (not shown). The baffle lifting drive mechanism, for example, includes a plurality of actuators that individually lift and lower the plurality of baffles 28. The plurality of actuators include at least one of an electric motor and a pneumatic cylinder.

The processing unit 2 includes: an air supply unit 31 such as a FFU (Fan Filter Unit) that delivers inert gas from outside the chamber 7 to inside the chamber 7; and an exhaust pipe 32 that exhausts the chamber 7. The air supply unit 31 is arranged on the upper wall 7a of the chamber 7. The exhaust pipe 32 is connected to the outer wall component 30. The inert gas delivered to the chamber 7 by the air supply unit 31 can be, for example, nitrogen, a rare gas, or a mixed gas thereof. The rare gas is, for example, argon.

The exhaust pipe 32 is connected to the exhaust duct (not shown). The gas in the exhaust duct is sucked by the suction device (not shown). The gas in the chamber 7 is discharged to the exhaust duct through the exhaust pipe 32. The suction device includes a suction pump for sucking the exhaust duct. The suction device is installed in the exhaust duct or connected to the exhaust duct. The exhaust duct and the suction device are installed in the clean room for installing the substrate processing device 1 or the equipment attached to the clean room. The exhaust duct and the suction device can also be part of the substrate processing device 1.

An ozone removal device 33 (ozone remover) is installed between the exhaust pipe 32 and the exhaust duct, or in the exhaust pipe 32. The ozone gas contained in the gas exhausted from the chamber 7 is decomposed when passing through the ozone removal device 33.

Through the action of the air supply unit 31 and the exhaust pipe 32, an airflow from the top to the bottom is formed in the inner space 7c of the chamber 7. The airflow passes through the inside of the processing cup 15 and flows into the exhaust pipe 32.

The processing liquid supplied to the substrate W is scattered from the periphery of the substrate W and received by any baffle 28. The processing liquid received by the baffle 28 is guided to the corresponding cup 29 and is recovered or discarded through the drainage pipe 35 corresponding to each cup 29.

The substrate heating component 14 has a circular plate-shaped heating plate shape for heating the substrate W from below. The substrate heating component 14 is arranged between the upper surface of the rotating base 21 and the lower surface of the substrate W. The substrate heating component 14 has a heating surface 14a facing the lower surface of the substrate W from below.

The substrate heating component 14 includes a plate body 60 and a heater 61. The plate body 60 is slightly smaller than the substrate W in a top view. The upper surface of the plate body 60 constitutes a heating surface 14a. The heater 61 can be a resistor built into the plate body 60. By energizing the heater 61, the heating surface 14a is heated.

The heater 61 is configured to heat the substrate W within a temperature range above room temperature (e.g., a temperature above 5°C and below 25°C) and, for example, below 400°C.

The processing unit 2 further includes a temperature sensor 62 for detecting the temperature of the substrate heating component 14. In the example shown in FIG. 2 , the temperature sensor 62 is built into the board body 60, but there is no particular limitation on the configuration of the temperature sensor 62. The temperature sensor 62 may also be mounted on the board body 60 from the outside, for example.

The heater 61 is connected to a power supply unit 63 via a power supply line 64. The temperature of the heater 61 is adjusted by adjusting the current supplied from the power supply unit 63 to the heater 61. For example, the current supplied from the power supply unit 63 to the heater 61 is adjusted based on the detected temperature of the temperature sensor 62.

A heater lifting shaft 65 is connected to the lower surface of the substrate heating component 14. The heater lifting shaft 65 is inserted into the through hole 21a formed in the central part of the rotating base 21 and the internal space of the rotating shaft 22.

The processing unit 2 further includes a heater drive mechanism 66 for driving the substrate heating member 14 to move in the up-down direction. The heater drive mechanism 66, for example, includes a heater actuator (not shown) for driving the heater lifting shaft 65 to move in the up-down direction. The heater actuator, for example, includes at least one of an electric motor and a cylinder. The heater drive mechanism 66 moves the substrate heating member 14 in the up-down direction via the heater lifting shaft 65. The substrate heating member 14 can move in the up-down direction between the lower surface of the substrate W and the upper surface of the rotating base 21.

When the substrate heating member 14 is raised, it can receive the substrate W from the plurality of holding pins 20 in the open position. The substrate heating member 14 can heat the substrate W because the heating surface 14a is arranged at a contact position in contact with the lower surface of the substrate W, or at a close position close to the lower surface of the substrate W without contact. The position where the substrate heating member 14 is sufficiently retreated from the lower surface of the substrate W to the extent that the heating of the substrate W by the substrate heating member 14 is relaxed is called the retreat position. In other words, the heating of the substrate W is sufficiently relaxed, which can be expressed as the heating of the substrate W is stopped.

When the substrate heating member 14 is arranged at the retreat position, the amount of heat transferred from the substrate heating member 14 to the substrate W is less than the amount of heat transferred from the substrate heating member 14 to the substrate W when the substrate heating member 14 is arranged at the approach position. The contact position and the approach position are also called heating positions. The retreat position is also called a heating relief position or a heating stop position.

FIG3 shows an example of the structure of a supply system for supplying a mixed fluid of water vapor, ozone gas and sulfuric acid. In this example, the mixed fluid supply system includes: a sulfuric acid supply unit 16, a water vapor/ozone supply unit 13, and a first movable nozzle 9 composed of a plurality of fluid nozzles (in this example, a two-fluid nozzle).

