TWI554849B - Substrate processing method and substrate processing device - Google Patents

Description

Substrate processing method and substrate processing device

The present invention relates to a substrate processing apparatus and a substrate processing method for use in removing a resist from a surface of a substrate. The substrate to be processed includes, for example, a semiconductor wafer, a liquid crystal display device substrate, a plasma display substrate, a field emission display FED (Field Emission Display) substrate, a disk substrate, a disk substrate, and a magnet disk. A substrate, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and the like.

Since the introduction, a method of removing a resist from the surface of a substrate by supplying SPM (sulfuric acid/hydrogen peroxide mixture) to the surface of the substrate has been proposed. A wafer having a high dose of ion implantation has a resistive carbonization deterioration (hardening) and a hardened layer is formed on the surface of the resist. For example, the method described in Patent Documents 1 and 2 below is proposed, for example, in order to remove the resist having a hardened layer on the surface from the surface of the substrate without ashing.

Patent Document 1 discloses that a jet of liquid droplets generated by IPA (isopropyl alcohol) and nitrogen gas is supplied to the surface of a substrate in order to break the hardened layer on the surface of the resist, and then SPM is supplied to the surface of the substrate. method.

Patent Document 2 describes a method of supplying the vapor of IPA to the surface of the substrate in order to dissolve the hardened layer on the surface of the resist, and then supplying the SPM to the surface of the substrate.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 4986565

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-103732

However, in the method described in Patent Document 1, since the organic solvent is supplied to the substrate in the form of fine droplets, the number of molecules of the organic solvent contacting the surface of the resist is small, and therefore, the organic solvent is used. At the time of supply, a sufficient amount of organic solvent molecules are not acted on the surface of the resist. Further, in order to mix the organic solvent with nitrogen, the jet of the droplets is lower than the desired temperature. As a result, there is a flaw in the hardened layer which does not sufficiently destroy the surface of the resist. Further, since the jet of the droplet is blown onto the surface of the substrate, there is also a risk of damage to the surface of the substrate.

Further, in the method described in Patent Document 2, since the surface supplied to the surface of the substrate is a vapor of an organic solvent, the number of molecules of the organic solvent contacting the surface of the resist is small, and therefore, when the organic solvent is supplied, only A small amount of organic solvent molecules act on the surface of the resist. Therefore, there is a flaw in the hardened layer which does not sufficiently dissolve the surface of the resist.

In other words, even if the method of any one of Patent Documents 1 and 2 is used, the hardened layer may not be sufficiently broken or dissolved, and a resist may remain on the surface of the substrate.

Accordingly, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus which can remove a resist from a surface of a substrate well.

The present invention relates to a substrate processing method for removing a resist from a surface of a substrate, and comprising: an organic solvent supply step which has a temperature higher than a normal temperature and which does not reach a boiling point The organic solvent of the liquid temperature liquid is supplied to the surface of the substrate in a continuous flow; and the SPM supply step is performed after the organic solvent supply step is performed, and the SPM is supplied to the surface of the substrate after the organic solvent is removed.

According to this method, an organic solvent having a liquid having a liquid temperature higher than a normal temperature and having a boiling point is supplied to the surface of the substrate before the supply of the SPM on the surface of the substrate. The organic solvent maintained at such a liquid temperature has a high thermal energy. Further, since the organic solvent is in a liquid form, the molecules of the organic solvent are in contact with the hardened layer on the surface of the resist with high contact efficiency. The organic solvent molecule having sufficient thermal energy penetrates into the hardened layer on the surface of the resist due to contact with the hardened layer with high contact efficiency. The hardened layer is degraded and softened by the penetration of an organic solvent.

After the supply of the organic solvent, the SPM is supplied to the surface of the substrate. Since the SPM is supplied to the softened hardened layer, the SPM is spread over the entire area inside the resist. Thereby, a substrate processing method capable of well removing the resist from the surface of the substrate can be provided.

The organic solvent contains at least one of IPA, methanol, ethanol, HFE (hydrofluoro-ether), and acetone.

In one embodiment of the present invention, the method further includes a drying step of removing the liquid from the surface of the substrate to cause the substrate before the execution of the SPM supply step. dry.

According to this method, the surface of the substrate is dried before the execution of the SPM supply step. Thereby, in the SPM supply step, the SPM can be applied to the surface of the substrate immediately after the supply thereof.

In this case, the drying step preferably includes a step of removing the drying of the substrate by drying the substrate by removing the liquid on the surface of the substrate to the periphery of the substrate.

The above method may further include a water washing step of supplying the water to the surface of the substrate and rinsing the organic solvent from the surface of the substrate before the execution of the SPM supply step, after the step of supplying the organic solvent.

According to this method, the environmental gas which is generated in the organic solvent supply step can be excluded from the periphery of the surface of the substrate by the water washing treatment after the organic solvent supply step. Thereby, generation of particles after the resist removal treatment can be suppressed or prevented.

The organic solvent supplied to the substrate in the organic solvent supply step may also contain a base. In this case, an organic solvent containing a base is supplied to the surface of the substrate. The hardened layer of the resist is easily dissolved in the alkali solution because the carbon contained therein has an amorphous portion. Therefore, by supplying an alkali-containing organic solvent to the surface of the substrate, the organic solvent penetrates the hardened layer of the resist while dissolving. Thereby, the hardened layer of the resist can be softened more effectively.

The alkali system contains at least one of NH ₄ OH (ammonium hydroxide), TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and NaOH (sodium hydroxide).

The above method may further include a temperature-adjusting fluid supply step performed in parallel with the organic solvent supply step, and supplying the temperature-regulated fluid after the adjusted temperature to the back surface opposite to the surface of the substrate.

According to this method, in parallel with the organic solvent supply step, a temperature-regulating fluid is supplied to the back surface of the substrate. The substrate can be warmed by supplying a temperature-controlling fluid to the back surface of the substrate, and the liquid temperature of the organic solvent supplied to the surface of the substrate can be maintained via the substrate. Thereby, the temperature of the organic solvent on the surface of the substrate can be suppressed from being lowered, and as a result, the hardened layer of the resist can be softened more effectively.

Moreover, the present invention is a substrate processing apparatus comprising: a substrate holding sheet And an organic solvent supply unit for supplying a liquid having a liquid temperature higher than a normal temperature and not reaching a boiling point on a surface of the substrate held by the substrate holding unit; An SPM supply unit that supplies SPM to a surface of a substrate held by the substrate holding unit; and a control unit that controls the organic solvent supply unit and the SPM supply unit; the control unit performs the following steps: an organic solvent supply step, The organic solvent is supplied to the surface of the substrate in a continuous flow; and the SPM supply step is performed after the organic solvent supply step is performed, and the SPM is supplied to the surface of the substrate after the organic solvent is removed.

According to this configuration, before the SPM is supplied to the surface of the substrate, an organic solvent having a liquid having a liquid temperature higher than a normal temperature and having a boiling point is supplied to the surface of the substrate. The organic solvent maintained at such a liquid temperature has a high thermal energy. Further, since the organic solvent is in a liquid form, the molecules of the organic solvent are in contact with the hardened layer on the surface of the resist with high contact efficiency. The organic solvent molecule having sufficient thermal energy penetrates into the hardened layer on the surface of the resist due to contact with the hardened layer with high contact efficiency. The hardened layer is degraded and softened by the penetration of an organic solvent.

After the supply of the organic solvent, the SPM is supplied to the surface of the substrate. Since the SPM is supplied to the softened hardened layer, the SPM is spread over the entire area inside the resist. Thereby, a substrate processing method capable of well removing the resist from the surface of the substrate can be provided.

The organic solvent contains at least one of IPA, methanol, ethanol, HFE (hydrofluoro-ether), and acetone.