The sulfuric acid supply unit 16 includes: a sulfuric acid piping 40 that allows sulfuric acid to flow from a sulfuric acid tank 55 as a sulfuric acid supply source to the first movable nozzle 9; a sulfuric acid valve 50A that is installed in the sulfuric acid piping 40; and a sulfuric acid flow regulating valve 50B that is also installed in the sulfuric acid piping 40. The sulfuric acid flow regulating valve 50B preferably adjusts the flow rate of sulfuric acid in the sulfuric acid piping 40 to less than 1 liter/minute. Furthermore, in this example, the sulfuric acid supply unit 16 includes a filter 50C, a pump 50D, and a heater unit 50E that are arranged in the sulfuric acid piping 40. The pump 50D draws sulfuric acid from the sulfuric acid tank 55 and transports the sulfuric acid from the sulfuric acid piping 40 to the first movable nozzle 9. The filter 50C removes foreign matter in the sulfuric acid flowing in the sulfuric acid piping 40. The heater unit 50E heats the sulfuric acid supplied to the first moving nozzle 9 through the sulfuric acid pipe 40. For example, the heater unit 50E heats the sulfuric acid so that the temperature of the sulfuric acid when it reaches the first moving nozzle 9 is above 120°C and below 190°C.

The sulfuric acid supplied by the sulfuric acid supply unit 16 is strictly a sulfuric acid-containing liquid, and is typically a sulfuric acid aqueous solution of a specific concentration, containing sulfuric acid (H ₂ SO ₄ ) and water (H ₂ O). The sulfuric acid aqueous solution is, for example, dilute sulfuric acid or concentrated sulfuric acid. The sulfuric acid-containing liquid may be a sulfuric acid aqueous solution prepared by mixing sulfuric acid with water such as deionized water. The sulfuric acid-containing liquid may contain substances other than sulfuric acid and water, but in the present embodiment, at least hydrogen peroxide is not contained. In this specification, "sulfuric acid" refers to the sulfuric acid-containing liquid as described above.

The water vapor/ozone supply unit 13 includes: a humidified ozone gas generating unit 56, which generates humidified ozone gas by bubbling ozone gas in water; and a humidified ozone gas piping 45, which supplies the humidified ozone gas generated by the humidified ozone gas generating unit 56 to the first movable nozzle 9. The humidified ozone gas generating unit 56 includes: a sealed container 57, which forms a closed space; and an ozone gas supply unit 58, which supplies ozone gas to water (e.g., deionized water) stored in the sealed container 57. In this embodiment, the humidified ozone gas generating unit 56 further includes a heater unit 59 for heating the water stored in the sealed container 57. The heater unit 59 can be configured to heat the sealed container 57. The ozone gas supply unit 58 includes: an ozone gas piping 70, which allows ozone gas to flow from the ozone gas supply source to the sealed container 57; an ozone gas valve 70A (open/close valve) disposed on the ozone gas piping 70; and an ozone gas flow regulating valve 70B disposed on the ozone gas piping 70. A filter 70C for removing foreign matter can be further disposed on the ozone gas piping 70. The front end of the ozone gas piping 70 is disposed in the water stored in the sealed container 57.

When the ozone gas valve 70A is opened, the ozone gas flows through the ozone gas pipe 70 at a flow rate (e.g., 1 to 2 liters/minute) limited by the ozone gas flow rate adjustment valve 70B, and is released into the water stored in the sealed container 57. In this way, the ozone gas can be bubbled in the water. As a result, water vapor is mixed with the ozone gas to generate wet ozone gas (wet ozone gas generation process). The inlet of the wet ozone gas pipe 45 opens in the sealed container 57 and is arranged in a closed space above the water level of the water stored in the sealed container 57. Therefore, the moist ozone gas generated in the sealed container 57 is guided to the first movable nozzle 9 through the moist ozone gas piping 45. By continuing to supply ozone gas from the ozone gas supply unit 58 to the sealed container 57, the gas pressure in the sealed container 57 becomes higher, so that the moist ozone gas can be pressed from the sealed container 57 to the first movable nozzle 9 through the moist ozone gas piping 45.

By using the heater unit 59 to heat the water in the sealed container 57 to make the water temperature higher than room temperature (e.g. room temperature ~ 80°C), the evaporation of water can be promoted, so that the water vapor can be mixed with the ozone gas in a proper mixing ratio to obtain moist ozone gas. The temperature of the water stored in the sealed container 57 is preferably set below 100°C to prevent the ozone gas from decomposing.

The first movable nozzle 9 is constituted by, for example, an external mixing type two-fluid nozzle. More specifically, the first movable nozzle 9 has: a nozzle housing 90, and a first passage 91 and a second passage 92 formed in the nozzle housing 90. The first passage 91 is connected to the sulfuric acid piping 40, and the second passage 92 is connected to the wet ozone gas piping 45. The following openings are formed at the front end of the nozzle housing: a first nozzle 91a, which sprays the fluid (in this case, sulfuric acid) flowing in the first passage 91; and a second nozzle 92a, which sprays the fluid (in this case, wet ozone gas) flowing in the second passage 92. The fluids ejected from the first nozzle 91a and the second nozzle 92a collide and mix outside the nozzle housing 90 near the nozzles 91a and 92a to generate a mixed fluid 100. The mixed fluid 100 is typically a fluid obtained by mixing wet ozone gas and sulfuric acid droplets. The mixed fluid 100 is supplied from the first movable nozzle 9 to the upper surface of the substrate W.

Of course, an internal mixing type two-fluid nozzle that mixes fluids in the nozzle housing may also be used as the first movable nozzle 9.

For the sulfuric acid tank 55, the new liquid valve 71A provided in the new liquid piping 71 can be opened to supply unused sulfuric acid (new liquid) therein, and in addition, the regenerated sulfuric acid can also be supplied therein from the sulfuric acid recovery/regeneration unit 80. The sulfuric acid recovery/regeneration unit 80 recovers the used sulfuric acid from the drain piping 35 (recovery pipeline), and regenerates the sulfuric acid for reuse. The drain piping 35 is connected to the cup 29 corresponding to the baffle 28 in the processing cup 15 (refer to FIG. 2) that receives the liquid discharged from the substrate W when the mixed fluid is used for processing. For example, the sulfuric acid recovery/regeneration unit 80 can be configured to restore the recovered sulfuric acid to the target concentration by heating the recovered sulfuric acid to evaporate the water in the sulfuric acid.

Specifically, the sulfuric acid recovery/regeneration unit 80 includes: a regeneration tank 81, which stores sulfuric acid to be regenerated; a heater unit 82, which heats the sulfuric acid in the regeneration tank 81; and a regeneration sulfuric acid piping 83, which supplies the regenerated sulfuric acid from the regeneration tank 81 to the sulfuric acid tank 55. The regeneration sulfuric acid piping 83 is provided with a regeneration sulfuric acid valve 83A, a pump 83B and a filter 83C. When the regeneration sulfuric acid valve 83A is opened, the regeneration sulfuric acid pumped out from the regeneration tank 81 by the pump 83B and the regeneration sulfuric acid from which foreign matter is removed by the filter 83C is supplied to the sulfuric acid tank 55. In this way, by regenerating sulfuric acid and reusing it, the amount of sulfuric acid used can be reduced.

In this example, a waste pipe 36 is branched from the drain pipe 35 (recovery line). By opening and closing the valve 37 provided on the drain pipe 35 between the branch portion of the waste pipe 36 and the regeneration tank 81, and the valve 38 provided on the waste pipe 36, the liquid collected in the cup 29 can be selected to be recovered for regeneration or discarded. For example, the liquid can be discarded when there are more foreign objects in the liquid, and the liquid can be recovered to the regeneration tank 81 when there are fewer foreign objects in the liquid, depending on the processing conditions on the substrate W.

FIG4 is a block diagram for explaining the electrical structure of the substrate processing device 1. The controller 3 is a computer including a computer body 3a and a peripheral device 3d connected to the computer body 3a. The computer body 3a includes: a processor (CPU) 3b for executing various commands, and a memory 3c for storing information.

The peripheral device 3d includes: an auxiliary memory device 3e, which stores information such as programs; a reading device 3f, which reads information from a removable medium (not shown); and a communication device 3g, which communicates with other devices such as a host computer (not shown).

The controller 3 is connected to the input device 3A, the display device 3B, and the alarm device 3C. The input device 3A is operated by the user or the maintenance person in charge when inputting information to the substrate processing device 1. The information is displayed on the screen of the display device 3B. The input device 3A can be any one of a keyboard, a pointing device, and a touch panel, or a device other than these. A touch panel display that also serves as the input device 3A and the display device 3B can also be set in the substrate processing device 1. The alarm device 3C uses one or more of light, sound, text, and graphics to issue an alarm. When the input device 3A is a touch panel display, the input device 3A can also serve as the alarm device 3C.

The auxiliary memory device 3e is a non-volatile memory that maintains memory even when no power is supplied. The auxiliary memory device 3e is, for example, a magnetic memory device such as a hard disk.

The auxiliary memory device 3e stores a plurality of process recipes. The process recipe is information that specifies the processing content, processing conditions, and processing steps of the substrate W. The plurality of process recipes differ from each other in at least one of the processing content, processing conditions, and processing steps of the substrate W.

The controller 3 controls the components of the substrate processing device 1 to process the substrate W according to the process recipe specified by an external device such as a host computer.

The objects to be controlled by the controller 3 include: the first transport robot IR, the second transport robot CR, the rotation drive mechanism 23, the first nozzle drive mechanism 25, the second nozzle drive mechanism 26, the third nozzle drive mechanism 27, the heater drive mechanism 66, the power supply unit 63, the air supply unit 31, the temperature sensor 62, the pumps 50D, 83B, the heater unit 50E, 5 9, 82, sulfuric acid valve 50A, sulfuric acid Flow regulating valve 50B, common valve 51, liquid valve 52A, liquid flow regulating valve 52B, flushing liquid valve 53A, flushing liquid flow regulating valve 53B, organic solvent valve 54A, organic solvent flow regulating valve 54B, ozone gas valve 70A, ozone gas flow regulating valve 70B, regeneration sulfuric acid valve 83A, valves 37, 38, etc.

Furthermore, although representative components are illustrated in FIG. 4 , it does not mean that the components not illustrated are not controlled by the controller 3 . The controller 3 can appropriately control the components of the substrate processing device 1 .

The following processes are executed by the controller 3 controlling the substrate processing device 1. In other words, the controller 3 is programmed to execute the following processes.

FIG. 5 is a flowchart for explaining an example of substrate processing performed by the substrate processing device 1. FIG. 6A to FIG. 6C are schematic diagrams for explaining the conditions of the substrate W and its periphery during substrate processing. An anti-etching film is formed on at least one of the main surfaces of one pair of substrates W used in substrate processing. The anti-etching film is typically an organic material film, and may also be an anti-etching film used as a mask for patterning processing (dry etching or wet etching) or ion implantation processing, etc.