The above and other objects, features, and advantages of the invention will be apparent from

1‧‧‧Substrate processing unit

2‧‧‧Processing unit

3‧‧‧Control device

4‧‧‧ chamber

5‧‧‧Rotary chuck

6‧‧‧SPM supply unit

7‧‧‧Organic solvent supply unit

8‧‧‧ rinse supply unit

9‧‧‧ cup

9a‧‧‧Upper

10‧‧‧Spinning base

11‧‧‧ chuck sales

12‧‧‧Rotary axis

13‧‧‧Rotary motor

14‧‧‧SPM nozzle

15‧‧‧1st nozzle arm

16‧‧‧1st nozzle moving unit

17‧‧‧ Sulfuric acid piping

18‧‧‧Hydrogen peroxide water piping

19‧‧‧ sulfuric acid valve

20‧‧‧ Sulfuric acid flow adjustment valve

21‧‧‧1st heater

22‧‧‧Hydrogen peroxide valve

23‧‧‧Hydrogen peroxide water flow adjustment valve

24‧‧‧Organic solvent nozzle

25‧‧‧2nd nozzle arm

26‧‧‧2nd Nozzle Moving Unit

27‧‧‧Organic solvent tank

28‧‧‧Organic solvent piping

29‧‧‧2nd heater

30‧‧‧ pump

31‧‧‧Filter

32‧‧‧Organic Solvent Valve

33‧‧‧Returning piping

34‧‧‧ return valve

35‧‧‧ rinse liquid nozzle

36‧‧‧ rinse liquid piping

37‧‧‧ rinse valve

38‧‧‧Infrared heater

39‧‧‧heater arm

40‧‧‧heater mobile unit

41‧‧‧Infrared light

42‧‧‧Light cover

43‧‧‧Temperature liquid circulation piping

44‧‧‧Temperature fluid supply piping

45‧‧‧temperature control valve

46‧‧‧Back nozzle

46A‧‧‧Export

47‧‧‧ heating device

61‧‧‧Organic solvent flow adjustment valve

62‧‧‧IPA liquid film

63‧‧‧SPM liquid film

A1‧‧‧Rotation axis

CR‧‧‧Substrate transfer robot

P1‧‧‧Measurement location

P2‧‧‧Measurement location

P3‧‧‧Measurement location

P4‧‧‧Measurement location

P5‧‧‧Measurement location

P6‧‧‧Measurement location

P7‧‧‧Measurement location

W‧‧‧Substrate

Fig. 1 is a schematic plan view showing the configuration of a substrate processing apparatus according to an embodiment of the present invention.

Fig. 2 is a schematic view showing the inside of a chamber provided in the substrate processing apparatus shown in Fig. 1 horizontally.

Fig. 3 is a flow chart showing a processing example of the resist removal processing by the processing unit shown in Fig. 2.

Fig. 4 is a schematic view showing the substrate when the organic solvent treatment step is performed horizontally.

Fig. 5 is a schematic view showing the substrate when the SPM processing step is performed horizontally.

6A and 6B are views showing the contents of the first resist removal test and the test results.

Fig. 7 is a view showing the test results of the second resist removal test.

Fig. 1 is a schematic plan view showing a substrate processing apparatus 1 according to an embodiment of the present invention. FIG. 2 is a schematic view showing the inside of the chamber 4 provided in the substrate processing apparatus 1 horizontally.

As shown in FIG. 1, the substrate processing apparatus 1 is a one-chip apparatus for processing a disk-shaped substrate W such as a semiconductor wafer in a single piece. The substrate processing apparatus 1 includes a plurality of processing units 2 that process the substrate W by a processing liquid or a processing gas, and a substrate transfer robot CR that carries in and out the substrate W into the chamber 4 of each processing unit 2; The control device (control unit) 3 controls the operation of the device provided in the substrate processing device 1, the opening and closing of the valve, and the like.

As shown in FIG. 2, each processing unit 2 is a monolithic unit. Each processing unit 2 includes a box-shaped chamber 4 having an internal space, and a rotating chuck (substrate holding unit) 5 that holds a substrate W in a horizontal position in the chamber 4 and surrounds the substrate W. The vertical axis of rotation A1 of the center of the substrate W is rotated; the SPM supply unit 6 is a SPM (containing a mixture of H ₂ SO ₄ (sulfuric acid) and H ₂ O ₂ (hydrogen peroxide water) or H ₂ O ₂ The substrate W is supplied to the spin chuck 5; the organic solvent supply unit 7 supplies the liquid IPA as an organic solvent to the substrate W held by the spin chuck 5; the rinse liquid supply unit 8; the cylindrical cup 9, which surrounds the spin chuck 5; and a heating device 47 that heats the substrate W.

As shown in FIG. 2, the spin chuck 5 includes a disc-shaped rotating base 10 that is held in a horizontal posture, and a plurality of chuck pins 11 that are held horizontally above the spin base 10. The substrate W; the rotating shaft 12 extends downward from a central portion of the rotating base 10; and a rotary motor 13 that rotates the rotating shaft 12 to rotate the substrate W and the rotating base 10 about the rotation axis A1. The spin chuck 5 is not limited to the grip chuck in which the plurality of chuck pins 11 are in contact with the peripheral end surface of the substrate W, and the back surface (lower surface) of the substrate W, that is, the non-device forming surface, may be adsorbed to the spin base 10 The vacuum chuck of the substrate W is horizontally held thereon.

Further, the rotating shaft 12 is formed to be hollow. A tempering liquid circulation pipe 43 is inserted into the inside of the rotating shaft 12. The temperature adjustment liquid supply pipe 44 is connected to the temperature adjustment liquid circulation pipe 43. The tempering liquid supply pipe 44 is supplied to the tempering liquid circulation pipe 43 as a warm water system as an example of the tempering liquid as the tempering fluid. A temperature control liquid valve 45 for opening and closing the temperature adjustment liquid supply pipe 44 is interposed in the middle of the temperature control liquid supply pipe 44. Further, the temperature-adjusting liquid circulation pipe 43 extends to a position close to the center of the back surface (lower surface) of the substrate W held by the spin chuck 5 (a plurality of chuck pins 11), and is provided at the front end thereof to be supplied to the temperature control liquid. The back nozzle 46 of the discharge port 46A from which the warm water of the circulation pipe 43 is discharged is discharged. The warm water discharged from the discharge port 46A is, for example, incident substantially perpendicularly with respect to the center of the back surface of the substrate W held by the spin chuck 5.

Further, warm water may be generated by heating water in a warm water generating cabinet placed separately from the substrate processing apparatus 1, and supplied from the warm water generating cabinet to the temperature adjusting liquid supply. When the temperature of the warm water line through which the warm water flows is provided in the factory in which the substrate processing apparatus 1 is installed, the piping 44 may be supplied to the temperature adjustment liquid supply pipe 44 from the warm water line. The warm water supplied to the temperature adjustment liquid supply pipe 44 is set to the same water temperature as the set temperature (for example, 70 ° C) of the IPA in the organic solvent tank 27. The water used in warm water is, for example, pure water (deionized water), but not limited to pure water, and may be carbonated water, electrolytic ionized water, hydrogen water, ozone water, and diluted concentration (for example, about 10 to 100 ppm). Any of the hydrochloric acid waters.

As shown in FIG. 2, the cup 9 is disposed on the outer side (the direction away from the rotation axis A1) of the substrate W held by the spin chuck 5. The cup 9 is surrounded by the periphery of the spin base 10. When the processing liquid is supplied to the substrate W in a state where the spin chuck 5 rotates the substrate W, the processing liquid supplied to the substrate W is separated from the periphery of the substrate W. When the processing liquid is supplied to the substrate W, the upper end portion 9a of the cup 9 that is opened upward is disposed above the rotating base 10. Therefore, the treatment liquid discharged to the periphery of the substrate W (containing SPM and organic solvent) or the rinse liquid, warm water or the like is taken up by the cup 9. Next, the treatment liquid received by the cup 9 is sent to a recovery device or a liquid discharge device (not shown).

As shown in FIG. 2, the SPM supply unit 6 includes an SPM nozzle 14 that selectively discharges SPM or H ₂ O ₂ toward the upper surface of the substrate W. The first nozzle arm 15 and the SPM nozzle 14 are attached to the front end portion thereof. The first nozzle moving unit 16 moves the SPM nozzle 14 by moving the first nozzle arm 15.

The SPM nozzle 14 is, for example, a DC nozzle that selectively discharges SPM and H ₂ O ₂ in a continuous flow state, and is attached to the first nozzle in a vertical posture in which the processing liquid is discharged to the upper surface of the substrate W in a vertical direction, for example. Arm 15. The first nozzle arm 15 extends in the horizontal direction and is provided to be rotatable around a first rocking axis (not shown) extending in the vertical direction around the spin chuck 5 . Further, the SPM nozzle 14 can be made SPM by the direction in which the SPM or the H ₂ O ₂ is placed on the inner side (the rotation axis A1 side) of the discharge port, and the discharge direction is inclined with respect to the upper surface of the substrate W. H ₂ O ₂ is held in the first nozzle arm 15 by the inward posture of the discharge, and may be liquided on the outer side (the side opposite to the rotation axis A1) by the SPM or H ₂ O ₂ liquid. The position is held by the first nozzle arm 15 in an outward posture in which the SPM or H ₂ O _{2 is} discharged in a direction in which the upper surface of the substrate W is inclined.

The first nozzle moving unit 16 horizontally moves the SPM nozzle 14 along a locus passing through the center portion of the upper surface of the substrate W in a plan view by rotating the first nozzle arm 15 around the first rocking axis. The first nozzle moving unit 16 is a processing position at which the SPM nozzle 14 is placed on the upper surface of the substrate W by the SPM discharged from the SPM nozzle 14 and the start position of the SPM nozzle 14 around the spin chuck 5 in a plan view. Move between horizontally. Further, the first nozzle moving unit 16 causes the SPM nozzle 14 to immerse the SPM or H ₂ O ₂ discharged from the SPM nozzle 14 at the center of the upper center portion of the substrate W and the SPM or H ₂ discharged from the SPM nozzle 14 . The O ₂ liquid is horizontally moved between the peripheral positions of the upper peripheral portion of the substrate W. Both the central position and the peripheral position are processing positions.

The SPM supply unit 6 further includes a sulfuric acid pipe 17 connected to the SPM nozzle 14 and supplied with H ₂ SO ₄ from a sulfuric acid supply source (not shown), and a hydrogen peroxide water pipe 18 connected to the SPM nozzle 14 . H ₂ O _{2 is} supplied from a hydrogen peroxide water supply source (not shown).

In the middle of the sulfuric acid pipe 17, a sulfuric acid valve 19 for opening and closing the sulfuric acid pipe 17, a sulfuric acid flow rate adjusting valve 20, and a first heater 21 are sequentially disposed from the SPM nozzle 14 side. The first heater 21 maintains H ₂ SO ₄ at a temperature higher than room temperature (a constant temperature in the range of 70 to 120 ° C, for example, 100 ° C). The first heater 21 for heating the H ₂ SO ₄ may be a unidirectional flow heater as shown in FIG. 2 or may be circulated by circulating H ₂ SO ₄ inside the circulation path including the heater. A circulating heater that heats H ₂ SO ₄ . Although not shown, the sulfuric acid flow rate adjustment valve 20 includes a valve body in which the valve seat is provided, a valve body that opens and closes the valve seat, and an actuator that moves the valve body between the open position and the closed position. The same is true for other flow regulating valves.

In the middle of the hydrogen peroxide water pipe 18, a hydrogen peroxide water valve 22 for opening and closing the hydrogen peroxide water pipe 18 and a hydrogen peroxide water flow rate adjusting valve 23 are sequentially disposed from the SPM nozzle 14 side. H ₂ O ₂ , which is not subjected to temperature adjustment at a normal temperature (about 23 ° C), is supplied to the SPM nozzle 14 through the hydrogen peroxide water pipe 18 . The hydrogen peroxide water valve 22 is opened and closed by the control of the control device 3.

The SPM nozzle 14 has, for example, a substantially cylindrical outer casing. Inside the casing, a mixing chamber (not shown) is formed in the compartment. The sulfuric acid pipe 17 is connected to a sulfuric acid inlet (not shown) disposed on the side wall of the outer casing of the SPM nozzle 14. The hydrogen peroxide water pipe 18 is connected to a hydrogen peroxide water introduction port (not shown) disposed above the sulfuric acid introduction port in the side wall of the outer casing of the SPM nozzle 14.

When the sulfuric acid valve 19 (refer to FIG. 2) and the hydrogen peroxide water valve 22 (refer to FIG. 2) are opened, the H ₂ SO ₄ from the sulfuric acid pipe 17 is supplied from the sulfuric acid inlet port to the mixing chamber in the SPM nozzle 14 and comes from The H ₂ O _{2 of the} hydrogen peroxide water pipe 18 is supplied from the hydrogen peroxide water inlet to the mixing chamber in the SPM nozzle 14. The H ₂ SO ₄ and H ₂ O ₂ flowing into the mixing chamber of the SPM nozzle 14 are sufficiently mixed (stirred) in the inside thereof. By this mixing, H ₂ SO ₄ and H ₂ O ₂ are uniformly mixed together, and a mixture of H ₂ SO ₄ and H ₂ O ₂ is produced by the reaction of H ₂ SO ₄ and H ₂ O ₂ (SPM) ). The SPM system contains a strong oxidizing power of Peroxymonosulfuric acid (H ₂ SO ₅ ) and is heated to a temperature higher than the temperature of H ₂ SO ₄ and H ₂ O ₂ before mixing (100 ° C or more. For example, 160 °C). The high-temperature SPM generated in the mixing chamber of the SPM nozzle 14 is discharged from the discharge port of the opening at the front end (lower end) of the outer casing.

As shown in FIG. 2, the organic solvent supply unit 7 includes an organic solvent nozzle 24 that discharges IPA (liquid) as an example of an organic solvent toward the substrate W held by the spin chuck 5, and a second nozzle arm 25, organic The solvent nozzle 24 is attached to the front end portion thereof, and the second nozzle moving unit 26 moves the organic solvent nozzle 24 by moving the second nozzle arm 25.

The organic solvent nozzle 24 is, for example, a DC nozzle that discharges a liquid IPA in a continuous flow state, and is attached to the second nozzle arm 25 in a vertical posture in which the processing liquid is discharged to the upper surface of the substrate W in a vertical direction, for example. The second nozzle arm 25 extends in the horizontal direction and rotates around a second rocking axis (an axis different from the first rocking axis in the horizontal direction, not shown) that can extend around the rotating chuck 5 in the vertical direction. It is set in the way. Further, the organic solvent nozzle 24 can eject the IPA in a discharge direction inclined with respect to the upper surface of the substrate W by IPA (liquid) liquid being placed on the inner side (the rotation axis A1 side) of the discharge port. The inward posture is held by the second nozzle arm 25, and may be relative to the substrate W by IPA (liquid) liquid being placed on the outer side (the side opposite to the rotation axis A1) from the discharge port. The upper surface of the upper nozzle arm 25 is held in an outwardly inclined position in which the upper surface of the IPA (liquid) is discharged.

The second nozzle moving unit 26 horizontally moves the organic solvent nozzle 24 in a plan view along a locus passing through the center portion of the upper surface of the substrate W by rotating the second nozzle arm 25 around the second rocking axis. The second nozzle moving unit 26 sets the organic solvent nozzle 24 to the processing position of the center portion of the upper surface of the substrate W by the IPA discharged from the organic solvent nozzle 24, and the organic solvent nozzle 24 is set to the spin chuck 5 in a plan view. Move horizontally between the starting positions around.