In the substrate processing performed by the substrate processing device 1, for example, a substrate carrying-in process (step S1), a substrate heating process (step S2), a nozzle configuration process (step S3), a supply process (step S4: a wet ozone gas supply process, a sulfuric acid supply process), a mixed fluid supply process (step S5), a first rinsing process (step S6), a chemical solution supply process (step S7), a second rinsing process (step S8), an organic solvent supply process (step S9), a spin drying process (step S10) and a substrate carrying-out process (step S11) are performed.

The unprocessed substrate W is carried from the carrier C to the processing unit 2 by the second transfer robot CR (see Figure 1) and handed over to the rotary chuck 8 (substrate carrying process: step S1). Thereby, the substrate W is held horizontally by the rotary chuck 8 (substrate holding process). At this time, the substrate W is held by the rotary chuck 8 in such a way that the main surface formed with the anti-etching film becomes the upper surface. The main surface of the substrate W before processing (the main surface formed with the anti-etching film) presents a dry surface without the presence of a liquid film. The substrate W is continuously held by the rotary chuck 8 until the rotation drying process (step S10) is completed.

With the substrate W held by the rotary chuck 8, the rotary drive mechanism 23 starts rotating the substrate W (substrate rotation process). In addition, during the process of substrate processing, an airflow from top to bottom is always formed in the internal space 7c of the chamber 7, and the airflow passes through the interior of the processing cup 15 and flows into the exhaust pipe 32.

After the second transfer robot CR retreats from the chamber 7, a substrate heating process (step S2) of heating the substrate W is performed. Specifically, the current is supplied to the heater 61 by the power supply unit 63, so that the temperature of the heater 61 begins to rise. Then, the heater drive mechanism 66 moves the substrate heating component 14 from the retreat position to the approach position. As shown in FIG. 6A, the temperature of the heater 61 begins to rise, and the substrate heating component 14 is arranged in the approach position, thereby starting to heat the substrate W (substrate heating start process: step S21).

On the other hand, the nozzle configuration process (step S3) is performed by executing the first nozzle driving mechanism 25 to move the first movable nozzle 9 to the processing position. The processing position is a position where the first movable nozzle 9 is opposite to the main surface of the substrate W (the main surface on which the anti-etching film is formed) so that the mixed fluid 100 can be supplied to the main surface of the substrate W.

When the temperature detected by the temperature sensor 62 reaches the processing temperature range, the ozone gas valve 70A and the sulfuric acid valve 50A are opened while the first movable nozzle 9 is at the processing position, thereby starting to supply the wet ozone gas and sulfuric acid to the first movable nozzle 9 (wet ozone gas supply start process: step S41; sulfuric acid supply start process: S42). As shown in FIG. 6B , the mixed fluid 100 of the wet ozone gas and sulfuric acid is sprayed from the first movable nozzle 9, and the mixed fluid 100 is started to be supplied to the upper surface of the substrate W (mixed fluid supply start process: step S51). On the other hand, the first nozzle driving mechanism 25 moves the first movable nozzle 9, so that the landing point of the mixed fluid on the upper surface of the substrate W moves along the radial direction of the substrate W (sweeping process: step S52). Since the substrate W is rotating around the rotation axis A1, the mixed fluid 100 ejected from the first movable nozzle 9 sweeps the entire area of the upper surface of the substrate W.

After a specific time has passed since the mixed fluid 100 was supplied, the ozone gas valve 70A and the sulfuric acid valve 50A are closed to stop the supply of the wet ozone gas and sulfuric acid to the first movable nozzle 9 (wet ozone gas supply stop process: step S43; sulfuric acid supply stop process: S44). Thus, the supply of the mixed fluid 100 to the upper surface of the substrate W is stopped (mixed fluid supply stop process: step S53).

After stopping the spraying of the mixed fluid 100, the first nozzle driving mechanism 25 causes the first movable nozzle 9 to retreat (step S54). On the other hand, the heater driving mechanism 66 causes the substrate heating component 14 to move from the approach position to the retreat position. By arranging the substrate heating component 14 at the retreat position (the position shown in FIG. 6C ), the heating of the substrate W is stopped (substrate heating stopping process: step S22). Thus, the substrate heating process (step S2) ends.

By using the mixed fluid 100 of moist ozone gas and sulfuric acid to sweep the upper surface of the substrate W, the mixed fluid 100 can be supplied to the entire area of the upper surface of the substrate W. By the action of the mixed fluid 100, the anti-etching agent on the main surface of the substrate W is decomposed, and the anti-etching film is removed (stripped) from the main surface of the substrate W. Then, the liquid component (mainly sulfuric acid) in the mixed fluid 100 flows along the upper surface of the substrate W to the outside of the rotation radius by the centrifugal force accompanying the rotation of the substrate W, thereby at least a portion of the anti-etching film stripped from the main surface of the substrate W is discharged outside the substrate W.

In the first movable nozzle 9, dilution heat is generated by bringing sulfuric acid into contact with water vapor in the humid ozone gas, and ozone in the humid ozone gas is decomposed at the interface of sulfuric acid heated by the dilution heat. In this way, persulfuric acid (monomonosulfuric acid with peroxide) is generated. By supplying the mixed fluid 100 containing the persulfuric acid (especially active oxygen) to the upper surface of the substrate W, the anti-etching agent is decomposed, thereby being able to efficiently remove (peel off) the anti-etching film from the main surface of the substrate W. Moreover, since sulfuric acid is in contact with water vapor just before being supplied to the substrate W, the ozone gas can be efficiently decomposed by dilution heat to generate persulfuric acid, and the newly generated persulfuric acid can be supplied to the main surface of the substrate W. Furthermore, the persulfuric acid is heated by the heat of dilution, and the persulfuric acid is supplied to the main surface of the substrate W at a higher temperature than the sulfuric acid before mixing. In this way, the anti-corrosion agent can be efficiently decomposed by the newly generated high-temperature persulfuric acid. Furthermore, in this embodiment, since the substrate heating process (step S2) is performed in parallel, the anti-corrosion film can be removed more efficiently.