The organic solvent supply unit 7 includes an organic solvent tank 27 that stores IPA, and an organic solvent pipe 28 that supplies the IPA stored in the organic solvent tank 27 to the organic solvent nozzle 24. The IPA system stored in the organic solvent tank 27 contains NH ₄ OH (base). Specifically, a high concentration (about 30 wt%) of NH ₄ OH in aqueous-based IPA: NH ₄ OH solution = 1000: 1 ratio is added to the IPA.

One end of the organic solvent pipe 28 is connected to the organic solvent tank 27, and the other end of the organic solvent pipe 28 is connected to the organic solvent nozzle 24. In the organic solvent pipe 28, a second heater 29 is disposed in order from the organic solvent tank 27, and the temperature is adjusted by heating the IPA flowing through the organic solvent pipe 28; the pump 30 is from the organic solvent tank 27 The IPA is taken out and sent to the organic solvent pipe 28; the filter 31 filters the IPA flowing through the organic solvent pipe 28, and the foreign matter is removed from the IPA; the organic solvent flow regulating valve 61; and the organic solvent valve 32, which are paired The organic solvent supply pipe 28 is switched to the supply and supply stop of the IPA of the organic solvent nozzle 24. Furthermore, the pump 30 is constantly driven when the processing unit 2 is started.

The partial difference between the organic solvent flow rate adjustment valve 61 and the filter 31 in the organic solvent pipe 28 is used to return the IPA flowing through the organic solvent pipe 28 to the return pipe 33 of the organic solvent tank 27. A return valve 34 is incorporated in the return pipe 33. The circulation path for circulating the IPA in the organic solvent tank 27 is formed by the more upstream side portion and the return pipe 33 than the branch position of the organic solvent pipe 28.

The control device 3 opens the return valve 34 while closing the organic solvent valve 32 while the pump 30 is being driven. Thereby, the IPA extracted from the organic solvent tank 27 is returned to the organic solvent tank 27 through the second heater 29, the filter 31, the return piping 33, and the return valve 34. Thereby, the IPA in the organic solvent tank 27 circulates in the above-described circulation path, and the IPA in the organic solvent tank 27 is regulated by the temperature of the second heater 29 by circulating in the circulation path, and is maintained at a predetermined high temperature (more Normal temperature (about 23 ° C) is higher and does not reach the boiling point temperature. For example, about 70 ° C).

On the other hand, the control device 3 opens the organic solvent valve 32 while closing the return valve 34 while the pump 30 is being driven. Thereby, the IPA extracted from the organic solvent tank 27 flows into the organic solvent nozzle 24 through the second heater 29, the filter 31, the organic solvent flow rate adjustment valve 61, and the organic solvent valve 32.

Further, a three-way valve is interposed between the organic solvent flow rate adjusting valve 61 and the filter 31 in the organic solvent pipe 28, and a return pipe 33 may be connected to the three-way valve. At this time, the IPA flowing through the organic solvent pipe 28 can be selectively sent to the organic solvent nozzle 24 side or the return pipe 33 side by the control of the three-way valve.

As shown in FIG. 2, the rinse liquid supply unit 8 includes a rinse liquid nozzle 35 that discharges the rinse liquid toward the substrate W held by the spin chuck 5, and a rinse liquid pipe 36 that supplies the rinse liquid to the rinse liquid nozzle 35. And a rinse liquid valve 37 that switches the supply and supply stop of the rinse liquid from the rinse liquid pipe 36 to the rinse liquid nozzle 35. The rinse liquid nozzle 35 is a fixed nozzle that discharges the rinse liquid in a state where the discharge port of the rinse liquid nozzle 35 is stationary. The rinsing liquid supply unit 8 may further include a rinsing liquid nozzle moving device that moves the priming position of the rinsing liquid on the upper surface of the substrate W by moving the rinsing liquid nozzle 35.

When the rinse liquid valve 37 is opened, the rinse liquid supplied from the rinse liquid pipe 36 to the rinse liquid nozzle 35 is discharged from the rinse liquid nozzle 35 toward the upper center portion of the substrate W. The rinsing liquid is, for example, pure water (deionized water: Deionized Water). However, the rinsing liquid is not limited to pure water, and may be any of carbonated water, electrolytic ionized water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 to 100 ppm).

As shown in FIG. 2, the heating device 47 includes a radiant heating device that heats the substrate W by radiation. The radiant heating device includes an infrared heater 38 that irradiates infrared rays to the substrate W, and a heater arm 39 that is mounted on the infrared heater 38. a front end portion thereof; and a heater moving unit 40 that moves the heater arm 39.

The infrared heater 38 includes an infrared lamp 41 (referred to in conjunction with FIG. 5) that emits infrared rays, and a lamp cover 42 (referred to in conjunction with FIG. 5) that houses the infrared lamp 41.

The infrared lamp 41 is disposed in the lamp housing 42. The lamp housing 42 is smaller than the substrate W in plan view. Therefore, the infrared heater 38 disposed in the lamp housing 42 is smaller than the substrate W in plan view. The infrared lamp 41 and the lamp cover 42 are attached to the heater arm 39. Therefore, the infrared lamp 41 and the lamp housing 42 move together with the heater arm 39.

The infrared lamp 41 includes a filament and a quartz tube for housing the filament. As the infrared lamp 41 (for example, a halogen lamp) in the heating device 47, a heating element such as a graphite heater can be used. At least a part of the lamp housing 42 is formed of a material having light transmittance and heat resistance such as quartz. When the infrared lamp 41 emits light, light containing infrared rays is emitted from the infrared lamp 41. The light including the infrared rays is transmitted from the outer surface of the lamp cover 42 through the lamp housing 42. The substrate W and the liquid film held thereon are heated by the transmitted light and the radiant light from the outer surface of the lamp housing 42.

The heater moving unit 40 maintains the infrared heater 38 at a predetermined height. The heater moving unit 40 causes the infrared heater 38 to move vertically. Further, the heater moving unit 40 surrounds the third rocking axis (the axis which is different from the first and second rocking axes in the horizontal direction) around the rotating chuck 5 by the heater arm 39. The image is shaken to move the infrared heater 38 in a horizontal plane above the spin chuck 5.

The control device 3 shown in Figs. 1 and 2 is constituted by, for example, a microcomputer. The control device 3 controls the operations of the rotary motor 13, the nozzle moving units 16, 26, the heater moving unit 40, the heaters 21, 29, and the like in accordance with a preset program. Further, control The device 3 controls opening and closing of the sulfuric acid valve 19, the hydrogen peroxide water valve 22, the temperature control liquid valve 45, the flushing liquid valve 37, and the like, and controls the actuators of the flow regulating valves 20, 23, 61 to control the flow regulating valve. 20, 23, 61 opening.

FIG. 3 is a flow chart showing a process example of the resist removal process performed by the processing unit 2. Fig. 4 is a schematic view showing the substrate W when the organic solvent treatment step (S3) is performed horizontally. Fig. 5 is a schematic view showing the substrate W when the SPM processing step (S3) is performed horizontally.

Hereinafter, a treatment example of the resist removal treatment will be described with reference to FIGS. 2 and 3. Reference is made to FIGS. 4 and 5 as appropriate.

When the substrate W is subjected to the resist removal treatment by the processing unit 2, the substrate W subjected to the ion implantation treatment at a high dose is carried into the inside of the chamber 4 (step S1). The substrate W that was carried in has not yet received a processor for ashing the resist. Specifically, the control device 3 enters the inside of the chamber 4 by the hand of the substrate transfer robot CR (see FIG. 1) holding the substrate W in a state where all of the nozzles are retracted from above the spin chuck 5 The substrate W is delivered to the spin chuck 5 with its surface facing upward. Thereafter, the control device 3 starts the rotation of the substrate W by the rotation motor 13 (step S2). The substrate W is raised to a predetermined organic solvent treatment rate (in the range of 100 to 500 rpm, for example, about 300 rpm), and is maintained at the organic solvent treatment rate.