After the substrate heating process (step S2) and the mixed fluid supply process (step S5), the first rinsing process (step S6) is performed, that is, the upper surface of the substrate W is cleaned by supplying a rinsing liquid to the upper surface of the substrate W.

Specifically, the second nozzle driving mechanism 26 moves the second movable nozzle 10 to the processing position. The processing position is, for example, the central position. When the second movable nozzle 10 is at the processing position, the common valve 51 and the rinse liquid valve 53A are opened. As a result, as shown in FIG. 6C , the rinse liquid is sprayed from the second movable nozzle 10, and the rinse liquid is supplied to the upper surface of the substrate W (rinse liquid supply start process, rinse liquid supply process). The rinse liquid landed on the upper surface of the substrate W moves toward the periphery of the upper surface of the substrate W, and the rinse liquid spreads to the entire upper surface of the substrate W.

After a specific time has passed since the start of the supply of the rinse liquid, the common valve 51 and the rinse liquid valve 53A are closed. Thus, the supply of the rinse liquid to the upper surface of the substrate W is stopped (rinsing liquid supply stop process). Thus, the first rinse process is completed. Through the first rinse process, sulfuric acid is discharged from the upper surface of the substrate W. The anti-etching film peeled off from the upper surface of the substrate W is rinsed away together with the sulfuric acid and discharged from the upper surface of the substrate W to the outside of the substrate W.

After stopping the supply of the rinse liquid to the upper surface of the substrate W, a liquid supply process of supplying the liquid to the upper surface of the substrate W is performed (step S7). Specifically, when the second movable nozzle 10 is located at the processing position, the common valve 51 and the liquid valve 52A are opened. Thus, the spraying of the rinse liquid is stopped, and then a continuous flow of the liquid is sprayed (supplied) from the second movable nozzle 10 to the upper surface of the substrate W (liquid spraying process, liquid supply process). Thus, the upper surface of the substrate W is processed by the liquid. Thus, the residue remaining on the upper surface of the substrate W is removed.

After the chemical liquid supply process (step S7), a second rinsing process (step S8) is performed to supply a rinse liquid to the upper surface of the substrate W to clean the upper surface of the substrate W. Specifically, while the second movable nozzle 10 is maintained opposite to the upper surface of the substrate W and the common valve 51 is opened, the chemical liquid valve 52A is closed and the rinse liquid valve 53A is opened. Thus, the spraying of chemical liquid from the second movable nozzle 10 is stopped, and then a continuous flow of rinse liquid is sprayed (supplied) from the second movable nozzle 10 to the upper surface of the substrate W (rinsing liquid spraying process, rinse liquid supply process). Thus, the chemical liquid on the upper surface of the substrate W is discharged to the outside of the substrate W together with the rinse liquid, and the upper surface of the substrate W is cleaned.

After the second rinsing process (step S8), an organic solvent supply process (step S9) is performed to supply an organic solvent to the upper surface of the substrate W. Specifically, the spraying of the rinsing liquid from the second movable nozzle 10 is stopped, and the second movable nozzle 10 is retracted. Then, the third nozzle driving mechanism 27 makes the third movable nozzle 11 face the upper surface of the substrate W, and opens the organic solvent valve 54A. Thereby, a continuous flow of organic solvent is sprayed (supplied) from the third movable nozzle 11 to the upper surface of the substrate W (organic solvent spraying process, organic solvent supply process). Thereby, the rinsing liquid on the upper surface of the substrate W is replaced by the organic solvent.

The organic solvent used in the substrate processing is preferably more volatile than the rinse liquid. In this way, by replacing the rinse liquid with the organic solvent, the substrate W can be dried well in the subsequent spin drying process (step S10). The organic solvent used in the substrate processing is preferably lower in surface tension than the rinse liquid. In this way, when a concave-convex pattern is formed on the upper surface of the substrate W, the surface tension acting on the concave-convex pattern when the upper surface of the substrate W is dried can be reduced, and the collapse of the concave-convex pattern can be suppressed.

Next, a rotation drying process is performed to dry the upper surface of the substrate W by rotating the substrate W at high speed (step S10). Specifically, the organic solvent valve 54A is closed to stop supplying the organic solvent to the upper surface of the substrate W. Then, the rotation drive mechanism 23 accelerates the rotation of the substrate W to rotate the substrate W at high speed (e.g., 1500 rpm). Thus, a larger centrifugal force acts on the rinse liquid attached to the substrate W, and the organic solvent is thrown off to the periphery of the substrate W.

After the spin drying process (step S10), the rotation drive mechanism 23 stops the rotation of the substrate W. Afterwards, the second transport robot CR enters the processing unit 2, receives the processed substrate W from the spin chuck 8, and carries it out of the processing unit 2 (substrate carrying process: step S11). The substrate W is handed over from the second transport robot CR to the first transport robot IR, and is stored in the carrier C by the first transport robot IR.