Next, an organic solvent treatment step (organic solvent supply step. S3) of supplying IPA as an organic solvent to the upper surface of the substrate W is performed. Specifically, the control device 3 moves the organic solvent nozzle 24 from the initial position to the above-described processing position by controlling the second nozzle moving unit 26. Thereby, the organic solvent nozzle 24 is disposed above the upper center portion of the substrate W.

After the organic solvent nozzle 24 is placed at the processing position, the control device 3 opens the organic solvent valve 32 while closing the return valve 34. Thereby, the IPA (IPA containing NH ₄ OH) circulating in the circulation path including the upstream side portion of the organic solvent pipe 28 and the return pipe 33 is supplied to the organic solvent valve 32 through the organic solvent pipe 28 . Thereby, the liquid IPA (IPA containing NH ₄ OH) from the predetermined high temperature (temperature higher than normal temperature and not reaching the boiling point, for example, about 70 ° C) of the organic solvent nozzle 24 is discharged in a continuous flow. At this time, the opening degree of the organic solvent pipe 28 is adjusted by the organic solvent flow rate adjustment valve 61 so that the discharge flow rate of the IPA becomes a predetermined process flow rate (for example, 0.2 liter/min or more).

The high-temperature liquid IPA (IPA containing NH ₄ OH) ejected from the organic solvent nozzle 24 is placed on the substrate by centrifugal force after being liquided on the substrate W which is rotated at the organic solvent treatment rate (for example, about 300 rpm). The top of W flows to the outside. Therefore, as shown in FIG. 4, IPA is supplied to the entire upper surface of the substrate W, and a liquid film 62 covering the entire upper surface of the substrate W is formed on the substrate W.

Moreover, warm water is supplied to the back surface of the substrate W from the discharge port 46A of the back surface nozzle 46 together with the organic solvent processing step (S3). Specifically, the control device 3 opens the temperature control liquid valve 45. As a result, as shown in FIG. 4, the warm water from the temperature adjustment liquid supply pipe 44 is discharged upward from the discharge port 46A of the back surface nozzle 46 through the temperature control liquid supply pipe 43, and is supplied to the center of the back surface of the substrate W. . The warm water that is liquid on the central portion of the back surface of the substrate W flows to the outside by the centrifugal force caused by the rotation of the substrate W, whereby the entire back surface of the substrate W is covered with a liquid film of warm water.

The substrate W is heated by the supply of warm water to the back surface of the substrate W. By supplying IPA on the upper surface of the heated substrate W, the IPA is heated via the substrate W. The water temperature of the warm water supplied to the back surface of the substrate W is set to the same temperature as the IPA supplied to the upper surface of the substrate W, so that the liquid film 62 of the IPA formed on the upper surface of the substrate W is The liquid temperature is maintained at the desired liquid temperature (i.e., at a predetermined elevated temperature (e.g., about 70 ° C)). Further, since the entire region of the substrate W is heated by warm water, the in-plane temperature distribution of the liquid film 62 of IPA is the same.

In the organic solvent treatment step (S3), the liquid film 62 of the IPA on the substrate W has a predetermined high temperature (liquid temperature higher than normal temperature and not reaching the boiling point, for example, about 70 ° C). The organic solvent maintained at such a liquid temperature has a high thermal energy. Further, since IPA is liquid, the molecular structure of IPA is in contact with the hardened layer on the surface of the resist with high contact efficiency. At the interface between the liquid film 62 of IPA and the surface of the resist, the molecular system of IPA having sufficient thermal energy contacts the hardened layer with high contact efficiency, whereby IPA penetrates into the hardened layer on the surface of the resist. By the penetration of IPA, the hardened layer deteriorates and softens.

Further, NH ₄ OH is contained in the organic solvent supplied to the substrate W. Since the hardened layer of the resist is easily dissolved in the NH ₄ OH solution because the contained carbon system has an amorphous portion, when the IPA containing NH ₄ OH is supplied to the upper surface of the substrate W, the NH is contained. The IPA of ₄ OH dissolves and penetrates into the hardened layer of the resist. Thereby, the softening of the hardened layer can be performed more efficiently.

When a predetermined processing time elapses from the start of the discharge of the IPA, the control device 3 closes the IPA valve 32 and stops the discharge of the IPA. Moreover, the control device 3 closes the back valve 45 and stops the discharge of warm water from the back nozzle 46. Further, by controlling the second nozzle moving unit 26, the organic solvent nozzle 24 is moved from the processing position to the starting position.

After the completion of the organic solvent treatment step (S3), a first rinse liquid supply step of supplying the rinse liquid to the substrate W (water washing step. Step S4) is performed. Specifically, the control device 3 opens the rinse liquid valve 37 and discharges the rinse liquid from the rinse liquid nozzle 35 toward the upper center portion of the substrate W. The rinse liquid discharged from the rinse liquid nozzle 35 is attached to the upper center portion of the substrate W covered by the IPA. Flushing the liquid at the upper center of the substrate W The liquid system is subjected to a centrifugal force caused by the rotation of the substrate W, and flows toward the peripheral portion of the substrate W on the upper surface of the substrate W. Thereby, the IPA on the substrate W is washed outward by the rinsing liquid, and is discharged to the periphery of the substrate W. Therefore, the liquid film 62 of the IPA on the substrate W is replaced with a liquid film covering the entire surface of the substrate W. Thereby, the IPA is washed in the entire area above the substrate W.

Further, since the ambient gas of IPA is generated in the organic solvent treatment step (S3), the flue gas having IPA floats in the cup 9 after the end of the organic solvent treatment step (S3). By flowing the rinsing liquid onto the substrate W, the smoke of the IPA floating in the cup 9 can be excluded from the periphery of the upper surface of the substrate W. Therefore, the smoke of the IPA floating in the cup 9 becomes fine particles, and the surface of the substrate W can be suppressed or prevented from being contaminated.

When a predetermined time elapses after the flushing liquid valve 37 is opened, the control device 3 closes the flushing liquid valve 37 to stop the discharge of the flushing liquid from the flushing liquid nozzle 35.

Next, a first drying step of drying the substrate W is performed (the drying step is removed. Step S5). Specifically, the control device 3 accelerates the substrate W to a dry rotation speed (for example, several thousand rpm) by controlling the rotation motor 13, and rotates the substrate W at a dry rotation speed. Thereby, the large centrifugal force is the rinsing liquid applied to the substrate W, and the rinsing liquid adhering to the substrate W is separated from the periphery of the substrate W. Thus, the rinsing liquid is removed from the substrate W, and the substrate W is dried. When a predetermined time elapses after the start of the high-speed rotation of the substrate W, the control device 3 decelerates the rotational speed of the substrate W held by the spin chuck 5 to the SPM processing speed (for example, about 300 rpm) by controlling the rotary motor 13. .

When the rotational speed of the substrate W reaches the SPM rotational speed, the control device 3 then performs an SPM processing step of supplying the SPM to the substrate W (SPM supply step. Step S6). Specifically, the control device 3 moves the SPM nozzle 14 from the initial position to the processing position by controlling the first nozzle moving unit 16. Thereby, the SPM nozzle 14 is matched Placed above the substrate W.

After the SPM nozzle 14 is disposed above the substrate W, the control device 3 simultaneously opens the sulfuric acid valve 19 and the hydrogen peroxide water valve 22. Thereby, the H ₂ SO ₄ flowing through the inside of the sulfuric acid pipe 17 is supplied to the SPM nozzle 14 , and the hydrogen peroxide water flowing through the hydrogen peroxide water pipe 18 is supplied to the SPM nozzle 14 . Next, H ₂ SO ₄ and H ₂ O ₂ are mixed in the mixing chamber of the SPM nozzle 14 to generate a high temperature (for example, 160 ° C) SPM. The SPM is discharged from the discharge port of the SPM nozzle 14 and is placed on the upper surface of the substrate W. The control device 3 controls the first nozzle moving unit 16 to move the liquid level of the SPM on the upper surface of the substrate W between the center portion and the peripheral portion in this state.

The SPM discharged from the SPM nozzle 14 flows on the upper surface of the substrate W which is rotated at the SPM processing speed (for example, 300 rpm), and then flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the SPM is supplied to the entire upper surface of the substrate W, and as shown in FIG. 5, the liquid film 63 covering the entire upper surface of the substrate W is formed on the substrate W.

The hardened layer on the surface of the resist is softened by the organic solvent treatment step (S3). Since the SPM is supplied to the softened hardened layer, the SPM is spread over the entire inner region of the resist, and the resist on the substrate W is removed from the substrate W by SPM by the chemical reaction of the resist with the SPM. Further, in the state in which the substrate W is rotated, the control device 3 moves the liquid level of the SPM on the upper surface of the substrate W between the center portion and the peripheral portion, so that the liquid level of the SPM passes through the entire upper surface of the substrate W. The entire area above the substrate W is scanned. Therefore, the SPM which is discharged from the SPM nozzle 14 is supplied to the entire upper surface of the substrate W, and the entire upper surface of the substrate W is uniformly processed.

Further, together with the SPM processing step (S6), the SPM of the substrate W and the substrate W is supplied to the SPM before being supplied to the substrate W by the infrared heater 38. The heating step of heating at a higher temperature and heating temperature. Specifically, as shown in FIG. 5, the control device 3 moves the infrared heater 38 from the retracted position to the processing position by controlling the heater moving unit 31. Thereby, the infrared heater 38 is disposed above the substrate W. Thereafter, the control device 3 causes the infrared heater 38 to start emitting light. Thereby, the temperature of the infrared heater 38 rises to a heating temperature (for example, 200 ° C or more) equal to or higher than the boiling point of the concentration of SPM, and is maintained at the heating temperature.

After the infrared heater 38 starts emitting light above the substrate W, the control device 3 moves the infrared heater 38 by the heater moving unit 31 as shown in FIG. 5 to make the infrared rays on the upper surface of the substrate W. The irradiation position moves within the upper surface of the substrate W. The substrate W and the SPM on the substrate W are heated in a state where the substrate W is rotated at the above-described SPM processing speed (for example, 300 rpm).

The control device 3 stops the light emission of the infrared heater 38 after the substrate W is heated by the infrared heater 38 for a predetermined period of time. Thereafter, the control device 3 controls the heater moving unit 31 to retract the infrared heater 38 from above the substrate W.

In this manner, the control device 3 moves the irradiation position of the infrared rays on the upper surface of the substrate W in the upper surface of the substrate W while the substrate W is being rotated. Therefore, the substrate W is uniformly heated. Therefore, the liquid film 63 of the SPM covering the entire upper surface of the substrate W is also uniformly heated. The heating temperature of the substrate W heated by the infrared heater 38 is set to, for example, a higher temperature than the boiling point of the concentration of the SPM, whereby the temperature of the interface between the substrate W and the SPM is maintained at a higher temperature than the boiling point, and is promoted. Removal of the resist from the substrate W.

In addition, in the state of being disposed at the processing position, the substrate facing surface of the infrared heater 38 can contact the liquid film 63 of the SPM on the substrate W, or as shown in FIG. It is shown that the substrate facing surface of the infrared heater 38 is separated from the liquid film 63 of the SPM on the substrate W by a predetermined distance.

Further, when the substrate W is heated by the infrared heater 38 (heating step), the infrared heater 38 disposed above the substrate W may be placed in a stationary state.

When the preset SPM processing time elapses from the start of SPM ejection, the SPM processing step (S6) is ended. Following the end of the SPM processing step (S6), a hydrogen peroxide water supply step of supplying H ₂ O ₂ to the substrate W is performed (step S7).

Specifically, the control device 3 controls the first nozzle moving unit 16 to arrange the SPM nozzle 14 above the upper center portion of the substrate W, and thereafter, the control device 3 maintains the hydrogen peroxide water valve 22 while In the open state, only the sulfuric acid valve 19 is closed. Thereby, H ₂ SO _{4 is} not caused to flow inside the sulfuric acid pipe 17, and only H ₂ O ₂ flows into the inside of the hydrogen peroxide water pipe 18 and is supplied to the SPM nozzle 14 . The hydrogen peroxide water supplied to the SPM nozzle 14 passes through the inside of the SPM nozzle 14 and is discharged from the discharge port of the SPM nozzle 14. The H ₂ O ₂ is applied to the upper central portion of the substrate W which is rotated at the SPM processing speed. That is, the treatment liquid discharged from the SPM nozzle 14 is switched from SPM to H ₂ O ₂ .

The H ₂ O ₂ liquid that is placed on the upper center of the substrate W faces the periphery of the substrate W and flows outward on the substrate W. The SPM on the substrate W is replaced with H ₂ O ₂ , and then the entire upper surface of the substrate W is covered with a liquid film of H ₂ O ₂ .

When the predetermined hydrogen peroxide water supply time elapses from the discharge of the hydrogen peroxide water, the control device 3 closes the hydrogen peroxide water valve 22 to stop the discharge of H ₂ O ₂ from the SPM nozzle 14 . Further, the control device 3 moves the SPM nozzle 14 from the processing position to the starting position. Thereby, the SPM nozzle 14 is disposed above the substrate W.

Next, a second rinse liquid supply step of supplying the rinse liquid to the substrate W is performed (step S8). Specifically, the control device 3 opens the rinse liquid valve 37 to discharge the rinse liquid from the rinse liquid nozzle 35 toward the upper center portion of the substrate W. The rinse liquid discharged from the rinse liquid nozzle 35 is attached to the upper center portion of the substrate W covered with H ₂ O ₂ . The rinsing liquid that is placed on the upper center portion of the substrate W is subjected to centrifugal force caused by the rotation of the substrate W, and flows toward the peripheral portion of the substrate W on the upper surface of the substrate W. Thereby, the H ₂ O ₂ on the substrate W is washed out to the outside by the rinse liquid, and is discharged around the substrate W. Therefore, the liquid film of H ₂ O ₂ on the substrate W is replaced with a liquid film of the rinse liquid covering the entire upper surface of the substrate W. Thereby, the H ₂ O ₂ system in the entire region above the substrate W is washed. Next, when a predetermined time elapses after the flushing liquid valve 37 is opened, the control device 3 closes the flushing liquid valve 37, and stops the discharge of the flushing liquid from the flushing liquid nozzle 35.

Next, a second spin drying step of drying the substrate W is performed (step S9). Specifically, the control device 3 accelerates the substrate W to a dry rotation speed (for example, several thousand rpm) by controlling the rotation motor 13, and rotates the substrate W at a dry rotation speed. Thereby, a large centrifugal force is applied to the liquid on the substrate W, and the liquid adhering to the substrate W is separated from the periphery of the substrate W. Thus, the liquid system is removed from the substrate W, and the substrate W is dried. Then, when a predetermined time elapses after the high-speed rotation of the substrate W is started, the control device 3 stops the rotation of the substrate W by the spin chuck 5 by controlling the rotary motor 13 (step S10).

Next, the substrate W is carried out from the chamber 4 (step S11). Specifically, the control device 3 causes the hand of the substrate transfer robot CR to enter the inside of the chamber 4 in a state where all of the nozzles are retracted from above the spin chuck 5 . Next, the control device 3 holds the substrate W on the spin chuck 5 on the hand of the substrate transfer robot CR. Thereafter, the control device 3 retracts the hand of the substrate transfer robot CR from the inside of the chamber 4. Thereby, the processed substrate W is carried out from the chamber 4.