FIG. 7 shows an example of the sweeping process (step S52 of FIG. 5 ). In this example, the initial position of the first movable nozzle 9 when the mixed fluid 100 is ejected is a position where the landing point 100a of the mixed fluid 100 is arranged on the outer periphery of the substrate W. When the mixed fluid 100 is supplied, the first movable nozzle 9 starts to move, whereby the landing point 100a of the mixed fluid 100 moves from the outer periphery of the substrate W to the rotation center (rotation axis A1). Thereafter, the first movable nozzle 9 can be moved as needed so that the landing point of the mixed fluid 100 repeatedly moves back and forth between the outer periphery of the substrate W and the rotation center (rotation axis A1). In FIG. 7 , a range of approximately the radius of the substrate W is shown as the scanning range, but a range of approximately the diameter of the substrate W may also be used as the scanning range.

The initial landing point of the mixed fluid 100 is set at the outer periphery of the substrate W, and the landing point 100a moves toward the rotation center (rotation axis A1), whereby the mixed fluid 100 lands on the liquid-free (substantially dry) surface of the substrate W. Therefore, the persulfuric acid in the mixed fluid 100 is not diluted and acts on the anti-corrosion film, so that the anti-corrosion agent decomposition reaction can occur efficiently. Thus, the anti-corrosion agent can be removed efficiently.

As described above, according to the present embodiment, a mixed fluid 100 of water vapor, ozone gas, and sulfuric acid is supplied to the main surface of the substrate W, and the anti-corrosion film is removed from the main surface of the substrate W by the mixed fluid 100. The sulfuric acid and water vapor are in contact, generating dilution heat, and the ozone is decomposed at the interface of the sulfuric acid heated by the dilution heat, thereby generating persulfuric acid (peroxymonosulfuric acid). The anti-corrosion agent is decomposed by the action of the persulfuric acid (especially active oxygen), so that the anti-corrosion film can be efficiently removed (stripped) from the main surface of the substrate W.

In the anti-etching agent removal process using the mixed fluid 100, high-cost hydrogen peroxide is not required (not used), so a low-cost anti-etching agent removal process with high stripping performance can be realized. In addition, since the sulfuric acid in the mixed fluid 100 flows down from the substrate W in the form of liquid, it can be recovered and reused. In addition, since the amount of water in the sulfuric acid flowing down from the substrate W is relatively small, the technical and cost barriers for regenerating the recovered sulfuric acid to the target concentration are not high. In this way, since sulfuric acid is easily reused, the amount of sulfuric acid used can be reduced. In this way, the anti-etching film on the substrate W can be efficiently removed while reducing the amount of chemical solution used.

In this embodiment, by bubbling ozone gas in water, wet ozone gas mixed with water vapor and ozone gas is generated in advance. Therefore, wet ozone gas and sulfuric acid can be mixed in the first movable nozzle 9 composed of a two-fluid nozzle to generate a mixed fluid 100. By making the wet ozone gas and sulfuric acid contact in the first movable nozzle 9 (two-fluid nozzle), the water (water vapor) in the wet ozone gas generates dilution heat, so that ozone can contact the interface of sulfuric acid heated by the dilution heat. In this way, persulfuric acid can be efficiently generated, and the newly generated persulfuric acid can be supplied to the main surface of the substrate to react with the anti-etching film. In this way, an efficient anti-corrosion agent removal process can be achieved. Generating wet ozone gas by bubbling ozone gas in water is a relatively simple method, and it also has the advantage of being able to use a two-fluid nozzle to mix three fluids of water vapor, ozone gas and sulfuric acid.

By preheating sulfuric acid (e.g. 120℃~190℃) and heating the water in which the ozone gas is to be bubbled, when the wet ozone gas comes into contact with the sulfuric acid, the interface of the sulfuric acid will definitely exceed the decomposition temperature of ozone (about 130℃). In this way, persulfuric acid containing a large amount of active oxygen (oxygen free radicals) can be efficiently generated. When the wet ozone gas is generated by bubbling in water, since the boiling point of water is lower than the decomposition temperature of the ozone gas, strict temperature management is not required to avoid the decomposition of the ozone gas.

Furthermore, in this embodiment, by supplying ozone gas to the water in the sealed container 57 forming a closed space for bubbling, it is possible to generate and pressurize wet ozone gas. In this way, the fluid in the first moving nozzle 9 (plural fluid nozzles) can be mixed with a simple structure. By heating the water in the sealed container 57, the generation of water vapor caused by bubbling can be promoted, so that wet ozone gas containing water vapor appropriately can be generated and pressed to the first moving nozzle 9.

Furthermore, in this embodiment, at least the main surface of the substrate W immediately after the mixed fluid 100 is supplied is a dry surface without a liquid film. Therefore, by supplying the mixed fluid 100, the persulfuric acid in the mixed fluid 100 is not diluted and acts on the anti-corrosion film. Therefore, the anti-corrosion agent decomposition reaction caused by the persulfuric acid occurs efficiently, so the anti-corrosion agent can be removed efficiently.

In particular, in the present embodiment, in the sweeping process (step S52 of FIG. 5 ) in which the first movable nozzle 9 sweeps while the substrate W is rotated around the rotation axis A1, the mixed fluid 100 is sprayed from the first movable nozzle 9 while the landing point 100a of the mixed fluid 100 is moved from the outer periphery of the substrate W toward the rotation axis A1. As the substrate W rotates, the liquid on the main surface of the substrate W flows toward the outer periphery due to the centrifugal force. Therefore, by sweeping the main surface of the substrate from the outer periphery of the substrate W with the mixed fluid 100 sprayed from the first movable nozzle 9 as a plurality of fluid nozzles, the mixed fluid 100 is supplied to a dry surface substantially free of a liquid film. Thus, the persulfuric acid in the mixed fluid 100 is not diluted and acts on the anti-corrosion film on the main surface of the substrate, thereby achieving highly efficient anti-corrosion agent removal.