Further, in the treatment example of Fig. 3, the liquid solution such as SC1 (ammonia hydrogen peroxide water mixed solution) may be performed after the second rinse liquid supply step (S8) and before the second drying step (S9). A chemical supply step of washing the upper surface of the substrate W, and a rinsing step of rinsing the chemical liquid from the upper surface of the substrate W.

Moreover, in the processing example of FIG. 3, although the hydrogen peroxide water supply step (S7) is performed after the SPM process step (S6), the hydrogen peroxide water supply step (S7) may be omitted.

Further, in the processing example of FIG. 3, the heating step is performed together with the SPM processing step (S6), but the heating step may be omitted. In this case, the configuration of the heating device 47 (radiation heating device, see FIG. 2) may be omitted from the substrate processing device 1.

Further, in the processing example of FIG. 3, in the SPM processing step (step S6), the substrate W is rotated at the SPM processing speed (for example, about 300 rpm), but the rotation speed of the substrate W at this time may be A low rotation speed (immersion rotation speed) in which the discharge of the SPM on the substrate W is suppressed and the liquid film of the SPM is held on the upper surface of the substrate W (immersed state) can be maintained. In this case, after the formation of the liquid film 63 of the SPM liquid, the supply of the SPM can also be stopped.

Next, the resist removal test will be described.

6A and 6B are views showing the contents of the first resist removal test and the test results.

The first resist removal test was conducted by comparing the resist removal performance at the peripheral portion of the substrate W by the examples and the comparative examples.

The pattern of the KrF (yttrium fluoride) excimer laser resist is formed on the entire surface of the wafer W having a diameter of 300 mm without any gap, as a mask, and the surface is used on the surface of the wafer W. (Arsenic) was prepared by ion implantation at a dose of 1 × 10 ¹⁵ atoms/cm ² and a dose energy of 10 keV, and the substrate processing apparatus 1 was used to carry out the resists of the examples and comparative examples described below. Removal processing. Next, the presence or absence of the resist residue after the resist removal treatment was observed with an electron microscope at the measurement points P1 to P7 of the seven portions of the peripheral portion of the wafer W. As shown in FIG. 6A, the measurement points P1 to P7 are each arranged in parallel at equal intervals on a straight line extending in the direction of the radius of rotation of the substrate W. The distance between the outermost peripheral measurement point P7 and the outer periphery of the crucible wafer W is 5 mm, and the distance between the innermost circumference measurement point P1 and the outer circumference of the crucible wafer W is 25 mm. Further, in the SPM used in the SPM processing step of step S6, the mixing ratio (weight ratio) of H ₂ SO ₄ and H ₂ O ₂ is set to 2:1, and the processing time of the SPM processing step of step S6 is set. It is 15 seconds.

<Example>

The processing equivalent to the processing example shown in FIG. 3 described above is executed. However, the IPA supplied in the organic solvent treatment step (S3) does not contain a base such as NH ₄ OH. Further, the liquid temperature of the IPA supplied in the organic solvent treatment step (S3) was 70 ° C, and the flow rate of the IPA was set to 0.2 liter / min.

<Comparative example>

The processing of the contents of steps S3 to S5 is omitted from the processing example shown in FIG. 3 described above. The result of this first resist removal test is shown in Fig. 6B. In Fig. 6B, the case where substantially no resist residue is generated is shown as "○" (Good), and the case where a small amount of resist residue is generated is shown as "△" (Fair), and the case where a large amount of resist residue is generated is shown as " ×" (Insufficient).

As shown in Fig. 6B, in the examples, substantially no resist residue was found except for the measurement point P7 closest to the outer periphery. In the examples, it can be known that even in twinning The peripheral portion of the circle W also has a high removal performance.

On the other hand, in the comparative example, the resist residue was found except for the measurement point P1 closest to the inner circumference. In particular, a large amount of resist residue was found at the measurement site P6 and the measurement site P7 near the outer periphery.

As a result of the first resist removal test, in the examples, the resist was well removed from the surface of the tantalum wafer W even if the wafer W was subjected to high-dose ion implantation.

Fig. 7 is a view showing the test results of the second resist removal test.

The second resist removal test is a high-temperature IPA used in the organic solvent treatment step (S3) for a beaker test in which the resist removal performance is compared in the case where no alkali is contained and the case where the base is contained.

A pattern of a KrF (yttrium fluoride) excimer laser resist is formed on the entire surface of the wafer W as a mask, and As (arsenic) is used as a dose on the surface of the wafer W. 10 ¹⁶ atoms/cm ² , a dose of 40 keV was ion-implanted, and the sample was cut into a sheet shape, and the samples were subjected to the first to third tests described below. Next, the presence or absence of the resist residue on the sheet after the test and the extent thereof were observed using an electron microscope. Further, in the SPM used in each test, the mixing ratio of H ₂ SO ₄ and H ₂ O ₂ was set to 2:1, and the immersion time of SPM was set to 1 minute.

<1st test>

In the beaker, the above sample was immersed in a high temperature IPA. The IPA system does not contain a base such as NH ₄ OH, and the liquid temperature of IPA is 70 ° C. Next, the sample was immersed in SPM.

<2nd test>

In the beaker, the above sample was immersed in a high temperature IPA. NH ₄ OH was added to the IPA. The added concentration of NH ₄ OH is the same as the added concentration of IPA used in the above organic solvent treatment step (S3). Also, the liquid temperature of IPA was 70 °C. Next, the sample was immersed in SPM.

<3rd test>

In the beaker, the above sample was not immersed in a high temperature IPA and immersed in SPM.

The results of the second resist removal test are shown in Fig. 7. In Fig. 7, the case where substantially no resist residue is generated is shown as "◎" (Very Good), and the case where only a few resist residues are generated is shown as "○" (Good), and a large amount of resist residue is displayed. It is "X" (Insufficient).

As shown in Fig. 7, in Test 1 in which the high temperature IPA was supplied before the SPM supply, only a few resist residues were found. Further, in the test 2 in which the IPA of the high temperature to which the alkali was added before the supply of the SPM was supplied, substantially no residue remained.

As a result of the second resist removal test, it was found that the supply of the base-added IPA before the SPM supply was more effective than the supply of the base-free IPA.

According to the embodiment described above, the IPA of the liquid having a high temperature (for example, about 70 ° C) is supplied on the upper surface of the substrate W before the supply of the SPM on the upper surface of the substrate W. The organic solvent maintained at such a high temperature has a high thermal energy. Further, since IPA is liquid, the molecules of IPA are in contact with the hardened layer on the surface of the resist with high contact efficiency. The IPA molecule with sufficient thermal energy is in contact with the hardened layer due to high contact efficiency. This IPA penetrates the hardened layer on the surface of the resist. By the penetration of IPA, the hardened layer deteriorates and softens.

After the supply of IPA, SPM is supplied on the upper surface of the substrate W. Since SPM is supplied to the softened hardened layer, the SPM is distributed throughout the entire interior of the resist. Thereby, the resist can be well removed from the upper surface of the substrate W.

Further, before the execution of the SPM processing step (S6), the upper surface of the substrate W is dried by the first drying step (S5). Thereby, in the SPM process step (S6), the SPM can be applied to the resist on the substrate W immediately after it is supplied.

Further, after the organic solvent treatment step (S3), the ambient gas of the IPA generated in the organic solvent treatment step (S3) can be excluded from the periphery of the upper surface of the substrate W by performing the first rinsing step (S4). Thereby, generation of particles after a series of resist removal treatments can be suppressed or prevented.

Further, IPA to which a base (NH ₄ OH) was added was supplied to the upper surface of the substrate W. The hardened layer of the resist is easily dissolved in the alkali solution because the carbon contained therein has an amorphous portion. Therefore, by supplying the base-added IPA to the upper surface of the substrate W, the IPA dissolves the hardened layer of the resist while dissolving. Thereby, the hardened layer of the resist can be softened more effectively.