Furthermore, in this embodiment, the anti-corrosion film on the main surface of the substrate W can be removed without contacting the hydrogen peroxide with the sulfuric acid. Since the hydrogen peroxide and the sulfuric acid are not in contact, a large amount of water can be prevented from mixing with the sulfuric acid. This can reduce the treatment for removing water from the sulfuric acid, making it easy to regenerate the sulfuric acid and reuse it, and accordingly can reduce the amount of sulfuric acid used.

FIG8 is a diagram for explaining the structure of other embodiments of the present invention. In this embodiment, a three-fluid nozzle is used as the first movable nozzle 9. Sulfuric acid (preferably heated sulfuric acid) is supplied from the sulfuric acid supply unit 16 to the first movable nozzle 9 composed of the three-fluid nozzle, ozone gas is supplied from the ozone gas supply unit 13A, and water vapor is supplied from the water vapor supply unit 13B. The ozone gas supply unit 13A and the water vapor supply unit 13B are preferably configured to pressurize ozone gas and water vapor to the first movable nozzle 9, respectively.

The three-fluid nozzle constituting the first movable nozzle 9 is configured to mix sulfuric acid, ozone gas and water vapor to generate a mixed fluid 100, and to spray the mixed fluid 100 toward the main surface of the substrate W. In this example, ozone gas and water vapor are mixed in the second passage 92 of the nozzle housing 90 (internal mixing) and then sprayed from the second nozzle outlet 92a. On the other hand, sulfuric acid passes through the first passage 91 in the nozzle housing 90 and is sprayed from the first nozzle outlet 91a. Then, sulfuric acid collides and mixes with the mixed gas of ozone gas and water vapor outside the nozzle housing 90 near the nozzle outlets 91a and 92a (external mixing), thereby forming a mixed fluid 100.

Of course, this structure is just an example, and a three-fluid nozzle having the following structure can also be used: three separate flow paths for sulfuric acid, ozone gas, and water vapor are formed in the nozzle housing, and sulfuric acid, ozone gas, and water vapor are mixed by contact inside or outside the nozzle housing.

The water vapor supply unit 13B preferably supplies heated water vapor to the first movable nozzle 9. For example, the water vapor supply unit 13B preferably supplies water vapor that is higher than room temperature and below 100°C (e.g., about 80°C) to the first movable nozzle 9. Thus, when the water vapor contacts the ozone gas, the ozone will not decompose, and when the water vapor and the ozone contact the sulfuric acid, high-temperature persulfuric acid can be generated.

The present invention is not limited to the implementation methods described above, and can be implemented in other forms, such as the contents listed below for example.

In each of the above embodiments, the processing liquid is sprayed from a plurality of movable nozzles. However, it may be different from the above embodiments, and the processing liquid may be sprayed from a fixed nozzle whose position in the horizontal direction is fixed, or it may be configured so that all the processing liquids are sprayed from a single nozzle.

In the above-mentioned embodiment, the sulfuric acid is heated by the heater unit 50E arranged in the sulfuric acid piping 40. However, the heating of the sulfuric acid can also be performed in the sulfuric acid tank 55. In addition, a circulation piping for circulating the sulfuric acid in the sulfuric acid tank 55 can also be provided, and a heater unit can be arranged in the circulation piping to heat the sulfuric acid.

The heating of the substrate W is not limited to the heating performed by the substrate heating component 14. Specifically, the substrate heating component may include an infrared lamp opposite to the upper surface of the substrate W, or may include a heater opposite to the upper surface of the substrate W. Alternatively, the substrate heating component may include a heating fluid nozzle that supplies a heating fluid such as nitrogen or warm water to the lower surface of the substrate W. The substrate heating component may also be configured to heat the plate body 60 by circulating the heating fluid in the plate body 60. When the heating fluid is used, the temperature of the substrate W is adjusted by adjusting the opening of the valve that controls the flow rate of the heating fluid. The substrate heating component 14 is not a necessary component in the present invention, and the substrate heating component 14 and the substrate heating process (step S2) may be omitted.

A cooling plate (not shown) for cooling the substrate W may be provided in the substrate processing device 1. The substrate W may be cooled to room temperature by the cooling plate after the substrate heating stop process (step S22).

In each of the above embodiments, the rotary chuck 8 is a holding type rotary chuck that holds the periphery of the substrate W with a plurality of holding pins 20, but the rotary chuck 8 is not limited to a holding type rotary chuck. For example, the rotary chuck 8 may also be a vacuum adsorption type rotary suction cup that adsorbs the substrate W onto the rotary base 21.

In each of the above-mentioned embodiments, the controller 3 controls the entire substrate processing device 1. However, the controllers for controlling the components of the substrate processing device 1 may also be distributed in multiple locations. In addition, the controller 3 does not need to directly control the components, and the signal output from the controller 3 can be received by the slave controllers for controlling the components of the substrate processing device 1.

Furthermore, in the above-mentioned embodiment, the substrate processing device 1 includes: a transport robot (a first transport robot IR and a second transport robot CR), a plurality of processing units 2, and a controller 3. However, the substrate processing device 1 may also be composed of a single processing unit 2 and a controller 3 without including a transport robot. Alternatively, the substrate processing device 1 may be composed of only a single processing unit 2. In other words, the processing unit 2 may be an example of a substrate processing device.