Further, warm water is supplied to the back surface of the substrate W together with the organic solvent treatment step (S3). By supplying warm water to the back surface of the substrate W, the substrate W can be warmed, and the IPA supplied to the upper surface of the substrate W can be held via the substrate W. Thereby, the temperature drop of the organic solvent on the surface of the substrate W can be suppressed, and as a result, the hardened layer of the resist can be softened more effectively.

Although an embodiment of the present invention has been described above, the present invention may be embodied in other forms.

In the above-described embodiment, the organic solvent treatment step (S3) will be described by exemplifying a case where IPA is continuously supplied to the upper surface of the substrate W while rotating the substrate at an organic solvent rotation speed (for example, about 300 rpm). It is also possible to form a liquid film covering the entire area of the upper surface of the substrate W by rotating the substrate W at a speed of zero or a low speed. In this case, since only zero or small centrifugal force acts on the IPA, a liquid film is formed by the IPA remaining on the substrate W, and then a liquid film of IPA is formed on the entire upper surface of the substrate W. That is, in this case, as in the case of the above embodiment, penetration into the hardened layer of the resist can be achieved. Further, after the IPA is filled on the upper surface of the substrate W, the supply of the IPA can be stopped.

In the above embodiment, the addition ratio of the NH ₄ OH (alkali) aqueous solution of IPA is preferably a high concentration (about 30%) of the NH ₄ OH aqueous solution is IPA: NH ₄ OH solution = 100:1 ratio or less. proportion. This is because if a large amount of alkali is contained, the moisture in the aqueous ammonia solution hinders the contact of the IPA with the resist, and thus the degree of penetration of the IPA of the hardened layer of the resist is lowered.

The temperature-regulating fluid supplied to the back surface of the substrate W in the organic solvent treatment step (S3) will be described by taking warm water as an example. However, dry gas or steam may be supplied to the back surface of the substrate W instead of warm water. . Further, the temperature-regulating fluid may not be supplied to the back surface of the substrate W at the organic solvent treatment step (S3).

Moreover, in the processing example of FIG. 3, the first rinse liquid supply step (S4) is provided, but the first rinse liquid supply step (S4) may be omitted. In this case, after the execution of the organic solvent treatment step (S3), the first drying step (step S5) is performed. At this time, the control device 3 accelerates the substrate W to a dry rotation speed (for example, several thousand rpm), and rotates the substrate W at a dry rotation speed. Thereby, a large centrifugal force is applied to the IPA on the substrate W, and the IPA adhering to the substrate W is separated from the periphery of the substrate W, and the substrate W is dried.

Further, in the above embodiment, IPA is exemplified as an example of the organic solvent, but as the organic solvent, methanol, ethanol, HFE (hydrofluoro-ether), and acetone may be used in addition to IPA. At least one of the liquids. Further, the organic solvent may be a liquid which is mixed with other components, not only in the case where only a monomer component is contained. For example, it may be a mixture of IPA and acetone, or a mixture of IPA and methanol.

Further, in the above-described embodiment, the nozzle mixing type in which the mixing of H ₂ SO ₄ and H ₂ O ₂ is performed inside the SPM nozzle 14 will be described as an example, but the piping may be provided via the piping. Further, the mixing portion connected to the upstream side of the SPM nozzle 14 is a pipe mixing type in which H ₂ SO ₄ and H ₂ O _{2 are} mixed in the mixing portion.

In the above-described embodiments, the substrate processing apparatus 1 is a device for processing a disk-shaped substrate W. However, the substrate processing device 1 may be a device for processing a polygonal substrate W such as a substrate for a liquid crystal display device. .

The embodiments of the present invention have been described in detail, but these are merely specific examples used to clearly understand the technical contents of the present invention, and the present invention should not be construed as limited to the specific examples. The spirit and scope are limited only by the scope of the patent application to which it is attached.

The present application is filed in the Japanese Patent Application No. 2013-255348, the entire disclosure of which is incorporated herein by reference.

1‧‧‧Substrate processing unit

2‧‧‧Processing unit

3‧‧‧Control device

4‧‧‧ chamber

5‧‧‧Rotary chuck

6‧‧‧SPM supply unit

7‧‧‧Organic solvent supply unit

8‧‧‧ rinse supply unit

9‧‧‧ cup

9a‧‧‧Upper

10‧‧‧Spinning base

11‧‧‧ chuck sales

12‧‧‧Rotary axis

13‧‧‧Rotary motor

14‧‧‧SPM nozzle

15‧‧‧1st nozzle arm

16‧‧‧1st nozzle moving unit

17‧‧‧ Sulfuric acid piping

18‧‧‧Hydrogen peroxide water piping

19‧‧‧ sulfuric acid valve

20‧‧‧ Sulfuric acid flow adjustment valve

21‧‧‧1st heater

22‧‧‧Hydrogen peroxide valve

23‧‧‧Hydrogen peroxide water flow adjustment valve

24‧‧‧Organic solvent nozzle

25‧‧‧2nd nozzle arm

26‧‧‧2nd Nozzle Moving Unit

27‧‧‧Organic solvent tank

28‧‧‧Organic solvent piping

29‧‧‧2nd heater

30‧‧‧ pump

31‧‧‧Filter

32‧‧‧Organic Solvent Valve

33‧‧‧Returning piping

34‧‧‧ return valve

35‧‧‧ rinse liquid nozzle

36‧‧‧ rinse liquid piping

37‧‧‧ rinse valve

38‧‧‧Infrared heater

39‧‧‧heater arm

40‧‧‧heater mobile unit

41‧‧‧Infrared light

42‧‧‧Light cover

43‧‧‧Temperature liquid circulation piping

44‧‧‧Temperature fluid supply piping

45‧‧‧temperature control valve

46‧‧‧Back nozzle

46A‧‧‧Export

47‧‧‧ heating device

61‧‧‧Organic solvent flow adjustment valve

A1‧‧‧Rotation axis

W‧‧‧Substrate

Claims (6)

A substrate processing method for a substrate processing method for removing a resist from a surface of a substrate, comprising: an organic solvent supply step of continuously flowing an organic solvent having a liquid temperature higher than a normal temperature and not reaching a boiling temperature The SPM is supplied to the surface of the substrate; and after the organic solvent supply step, the SPM is supplied to the surface of the substrate after the organic solvent is removed. The substrate processing method according to claim 1, further comprising a drying step of removing the liquid from the surface of the substrate before the execution of the SPM supply step after performing the organic solvent supply step The substrate is dry. The substrate processing method according to claim 1 or 2, further comprising a water washing step of supplying water to the surface of the substrate before the execution of the SPM supply step after performing the organic solvent supply step The organic solvent is washed from the surface of the above substrate. The substrate processing method according to claim 1 or 2, wherein the organic solvent supplied to the substrate in the organic solvent supply step contains a base. The substrate processing method according to claim 1 or 2, further comprising a temperature-adjusting fluid supply step, which is performed in parallel with the organic solvent supply step, and supplies the temperature-adjusted temperature-adjusted fluid to the substrate The back side of the opposite side of the surface. A substrate processing apparatus comprising: a substrate holding unit that holds a substrate on a surface of which a resist is formed; An organic solvent supply unit for supplying an organic solvent having a liquid having a liquid temperature higher than a normal temperature and not reaching a boiling point on a surface of the substrate held by the substrate holding unit; and an SPM supply unit for supplying the SPM to the substrate a surface of the substrate held by the unit; and a control unit that controls the organic solvent supply unit and the SPM supply unit; the control unit performs the step of: an organic solvent supply step of supplying the organic solvent to the above-mentioned continuous flow a surface of the substrate; and an SPM supply step of supplying the SPM to the surface of the substrate after the organic solvent is removed after performing the organic solvent supply step.