Although the implementation methods of the present invention have been described in detail, they are only used to clarify the specific examples of the technical content of the present invention. The present invention should not be limited to these specific examples. The scope of the present invention is limited only by the scope of the attached patent application.

[Related applications]

This application claims priority based on Japanese Patent Application No. 2023-028824 filed on February 27, 2023, the entire contents of which are incorporated herein by reference.

S1: Steps

S2: Step

S3: Step

S4: Step

S5: Step

S6: Step

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S9: Step

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S21: Step

S22: Step

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Claims (11)

A substrate processing method is a method for processing a substrate having an anti-corrosion film formed on the main surface, comprising: a nozzle configuration step, which is to configure a plurality of fluid nozzles toward the main surface of the substrate; a supply step, which is to supply water vapor, ozone gas and sulfuric acid to the plurality of fluid nozzles; and a mixed fluid supply step, which is to supply a mixed fluid of water vapor, ozone gas and sulfuric acid from the plurality of fluid nozzles to the main surface of the substrate, and remove the anti-corrosion film from the main surface of the substrate, and remove the anti-corrosion film on the main surface of the substrate without bringing hydrogen peroxide into contact with the sulfuric acid. A substrate processing method is a method for processing a substrate having an anti-corrosion film formed on a main surface, comprising: a nozzle configuration step, which is to configure a plurality of fluid nozzles toward the main surface of the substrate; a supply step, which is to supply water vapor, ozone gas and sulfuric acid to the plurality of fluid nozzles; and a mixed fluid supply step, which is to supply a mixed fluid of water vapor, ozone gas and sulfuric acid from the plurality of fluid nozzles to the main surface of the substrate. The above-mentioned supply process includes a wet ozone gas supply process, which is to supply a mixture of water vapor and ozone gas to the above-mentioned multiple fluid nozzles. The above-mentioned wet ozone gas supply process includes a wet ozone gas generation process, which is to generate wet ozone gas by bubbling ozone gas in water. The substrate processing method of claim 2, wherein the above-mentioned wet ozone gas supply process includes the following process: bubbling the ozone gas supplied by the ozone gas supply source in the water in the closed space to generate wet ozone gas in the closed space, and pressurizing the above-mentioned wet ozone gas from the closed space to the above-mentioned multiple fluid nozzles. A substrate processing method as claimed in any one of claims 1 to 3, wherein the mixed fluid supplying step is to supply the mixed fluid containing persulfuric acid produced by mixing the ozone gas and the sulfuric acid to the main surface of the substrate. The substrate processing method of claim 4, wherein the mixed fluid supply process is to supply the mixed fluid containing the persulfuric acid having a higher temperature than the sulfuric acid to the main surface of the substrate by using the dilution heat generated by the contact between the water vapor and the sulfuric acid. A substrate processing method as claimed in any one of claims 1 to 3, wherein the water vapor supplied to the above-mentioned multiple fluid nozzles is below 100°C. A substrate processing method as claimed in any one of claims 1 to 3, wherein the main surface of the substrate before supplying the mixed fluid in the mixed fluid supplying process presents a dry surface without a liquid film. The substrate processing method of any one of claims 1 to 3 further comprises a substrate rotating step, wherein the substrate is rotated around the rotation axis passing through the main surface, and the mixed fluid supply step comprises a sweeping step, wherein the sweeping step is performed in parallel with the substrate rotating step, wherein the mixed fluid is sprayed from the plurality of fluid nozzles while the landing point of the mixed fluid on the main surface is moved from the outer periphery of the substrate to the rotation axis. A substrate processing device comprises: a substrate holding unit that holds a substrate; a plurality of fluid nozzles that are arranged toward the main surface of the substrate held by the substrate holding unit; a water vapor/ozone supply unit that supplies water vapor and ozone gas to the plurality of fluid nozzles; and a sulfuric acid supply unit that supplies sulfuric acid to the plurality of fluid nozzles; and the substrate processing device is configured to supply a mixed fluid of water vapor, ozone gas and sulfuric acid from the plurality of fluid nozzles to the main surface of the substrate held by the substrate holding unit, and remove the anti-corrosion film on the main surface of the substrate without bringing hydrogen peroxide into contact with the sulfuric acid. A substrate processing device comprises: a substrate holding unit that holds a substrate; a plurality of fluid nozzles that are arranged toward the main surface of the substrate held by the substrate holding unit; a water vapor/ozone supply unit that supplies water vapor and ozone gas to the plurality of fluid nozzles; and a sulfuric acid supply unit that supplies sulfuric acid to the plurality of fluid nozzles; and the substrate processing device is configured to supply sulfuric acid from the plurality of fluid nozzles to the substrate held by the substrate holding unit. The main surface of the substrate held by the substrate holding unit is supplied with a mixed fluid of water vapor, ozone gas and sulfuric acid. The water vapor/ozone supply unit supplies humid ozone gas, which is a mixed gas of water vapor and ozone gas. The water vapor/ozone supply unit includes a humid ozone gas generating unit, which generates the humid ozone gas by bubbling ozone gas in water. The substrate processing device of claim 10, wherein the above-mentioned wet ozone gas generating unit includes a sealed container forming a closed space, and an ozone gas supply unit that supplies ozone gas to water stored in the above-mentioned sealed container, and pressurizes the above-mentioned wet ozone gas to the above-mentioned multiple fluid nozzles.